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CROSS-REFERENCE TO RELATED APPLICATION
[0001] The following application and this application are being filed concurrently, and the disclosure of the following application is incorporated by reference into this application for all purposes: U.S. patent application Ser. No. ______(Attorney Docket No. 10002302-1), entitled “Regulatory Classification System”, filed Oct. 1, 2001.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to a customs invoice and, more particularly, to methods of creating electronic customs invoices.
[0004] 2. Description of the Related Art
[0005] Transporting goods and supplies from one country to another has become very common. For example, goods are often manufactured in one country and then shipped to and sold in another country. Once the goods are manufactured, the shipping entity prepares a billing invoice, which includes billing information such as the name and address of the shipping entity, the name and address of the purchasing entity, the name and address of the consignee, a marketing description of the goods, the value of the goods, and the quantity of the goods. The billing invoice is either attached to the goods before they are transported to the consignee or electronically sent to the consignee.
[0006] Upon arrival of the goods at the port of destination, the carrier's representative notifies the customs broker that the goods have arrived. The goods are temporarily held in a bonded area until released by customs. A customs broker is hired by the purchasing entity to prepare and submit the customs declaration. The customs broker prepares the customs declaration using information on the billing invoice, airway bill, packing list, and other related documents. The customs declaration is a form that is unique to each individual country and includes information that describes details about the goods or shipment to the particular country. For example, the customs declaration will include a classification number (also referred to as a harmonized tariff schedule (HTS) number) representing the category of the goods, a commercial description of the goods, and the value of the goods.
[0007] The local HTS is used to assist customs brokers with classifying goods. The local HTS includes a list of goods with a corresponding classification number. Generally, each classification number is 10 characters in length, where the last 4 characters are determined by each country's local interpretation of the goods. Accordingly, each country has its own unique HTS, e.g., the Mexico HTS. With each country having its own interpretations of the HTS, several different classification numbers can be assigned to the same type of goods. Hence, it is difficult to have a centrally assigned classification number system. To make the classification task even more difficult, the classification numbers are periodically modified.
[0008] After the customs declarations are completed, the customs broker calls the customs inspector or stands in a line waiting for the customs inspector to review the customs declaration and the accompanying documents and to clear the shipment. Alternatively, the customs broker may be allowed to electronically submit the customs declaration for review and clearance of the shipment.
[0009] It should therefore be appreciated that there is a need for methods of creating an electronic customs invoice that has an accurately assigned HTS number, the acceptable description of the goods, and the representation of the value of goods. The present invention fulfills this need as well as others.
SUMMARY OF THE INVENTION
[0010] A method of creating an electronic customs invoice which includes receiving order information, creating an order request using the order information, and verifying the accuracy of the order request. The method further includes organizing the order request based on a plurality of categories, generating a billing statement using the order request, generating a billing file using the billing statement, and creating a customs invoice using the billing file. The method further includes creating an electronic file that includes the customs invoice, and transmitting the electronic file via email.
[0011] Advantages of the present invention include providing methods for creating an electronic customs invoice that has an accurately assigned local HTS number, the acceptable description of the goods, and the representation of the value of goods.
[0012] Other features and advantages of the present invention should become apparent from the following description of the preferred embodiment, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Embodiments of the present invention will now be described, by way of example only, with reference to the following drawings in which:
[0014] FIG. 1 is a simplified block diagram of an order fulfillment architecture having an electronic customs invoice system;
[0015] FIG. 2 is a simplified block diagram of the client device of the electronic customs invoice system of FIG. 1 ; and
[0016] FIG. 3 is a simplified flow chart of a method of creating an electronic customs invoice.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] With reference to the illustrative drawings, and particularly to FIG. 1 , there is shown a simplified block diagram of an order fulfillment architecture 10 having an electronic customs invoice system 12 . The order fulfillment architecture includes an order processing system 14 , a central processing system 16 , a distribution center 18 , a rebilling system 20 , an enterprise resource planning (ERP) system 22 , a server 24 , a database 26 , a product regulatory reference server 28 , and a client device 30 . The electronic customs invoice system includes the server, the database, and the client device. The connections between these components and systems are shown using arrows, which may represent a network physical, fiber optic, wireless, or any other type of connection. Furthermore, even though one order processing system, one central processing system, one distribution center, one rebilling system, one enterprise resource planning system, one server, one database, one product regulatory reference server, and one client device are depicted, any number of systems, servers, databases, centers, and devices can be used. The order fulfillment architecture may be implemented using hardware, software, or a combination of the two. For example, the order fulfillment architecture may be implemented using existing hardware entirely, making appropriate software updates.
[0018] Preferably, the order processing system 14 is a SAP system, Oracle system, or Legacy computer system. The order processing system 14 is configured to receive, modify, and store order information (step S- 1 ). The order processing begins when a user inputs order information into the order processing system based on a customer's order. For example, the customer might look through a catalog or on a web page for the product desired and call the user to place an order for the particular product or select the product on the web page. Each product in the catalog or on the web page has a unique product number. In the same manner as described above, the customer can place an order for multiple products. For example, the customer might order two servers, a CD burner, a monitor, and a printer. The order processing system is configured to create a record of the order information, which might includes an order number, invoice number, invoice date, line item number, unique product number of each product, marketing product description, serial number of each product, quantity by line item, unit price by line item, amount by line item (quantity x unit price), delivery method, delivery date, ship to address, sold to address, and sold by address.
[0019] Using the order information, the order processing system 14 determines which distribution center 18 can supply the goods by first determining the distribution centers that are within a certain area of the ship to address. Once the distribution centers are identified, the order processing system selects a distribution center that has the product in stock, can sell the product with the supplier discount (if any), and can ship the product within the allotted time. Once the distribution center is selected, the order processing system creates an order request using the order information and sends the order request to the central processing system 16 (step S- 2 ). The order request might include a plurality of codes that represent the order information. Each code might be a series of alphanumeric characters. For example, the code for a ship to address in the United States might be represented as “US”. One of the plurality of codes is a consignee code that represents the consignee or recipient of the goods.
[0020] The central processing system is configured to receive the order request and verify the accuracy of the order request (step S- 3 ). For example, if the possible codes for the supplier discount are 10, 20, and 30, but a 25 is received, the central processing system detects an error with the supplier discount code. If the central processing system detects one or more errors with the plurality of codes then the order request is sent back to the order processing system 14 for modification to the particular entry of the order information. Once the order information is modified, the order request is sent to the central processing system to once again verify the accuracy of the plurality of codes.
[0021] If the plurality of codes are correct, the central processing system 16 groups or organizes-the order request into categories and line items (step S- 4 ). For example, the order request can be grouped by category, i.e., product type, to form a plurality of line items. Each line item might include the category, the number of products desired for each category, and the delivery date. For example, the product type might be printers, the number of printers desired might be 1,000, and the delivery date might be Oct. 1, 2001. The categories might also be organized based on the ship to information. That is, all printers being shipped to the east coast might be grouped together and all printers shipped to the west coast might be grouped together. The information contained in each line item is then sent to the appropriate distribution center 18 . For example, the categories relating to printer orders might be sent to the printer distribution center.
[0022] The distribution center 18 is a warehouse that assembles or manufactures the products and has a SAP/ERP system, Oracle system, or Legacy computer systems. The system at the distribution center is configured to receive the order request, i.e., the plurality of codes, which is typically received in the form of a plurality of line items, from the central processing system 16 , and to determine whether the order request can be completed in the requested time period and whether the terms of the order request are acceptable to the distribution center.
[0023] If the system accepts the order request, then an accept response is sent to the order processing system 14 and the distribution center proceeds to process the order request and ship the products to the ship to address. If the system rejects the order request, then a reject response is sent to the order processing system. The reject response indicates that the distribution center is unable to process the order request due to time, material or labor constraints. If the system sends a reject response, the order processing system might modify the requested time period or the terms of the order request and resends the order request to the system at the distribution center. Once the products are shipped, the system generates a billing statement for the products using the order request that is sent to the central processing system 16 (step S- 5 ). The order processing system can simultaneously or alternatively send the order request to other systems at different distribution centers.
[0024] Using the billing statement, the central processing system 16 determines whether a discount code is present in the plurality of codes. If the discount code is present, the central processing system sends the billing file to the rebilling system 20 . The rebilling system applies the discount code, i.e., an inter-corporate (IC) discount, to the billing statement and then generates a billing file that is sent to the server 24 (step S- 6 ). If no discount code is present, the central processing system generates a billing file and sends the billing file to the server. The billing file is generated using information from the billing statement. For example, the billing file can be made up of a plurality of billing statements.
[0025] The server 24 is configured to receive the billing file, to read and parse the billing file, to organize each billing file according to a particular category, i.e., ship to country, and to create customs invoices for a particular country using information contained in the billing file (step S- 7 ). Once the billing file is received, the server is configured to adjust the value of the goods based on the discount code. The server uses the country code to determine the format of the customs invoice from the tables, e.g., customs invoice configuration tables, managed in the server. Information pertaining to each country is input into tables contained in the server. Further, the server is configured to group the products from the billing file into a list sorted by product number and country code, and to delete duplicate product numbers from the list. Using the product number and the country code as the query, the server makes a call to the product regulatory reference server 28 , which returns a classification number, i.e., a local HTS number, for the product, an export control commodity number (ECCN), and an acceptable description of the goods. For further details regarding the product regulatory reference server, refer to copending U.S. patent application Ser. No. ______(Attorney Docket No. 10002302-1), entitled “Regulatory Classification System”, filed concurrently with this application and owned by a common assignee. Each product number has a unique ECCN. The local HTS number, the ECCN, and the acceptable description of the goods are returned and incorporated into the billing file. The server creates a customs invoice for the particular country using the billing file and creates an encrypted electronic file of the customs invoice (step S- 8 ). The server also creates an envelope containing the encrypted electronic file and serializes the envelope. The encrypted electronic file is stored in the database 24 and the envelope is transmitted via email to an email address that is accessed by the client device 30 (step S- 9 ). To obtain the email address, the server retrieves the consignee code from the billing file, finds the consignee code in one of the tables, and retrieves the corresponding email address, which is stored in the same table. All customs invoices having the same consignee code are sent to the email address. There can be multiple email addresses assigned to each consignee code.
[0026] The ERP system 22 is typically a SAP system, or alternatively an Oracle system. The ERP system is a combination of and performs the functions of the order processing system 14 , the central processing system 16 , and the system of the distribution center 18 . In addition, the ERP is configured to create a billing file and to calculate the value of the products. If the billing statement does not have the discount code, the ERP system creates a billing file and send the billing file to the server. If the billing statement has the discount code, the ERP system sends the billing file to the central processing system for further processing by the rebilling system 20 .
[0027] FIG. 2 is a simplified block diagram of the client device 30 of the electronic customs invoice system 12 of FIG. 1 . The client device is illustrated as a personal computer (PC). The customs broker uses the client device to display, edit, retrieve, and print the customs invoice.
[0028] The PC includes a central processing unit (CPU) 32 , a read only memory (ROM) 34 , a random access memory (RAM) 36 , a main memory 38 , a video driver 40 , a communication port 42 , a monitor 44 , a keyboard 46 , and a mouse 48 . The CPU executes instructions that are stored in the ROM, RAM, and main memory. The ROM is used to store some of the program instructions, the RAM is used for the temporary storage of data, and the main memory is used to store instructions and data. The video driver configures the data received from the CPU so that it can be displayed using the monitor. While the preferred monitor is a CRT, other video display devices may be used including thin film transistor panels. The keyboard and mouse allow the user to edit, retrieve, print, and input information. The communication port is connected to the CPU and interfaces with a modem, cable, DSL line, wireless link, or any other technology connection that facilitates communication amongst the client device 30 . The use of the CPU in conjunction with the ROM, RAM, main memory, video driver, communication port, and modem is well known to those of ordinary skill in the art. A standard PC such as an IBM PC, running the software of the present invention, may be used as the client device. One of ordinary skill in the art will know that the client device can include fewer components than described above.
[0029] Now referring back to FIG. 1 , the client device 30 is further configured to decrypt and manage the electronic file of the customs invoice and allow the customs broker or user the ability to view, edit and print the customs invoice. To view, edit and print the customs invoice, the customs broker or user logs onto their client device and accesses their email account to download the file. Once the file is downloaded, the user can view, edit and print the customs form in the format of the particular country. The client device is also configured to allow the user to edit fields in the customs invoice. The user is given permission to edit certain fields to ensure data integrity. A hidden log or history of the edits to the customs invoice is also stored with the history database in the client device. The user can also assign each customs invoice to a certain group so the user can easily print all the customs invoices that belong to a particular group. For example, all the customs invoices that have the same airway bill number are assigned a group number of 1 . Hence, the user can print all the same customs invoices with the same airway bill by inputting 1 as the group number. The user can also create a summary invoice that includes all the customs invoices from a particular group or groups. The summary invoice might include a line item listing of each customs invoice. In sum, the server allows the user to edit, group, and manage customs invoices using the client device.
[0030] The foregoing detailed description of the present invention is provided for the purposes of illustration and is not intended to be exhaustive or to limit the present invention to the precise embodiment disclosed. Accordingly, the scope of the present invention is defined by the following claims.
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A method of creating an electronic customs invoice which includes receiving oder information, creating an order request using the order information, and verifying the accuracy of the order request. The method further includes organizing the order request based on a plurality of categories, generating a billing statement using the order request, generating a billing file using the billing statement, and creating a customs invoice using the billing file. The method further includes creating an electronic file that includes the customs invoice, and transmitting the electronic file via email.
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[0001] This application claims the benefit of the filing date of and is a continuation-in-part of United States Utility Patent Application having a title of DECORATIVE GRID SYSTEM AND METHOD, filed on Jan. 24, 2006 and assigned Ser. No. 11/338,357.
FIELD OF THE INVENTION
[0002] The technology described herein relates generally to the field windows and more particularly to a decorative grid and muntin system and method.
BACKGROUND OF THE INVENTION
[0003] Muntins are typically used in many types of windows in order to provide decoration for both insulated glass also known as Grill-Between-Glass (“GBG”) and Simulated Divided Lite (“SDL”) windows. Insulated glass (IG) windows are known as multiple panes of glass, typically two panes, being spaced thereby creating an air space between the panes. The panes are sealed, thereby becoming what is considered a single pane of glass having an insulating air space. GBG windows are advantageous because the insulating barrier between the panes results in energy conservation. Prior to sealing the two panes together, muntins are often placed between the panes to provide decoration.
[0004] Typical muntins are metal, plastic or wood. Regardless of the type of material, muntins present several problems in the GBG windows. For example, excessive heating and exposure to sunlight cause the muntins to warp and discolor causing a permanent unaesthetic appearance of the GBG window. Furthermore, the heat and light causes outgassing of the muntins, which is the release of moisture, liquid and/or chemical gases from the material.
[0005] The outgassing causes the moisture to be retained between the panes resulting in permanent clouding on the panes of glass that cannot be removed. For several of the materials used in present muntins, expensive and prolonged treatment, such as painting and heat curing, is required before placement of the muntins between the panes of glass. Muntins can also be used on SDL glass to give the appearance of True Divided Lite (“TDL”) windows, which are typically more difficult and time consuming to manufacture. The use of muntins for SDL windows can also cause similar problems associated with GBG window muntins, such as warping and discoloring, often cause by heat, sunlight and local outgassing.
[0006] These and other problems exist. Previous attempts to solve these and other problems include U.S. Pat. No. 7,318,301.
[0007] The foregoing patent reflects the state of the art of which the inventor is aware and is tendered with a view toward discharging the inventor's acknowledged duty of candor in disclosing information that may be pertinent to the patentability of the technology described herein. It is respectfully stipulated, however, that the foregoing patent and other information do not teach or render obvious, singly or when considered in combination, the inventor's claimed invention.
BRIEF SUMMARY OF THE INVENTION
[0008] In general, the technology described herein features a decorative (muntin) system and method. The muntins are formed from a substrate of expanded cellular polyvinyl chloride (“PVC”) material that has been applied with a desired muntin shape and machined by a computerized numerically controlled (CNC) machine.
[0009] In general, in one aspect, the technology described herein features a window system, including a pane of glass and a window muntin located adjacent the pane of glass, wherein the window muntin is formed from a substrate of expanded cellular polyvinyl chloride (“PVC”) material.
[0010] In one implementation, the substrate of expanded cellular polyvinyl chloride material is ultraviolet (UV) resistive.
[0011] In another implementation, the pane of glass and the muntin are adhered together as an SDL application.
[0012] In another implementation, the system further includes a second pane of glass generally parallel to the pane of glass, the muntin being located therebetween.
[0013] In another implementation, the system further includes a spacer connected along outer edges of the panes of glass and the muntin.
[0014] In another implementation, the panes of glass and the muntin are connected together in a GBG configuration.
[0015] In another aspect, the technology described herein features a method of manufacturing a window muntin, including creating a design of the window muntin, forming a substrate of expanded cellular polyvinyl chloride (“PVC”) material, forming the design of the window muntin on the substrate of the expanded cellular polyvinyl chloride (“PVC”) material and cutting the design of the window muntin from the substrate of the expanded cellular polyvinyl chloride (“PVC”) material.
[0016] In another aspect, the technology described herein features an improved window muntin being positioned between two panes of glass and sealed there-between, wherein the improvement comprises means for eliminating the outgassing and UV deterioration of the muntin.
[0017] In another implementation, the technology described herein features an improved method of forming a window of the type having two panes of glass having a space defined therebetween, the spaces being sealed from external environmental conditions, the improvement comprising forming a muntin for placement within the airspace prior to sealing the airspace, the muntin being formed by a substrate of expanded cellular polyvinyl chloride (“PVC”) material.
[0018] In another aspect, the technology described herein features a window muntin made by the process, including forming a planar sheet from a substrate of expanded cellular polyvinyl chloride (“PVC”) material, forming a decorative grid design on the planar sheet and cutting out the decorative grid design with a computerized numerically controlled (CNC) machine to form the muntin.
[0019] In one implementation, the process further includes optionally smoothing rough portions from the muntin and optionally finishing the muntin with at least one of paint and stain, and optionally air dried.
[0020] In another implementation, the process further includes placing the muntin in a Grill-Between-Glass (GBG) configuration.
[0021] In another implementation, the process further includes placing the muntin in a Simulated Divided Lite (SDL) configuration.
[0022] One advantage of the technology described herein is that it provides a muntin that does not degrade or warp.
[0023] Another advantage of the technology described herein is that it provides a muntin that does not yellow, fade or otherwise discolor.
[0024] Another advantage of the technology described herein is that it provides a muntin that does not require heat curing during production.
[0025] Another advantage of the technology described herein is that it provides a muntin that does not offgas.
[0026] Another advantage of the technology described herein is that it provides a muntin that does not contribute to moisture sealed between double pane windows.
[0027] Another advantage of the technology described herein is that it provides a muntin that does not absorb moisture.
[0028] Another advantage of the technology described herein is that it provides a muntin that can be painted or otherwise coated or not and air dried.
[0029] Another advantage of the technology described herein is that it can easily be beveled, textured or otherwise shaped.
[0030] Another advantage of the technology described herein is that a unitary one piece window muntin can be manufactured.
[0031] Another advantage of the technology described herein is that the methods described herein can be used to form window muntins as well as muntins for doors and other shaped windows.
[0032] There are additional features of the technology that will be described hereinafter and which will form the subject matter of the claims appended hereto. In this respect, before explaining at least one embodiment of the technology in detail, it is to be understood that the technology described herein is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The technology described herein is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
[0033] As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the technology described herein. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the technology described herein.
[0034] Other objects, advantages and capabilities of the technology described herein are apparent from the following description taken in conjunction with the accompanying drawings showing the preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The technology described herein is illustrated with reference to the various drawings, in which like reference numbers denote like system components and/or method steps, respectively, and in which:
[0036] FIG. 1 illustrates an embodiment of a window muntin 100 formed of expanded cellular polyvinyl chloride (“PVC”) material and shaped into a desired configuration;
[0037] FIG. 2A & FIG. 2B illustrate two embodiments of muntin retaining pins;
[0038] FIG. 3 illustrates an end view of an embodiment of the muntin as illustrated in FIG. 1 showing holes drilled into ends; and
[0039] FIG. 4 illustrates an embodiment of a GBG window system.
DETAILED DESCRIPTION OF THE INVENTION
[0040] Before describing the disclosed embodiments of this technology in detail, it is to be understood that the technology is not limited in its application to the details of the particular arrangement shown here since the technology described is capable of other embodiments. Also, the terminology used herein is for the purpose of description and not of limitation.
[0041] The embodiments described herein can be used for a large variety of muntin types, including but not limited to GBG and SDL windows. Regardless of the type of window, the muntin is typically formed by creating a desired muntin pattern on a substrate or board of expanded cellular polyvinyl chloride (“PVC”). The desired pattern is then cut from the board, typically using a CNC overhead router previously drawn on a CAD program. In a typical embodiment, the board used to form the muntins from the computerized numerically controlled (CNC) overhead router is 5′×10′. In addition, the board can generally have a thickness of 0.238-1.27 cm, and having typical thickness of, including but not limited to 0.318, 0.635 and 0.953 cm.
[0042] Typical muntins have a larger variety of shapes and sizes. FIG. 1 illustrates an embodiment of a window muntin 100 formed of expanded cellular polyvinyl chloride (“PVC”) and shaped into a desired configuration. In the embodiment, the muntin 100 has a semi-circular inner rim 105 having terminal ends 110 , 115 and three protruding bars 120 connected generally along the circumference of the inner rim 105 . A patterned outer rim 130 is connected to the ends of the bars 120 , the outer rim 130 being generally concentric with the semi-circular inner rim 105 . The outer rim 130 typically includes terminal ends 135 , 140 . It is appreciated that the rims 105 , 130 and bars 120 are typically an integral piece formed and cut from the expanded cellular polyvinyl chloride (“PVC”), and share a common plane of orientation.
[0043] After the cutting machine has cut out the muntin 100 , the muntin 100 is typically checked for smoothness. If desired, the muntin 100 can be sanded, typically with fine grit sandpaper and then cleaned. When a desired texture is achieved the muntin 100 is optionally painted or stained. When the paint has cured, the muntin 100 can be further processed, the processing depending on the muntin 100 types. For grid between glass (GBG) muntins, as shown with muntin 100 in FIG. 1 , a 0.159 cm ( 1/16 inch) wide hole is typically drilled into the ends of the bars 120 , and the terminal ends 110 , 115 of the inner rim 105 and the terminal ends 135 , 140 , of the outer rim 130 . The holes are drilled parallel to the plane of orientation, to a depth generally ranging from about 0.841 to 1.27 cm. It is understood that a variety of depths are possible depending on the application. A retaining pin 150 is used to connect the muntin 100 to its final position between panes of glass typically to a spacer as described further below, directly into a frame or into other orientation.
[0044] FIG. 2A and FIG. 2B illustrate two embodiments 150 a , 150 b of retaining pins 150 as just described. In one embodiment, the retaining pin 150 a is a pin having a generally planar head 155 , which can be square or rectangular, and a shaft 165 having a depth suitable to fit into holes drilled into the ends 110 , 115 , 135 , 140 as described above. The shaft 165 can further be advantageously tapered at the end in order to provide ease of insertion into the holes and thicker toward the head 155 to provide a snug fit. The head 155 can further include one or more dimples 160 positioned along an upper surface 156 of the head 155 , the dimples 160 generally providing a frictional fit when placed adjacent a spacer as described further below.
[0045] In another embodiment, the retaining pin 150 b is an elongated cylindrical shaft having tapered ends for affixation into the holes of the ends 110 , 115 , 135 , 140 as described above and for insertion into holes provided on window frames when fit directly into structures.
[0046] FIG. 3 illustrates an end view of an embodiment of the muntin 100 as illustrated in FIG. 1 showing holes 111 drilled into ends 110 , 115 .
[0047] FIG. 4 illustrates an embodiment of a GBG window system 200 . The system 200 includes an embodiment of a muntin 100 as described above. The muntin 100 is connected to a spacer 205 that is connected to a window frame 210 . As described above, either embodiment of the connector pins 150 a , 150 b can be used to connect the muntin 100 to the spacer 205 .
[0048] In another implementation, the muntin 100 can be formed as described for GBG use, but be modified for SDL use. For SDL muntins, no holes are typically drilled into the ends 110 , 115 , 135 , 140 . Instead, one side of the SDL muntin is wiped clean providing a clean, smooth and dry surface onto which adhesive, such as two-sided tape can be affixed for subsequent attachment to glass for an SDL window.
[0049] In one embodiment the technology described herein is a window system, comprising: a first pane of glass; a second pane of glass generally parallel to the first pane of glass; a window muntin located therebetween the first pane of glass and the second pane of glass, where the window muntin is formed from a substrate of UV resistive expanded cellular polyvinyl chloride (“PVC”) material, and the first pane of glass, the second pane of glass and the window muntin are adhered together as a Simulated Divided Lite (“SDL”) configuration; and a spacer disposed along outer edges of the panes of glass and the muntin.
[0050] In another embodiment the technology described herein is a window system, comprising: a pane of glass; and a window muntin located proximate the pane of glass, where the window muntin is formed from a substrate of expanded cellular polyvinyl chloride (“PVC”) material. In this window system the pane of glass and the window muntin are adhered together as a Simulated Divided Lite (“SDL”) configuration.
[0051] In another embodiment the technology described herein is a window system, comprising: a pane of glass; and a window muntin located proximate the pane of glass, where the window muntin is formed from a substrate of expanded cellular polyvinyl chloride (“PVC”) material. This window system is further comprised of a second pane of glass generally parallel to the pane of glass, the muntin being located therebetween; it is furthermore comprised of a spacer disposed along outer edges of the panes of glass and the muntin. In one implementation the panes of glass and the muntin are connected together in a GBG configuration and are further comprised of means for eliminating outgassing and UV deterioration of the muntin.
[0052] The technology described herein includes a method of manufacturing a window muntin, the method comprising: creating a design of the window muntin; forming a substrate of expanded cellular polyvinyl chloride (“PVC”); forming the design of the window muntin on the substrate of expanded cellular polyvinyl chloride (“PVC”) material; and cutting the design of the window muntin from the substrate of the expanded cellular polyvinyl chloride (“PVC”) material.
[0053] The technology described herein includes an improved method of forming a window having two panes of glass having an airspace defined therebetween, the airspace being sealed from external environmental conditions, the improvement comprising forming a muntin for placement within the airspace prior to sealing the airspace, the muntin being formed from a substrate of expanded cellular polyvinyl chloride (“PVC”) material.
[0054] The technology described herein includes a window muntin made by the process, comprising: forming a planar sheet from a substrate of expanded cellular polyvinyl chloride (“PVC”) material; programming a CNC machine to form a decorative grid design on the planar sheet; and cutting out the decorative grid design with a CNC machine to form the muntin. This process further comprises: optionally smoothing rough portions from the muntin; and optionally finishing the muntin with a coating chosen from the group consisting of paint and stain. This process further comprises placing the muntin in a Grill-Between-Glass (“GBG”) configuration or placing the muntin in a Simulated Divided Lite (“SDL”) configuration.
[0055] The foregoing description and drawings comprise illustrative embodiments of the technology described herein. Having thus described exemplary embodiments of the technology described herein, it should be noted by those skilled in the art that the within disclosures are exemplary only, and that various other alternatives, adaptations, and modifications may be made within the scope of a method in a certain order does not constitute and limitation on the order of the steps of the method. Merely listing or numbering the steps of a method in a certain order does not constitute any limitation on the order of the steps of that method. Many modifications and other embodiments of the technology described herein will come to mind to one skilled in the art to which this technology described herein pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Although specific terms may be employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Accordingly, the technology described herein is not limited to the specific embodiments illustrated herein, but is limited only by the following claims.
[0056] Although this technology has been illustrated and described herein with reference to preferred embodiments and specific examples thereof, it will be readily apparent to those of ordinary skill in the art that other embodiments and examples can perform similar functions and/or achieve like results. All such equivalent embodiments and examples are within the spirit and scope of the invention and are intended to be covered by the following claims.
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A window muntin apparatus and system, and methods for forming the same is disclosed. The muntins are formed from a substrate of expanded cellular polyvinyl chloride (“PVC”) that has been applied with a desired muntin shape and machined by a computerized numerically controlled (CNC) machine such as a 3-axis router. Muntins are then sealed between two pieces of glass to create a sealed insulated glass unit.
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FIELD OF INVENTION
Multi-story, poured-in-place reinforced concrete building columns are joined at each floor level by beams or girders which brace and transmit floor loads to the columns. The beams or girders may pass in pairs on either side of the columns in continuous manner to provide both rigid column bracing and even distribution of floor loading.
PRIOR ART
U.S. Pat. No. 2,783,638 shows extended lengths of vertically facing precast reinforced concrete girders which are placed in pairs abutting opposite planar faces of a line of columns and are retained in place either by being pinned on upstanding dowels embedded in haunches which extend from the columns only in the axial directions of the girders or by bolts which pass laterally through the columns and paired girders and through which floor loading is transmitted from the girders to the columns by stressing the bolts in shear. U.S. Pat. No. 3,074,209 shows end-notched precast reinforced concrete girders placed to abut end-to-end on column haunches and be joined into continuous lengths by the exposed ends of aligned reinforcing rods being welded together.
The prior art showing requires column girdling beams and girders to be secured on muti-story high columns either by fastening or positioning with mechanical means disposed in or through the columns or by fabrication operations performed in locations too spacially restricted and conjested by the proximity of columns and adjacent members to afford a proper environment for the performance and inspection of work.
SUMMARY OF THE DISCLOSURE
The skeletal structure of a multi-story reinforced concrete building is fabricated using longitudinally extending, vertically facing girder or beam pair members bolted face-to-face, clamped about and engaged in recessed belts about multi-story high reinforced concrete columns which may be further configured with haunches or keys projecting transversely through vertical planes interfacing the column and beam or girder members to form shoulders upon which the members bear. Fabrication such as bolting the member pairs together may be performed away and apart from the situs and operations involving the column, thus facilitating the ease and expedition and enhancing the quality of reinforced concrete building structure erection.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing a portion of a reinforced poured concrete column for building construction and a pair of girder members configured to be operably engaged with the column;
FIG. 2 is a perspective view showing a portion of a column together with a quoin and one member of a girder pair for being operably engaged with said column;
FIG. 3 is a perspective view of another embodiment of a column of this invention;
FIG. 4 is a perspective view of a portion of a round column of this invention and a cap for being placed thereon;
FIG. 5 is a perspective view of a form suitable for providing a poured concrete column of the configuration shown in FIG. 2.
DESCRIPTION OF THE INVENTION
In FIG. 1 poured-in-place reinforced concrete column 10 is shown in partial extent and is configured with haunch 11 disposed with bearing surface 12 extending horizontally from the face of belted recess portion 13. The thickness of column 10 between planar faces 17' and 18' of portion 13 is of lesser dimension than that of column 10 either below haunch 11 or above portion 13. As shown end faces 19' and 20' of portion 13 are recessed from the plane of the normal endface of column 10 and are angulated slightly one to the other with apex line 14 being disposed in the centerline plane of column 10. Beam pair members 15, 15' are disposed for being placed with faces 16, 16' coextensively faying with faces 17', 18' of portion 13 of column 10, the two members 15, 15' being symmetrical, and if desired, indentically configured and interchangeable. Faces 17, 18, 19, and 20 of members 15, 15' respectively fay with surfaces 17', 18', 19' and 20' of portion 13 of column 10 providing thereby a close fitting girdler about column 10. Faces 19" and 20" of members 15, 15' similarly fay with corresponding surfaces of portion 13, which are hidden from view in FIG. 1.
Openings 21, 21' run transversely through members 15, 15', respectively, and are disposed in alignment for receiving fastening means, preferably bolts 27 as shown with nuts 29 secured thereon for clamping members 15, 15' into substantial contact and against faces 17', 18' of portion 13 of column 10. End faces 19, 19", 20, 20" members 15, 15' are similarly brought into near adjacency or faying contact with end faces of portion 13 such as 19', 20' and the irregularities between facing surfaces are preferably filled with grout or other caulking or bedding material applied to the column faces including face 12 before placing members 15, 15' in position on column 10.
End extremities 25, 25' of members 15, 15', respectively, are shown with recessed pockets 26, 26' configured to support the end extremity of a suspended beam or girder. While members 15, 15' may span a bay between columns, in usual practice unless such a span is relatively short, a simple beam is laid to bear upon and be supported on bearing surfaces laterally extending from the columns, members 15, 15' fulfilling such function. A suspended simple beam supported in pockets 26, 26' may be of lesser depth and width dimension than that of the beam fabricated from members 15, 15', however, any size beam may be end-sized to be carried in pockets 26, 26'. The opposite end extremities of members 15, 15' from those of 25, 25' may be configured in similar manner for receiving a simple beam end, or may be configured in any other operable manner suitable for the particular construction. Notches 28, 28' run along the top of the outside faces of members 15, 15' for receiving and carrying reinforced concrete slab which constitutes floor decking or precast decking or other floor material as may be provided. Haunch 11 is shown in FIG. 1 as a preferred embodiment of the invention, but may be eliminated from the embodiment of FIG. 1, if desired. Members 15, 15' are assembled about column 10 being engaged in belted recess portion 13 properly bedded in grout and bolted together with the heads of bolts 27 and with nuts 29 being recessed in countersinking provided in members 15, 15' and covered with grout; grout may also be provided between faces 16, 16' of members 15, 15' to bond and integrally unify the two members. Vertical opening 24 may optionally be provided to receive a centering or positioning pin, if desired.
In FIG. 2, column 10' is shown as being of lesser width than column 10 of FIG. 1 such as might be used to define narrow bays. Belted recess portion 33, similar to portion 13 of FIG. 1, is of lesser height than beam member 35 and is defined at its lower extremity by a shoulder formed by an indentation into column 10' and not by a haunch as in FIG. 1. Beam member is one of a pair of symmetrical or identical members, the other beam member being omitted from showing in FIG. 2 for convenience. Face 30 of beam member 35 fays with the face of column 10' and key 34, which is integrally cast into beam 35, is operably received in belted recess portion 33 of column 10' thereby providing support for the beam member on the column. As shown, face 30 of beam member 35 extends beyond the width of column 10', but may operably be used with the beam member by inserting quoin 36 with key 37 being received in the transverse face of recess portion 33 and with keyway 33' disposed to receive key 34 ofbeam 35. Quoin 36 fills the unoccupied space of face 30 of beam 35 which projects beyond face 39 of column 10'. Assembly of beam member 35 with its paired member, not shown, is accomplished in similar manner to that described in relation to FIG. 1 Quoins can be used as necessary against either of the transverse faces of column 10', or against both faces, and may be used to fill space otherwise unoccupied and provide additional bearing surface for the beam members.
In FIG. 3, column 10" is shown with keyways 43 recessed from the plane of face 44 and disposed between keys 40 which project laterally beyond the plane of face 44. Beam member 46, one of a pair of beam members arranged in manner similar to that shown in FIG. 1, but with the complementary member being omitted from showing in FIG. 3, is configured with keys 42 running the length of indented face 41 and terminating with portions 42' across the transverse face of column 10". The beam members are assembled to girdle column 10" in manner similar to that above described.
In FIG. 4 column 10"' is shown as round and provided with haunch 51 defining the lower boundry of portion 54 which is of lesser diameter than the rest of column 10"' and is operably configured to receive cap 52 with surface 53 faying with the surface of portion 54. Openings 55, 56, and 57 are provided through cap 52 for receiving tendons, not shown, for being fully tensioned in post construction stressing. Provision of tendons obviates the need for other fastening means being provided to secure cap 52 in place, however, other operable means may be used, if desired, for securing cap 52. An adjacent cap member, not shown, will be understood to be provided about column portion 54 in the manner described for other embodiments of this invention.
FIG. 5 shows form 60 fabricated from metal sheet or plate, suitable for forming the portion of column 10' of FIG. 2 comprising belted recess portion 33. Two identical box angles 61 are shown for being bolted together through openings 62 to provide a removeable form which may be reused. Flanges 63, 64 are provided about the top and bottom edges, respectively, of form 60 for strengthening the edges and providing surfaces against which adjacent forms may be set. Inwardly projecting rib 64 formed in each of box angles 61 is configured with dihedral angle 65 at the center of the transverse face. Wood, treated cardboard or similar conventional materials may be used for the forms instead of metal, and other forms suitable for forming embodiments of other figures of this invention may be similarly made. Although preferred the draft angle shown in the drawings and represented by dihedral angle 65 in FIG. 5 may be eliminated, if desired, however, the provision of such an angle is useful not only in removing casting forms, but particularly in assisting in the proper positioning of beam members against columns during erection of a building.
The articles of this invention comprise vertically facing paired beam or girder members configured for being placed to continuously pass on either side of a continuous length of column and be engaged therewith in at least one recess which belts the column and which provides a horizontal bearing surface for supporting the horizontal members. Bearing surfaces may be provided by haunches or keys or both, and extend from the face of the column in a direction transverse to the axial direction of the beam or girder members. Columns may be configured with any desired cross sectional configuration such as round, rectilinear, polygonal, elliptical or other and be configured with keys and keyways which may be of the same or different configuration either completely belting the column or extending only along the axial directionof the girder or beam, and such girder or beam may be configured in complementary fashion or have more elongated key or keyway surfaces, in which case a quoin or quoins are desirably provided. Casting forms for girders, beams and columns configured in the manner described for this invention are within the scope of invention, the form shown in FIG. 5 being modified for casting of beams or girders by elimination of vertical flanges shown on the corners of box angles 61.
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Precast reinforced concrete girder pairs are placed to pass in parallel along either side of multi-story poured-in-place reinforced concrete building construction columns and be supported on haunches or be keyed to the columns, and are fastened in face-to-face contact to provide a rigidly braced, evenly loaded and easily fabricated skeletal building structure.
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FIELD OF THE INVENTION
This invention concerns organosilicon compounds soluble in silicone oils, and more particularly, novel organosilicon compounds which strongly absorb ultraviolet radiation.
BACKGROUND OF THE INVENTION
Ultraviolet absorbing compounds with a benzotriazole skeleton have conventionally been used as blending agents in medical preparations and cosmetics, or as additives to plastics. These compounds however all have poor dispersibility and solubility in substrates, and as there was a limit to their blending proportion and stability in dispersion, they suffered from bleeding and other disadvantages.
Further, although silicone oils find application in a variety of different fields, benzotriazole type compounds suffered from the disadvantage of being difficulty soluble in silicone oils.
To remedy these disadvantages, alkoxysilyl groups may for example be introduced into the benzotriazole skeleton, and the benzotriazole skeleton then introduced into polysiloxane molecules by cohydrolysis with chlorosilanes or alkoxysilanes (Unexamined Published Japanese Patent Application No. 57-21391).
When this method was applied to polysiloxanes without reactive functional groups, however, the benzotriazole type compound tended to be hydrolyzed due to the presence of the alkoxysilyl groups, and it lacked stability. In particular when these hydrolyzable substances were used for medical or cosmetic applications, moreover, the hydrolysis products had an irritating effect on the skin and membranes.
Another method has been proposed whereby the phenolic hydroxyl groups of compounds with a benzotriazole skeleton have been utilized to make alkyl ether derivatives with vinylsilyl groups, and hydrosilylation carried out on these vinyl groups so as to introduce benzotriazole type compounds into polysiloxane molecules (Unexamined Published Japanese Patent Application No. 63-230681).
In the case of compounds with this alkyl phenyl ether skeleton, however, radical cleavage via quinone intermediates tended to occur when ultraviolet radiation was absorbed or showed a tendency to hydrolysis under acidic conditions, and stability was poorer than in the case of alkylation via carbon-carbon bonds.
As described above, despite the fact that the use of silicone oils has been increasing in recent years in the medical and cosmetic fields, compounds which are alkyl modified via carbon-carbon bonding with a benzotriazole compound so as to introduce the benzotriazole skeleton into a polysiloxane molecule, or compounds which do not have hydrolyzable alkoxysilyl groups, which are stable and yet are highly soluble in silicone oils, had still not been obtained.
SUMMARY OF THE INVENTION
The aim of this invention is therefore to provide novel ultraviolet absorbing agents which have excellent solubility in substrates, and especially in silicone oils.
The above object is achieved by organosilicon compounds represented by the general formula: ##EQU2## and a preparing process for the preparation thereof; where a lies in the range 1≦a≦3 and b lies in the range 0.001≦b≦2,
R 1 are identical or dissimilar monovalent saturated or unsaturated hydrocarbons with 1-30 carbon atoms,
R 2 is a monovalent organic group represented by the formula --CR 3 2 CR 3 (H)CR 3 2 --R 4 ,
R 3 are hydrogen atoms or monovalent saturated hydrocarbon groups with 1-5 carbon atoms,
R 4 are groups represented by the formula: ##STR2## R 5 being identical to said R 1 or halogen atoms, alkoxy groups, carboxyl groups, hydroxyl groups or amino groups, d is an integer from 0 to 4, and c is an integer from 0 to 3.
The organosilicon compounds of this invention have an ultraviolet absorbing benzotriazole skeleton, and they are therefore extremely useful as blending agents in the medical and cosmetic fields, and as additives to plastics.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows the infrared absorption spectra of the organosilicon compound of the present invention which was obtained in Example 1.
FIG. 2 shows the ultraviolet absorption spectra of the organosilicon compound of the present invention which was obtained in Example 1.
FIG. 3 shows the infrared absorption spectra of the organosilicon compound of the present invention which was obtained in Example 2.
FIG. 4 shows the ultraviolet absorption spectra of the organosilicon compound of the present invention which was obtained in Example 2.
FIG. 5 shows the infrared absorption spectra of the organosilicon compound of the present invention which was obtained in Example 3.
FIG. 6 shows the ultraviolet absorption spectra of the organosilicon compound of the present invention which was obtained in Example 3.
FIG. 7 shows the infrared absorption spectra of the organosilicon compound of the present invention which was obtained in Example 4.
FIG. 8 shows the ultraviolet absorption spectra of the organosilicon compound of the present invention which was obtained in Example 4.
FIG. 9 shows the infrared absorption spectra of the organosilicon compound of the present invention which was obtained in Example 5.
FIG. 10 shows the ultraviolet absorption spectra of the organosilicon compound of the present invention which was obtained in Example 5.
DETAILED DESCRIPTION OF THE INVENTION
The novel organosilicon compounds of this invention which is represented by the general formula ##EQU3## may be synthesized by a rearrangement reaction according to known methods to obtain an allylation precursor, and then carrying out a hydrosilylation. The benzotriazole type ultraviolet absorption agent which is the starting material may be represented by the general formula: ##STR3## typical compounds of this type being: ##STR4## 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, ##STR5## 2-(2'-hydroxy-5'-tert-octylphenyl) benzotriazole, ##STR6## 2-(2'-hydroxy-5'-tert-butylphenyl) benzotriazole, ##STR7## 2-(2'-hydroxyphenyl) benzotriazole, ##STR8## 2-(2'-hydroxyphenyl)-5-chlorobenzotriazole, ##STR9## 2-(2',4'-dihydroxyphenyl)-5-chlorobenzotriazole, ##STR10## 2-(2'-hydroxyphenyl)-5-carboxybenzotriazole, and ##STR11## 2-(2'-hydroxy-5'-tert-butylphenyl)-5-aminobenzotriazole.
The phenolic hydroxyl parts of these compounds are allyl etherified under basic conditions, and the allylated benzotriazole derivative: ##STR12## is then obtained by a heat-induced rearrangement reaction.
To promote the rearrangement of the allyl ether, it is a necessary condition that either the ortho or para position with respect to the phenolic --OH group of the benzotriazole type compound which is the starting material, is unsubstituted.
The allylated benzotriazole derivative thus obtained is then made to undergo an addition reaction with an organohydrogen silane or an organohydrogen polysiloxane represented by the general formula: ##EQU4## using catalyst such as platinic compound, palladic compound or rhodium compound so as to obtain the novel organosilicon compound of this invention represented by the general formula: ##EQU5##
In this formula, R 1 are identical or dissimilar saturated or unsaturated hydrocarbon groups with 1-30 carbon atoms. Examples of R 1 are saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; saturated alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; unsaturated hydrocarbon groups such as vinyl and allyl; and aromatic hydrocarbon groups such as phenyl and tolyl. It is however particularly preferable that methyl groups account for no less than 50 mol % of R 1 .
R 2 in this formula, is a monovalent organic group represented by the formula --CR 3 2 CR 3 (H)CR 3 2 --R 4 ; R 3 is a hydrogen or a monovalent saturated hydrocarbon group with 1-5 carbon atoms; and R 4 is a group containing the benzotriazole skeleton and represented by the formula: ##STR13## R 5 is the same as R 1 , or is chosen from a halogen atom such as fluorine, chlorine or bromine, alkoxy groups with 1-10 carbon atoms, carboxyl, hydroxyl, and amino groups.
Also in this formula, a lies in the range 1.0-3.0 and preferably in the range 1.5-2.5; b lies in the range 0.001-2.0 and preferably in the range 0.01-1.0. If a is less than 1.0, sufficient solubility in silicone substrates is not obtained, while if it is greater than 3.0, the content of the group R 2 which is effective for ultraviolet absorption cannot be sufficient. Further, if b is less than 0.001, the content of the group R 2 which is effective for ultraviolet absorption cannot be sufficient, while if it is greater than 2.0, sufficient solubility in silicone substrates is not obtained.
Finally, in this formula, d is an integer lying in the range 0-4, and c is an integer lying in the range 0-3.
The organosilicon compounds of this invention not only have a high ultraviolet absorption coefficient, but also have a high solubility in silicone oils. Ultraviolet absorption properties may therefore be imparted easily to silicone oils by adding these compounds to them. Further, these compounds do not contain alkoxy or other reactive groups attached to the silicon atoms, they are stable and they do not cause much irritation to the skin. They will therefore prove particularly useful when applied to cosmetic preparations.
EXAMPLES
We shall now describe this invention in more detail with reference to specific examples, but it should be understood that the invention is by no means limited to them.
EXAMPLE 1 ##STR14##
The above reagent I (98.4 g) and toluene (250 g) were introduced into a reaction vessel, and the mixture was stirred for 30 min. while gradually adding a 28 weight % solution of sodium methoxide in methanol (127 g) by means of a dropping funnel. Next, the internal temperature was raised to 70°-85° C. and after removing 100 g of solvent, the internal temperature was lowered to 40° C. by air-cooling, and allyl bromide (106.4 g) was added gradually by means of a dropping funnel. After the addition was complete, the salt produced by refluxing for 2 hours was filtered and washed with water. After again removing solvent under reduced pressure, the residue was distilled under reduced pressure.
During this distillation, a rearrangement reaction was carried out under full reflux without collecting any fractions until the temperature rose to over 200° C. In this way, 106.4 g of a rearrangement fraction was obtained directly in the temperature range 211°-222° C. at a reduced pressure of 7 mmHg without isolating the allyl ether intermediate. This fraction was recrystallized from 1,000 g of a mixed solvent of toluene and methanol in the proportion (by weight) of 1:9, so as to obtain the allyl derivative represented by the formula: ##STR15##
This consisted of white needle-like crystals of melting point 100°-102° C., yield 87.9 g.
Next, the above allyl derivative (30 g) was introduced into a reaction vessel together with 2-propanol (150 g), a 10 weight % solution of potassium acetate in ethanol (0.3 g) and a 2 weight % chloroplatinic acid solution in 2-propanol (0.05 g), and after raising the internal temperature to 80° C., 49.8 g of the following methyl hydrogen polysiloxane reagent; ##STR16## was gradually added by means of a dropping funnel. After the addition was complete, the resulting mixture was stirred for 8 hours while maintaining the internal temperature at 80°-90° C.
The reaction solution was air-cooled to room temperature, 0.5 g of active carbon was added and stirring was continued for 2 hours. After filtering off the active carbon, the solution was heated to 150° C. under reduced pressure (5 mmHg) for 2 hours to remove solvent and unreacted methylhydrogenpolysiloxane, and the desired organosilicon compound: ##STR17## was obtained. This consisted of a yellow transparent liquid of viscosity 54.8 cs at 25° C., yield 70.0 g.
FIG. 1 and FIG. 2 respectively show the infrared and ultraviolet absorption spectra of the product, while Table 1 shows its solubility in various silicone oils.
Infrared absorption spectra were measured by a Perkin-Elmer Inc. 1640 Fourier Transformation Infrared Spectroscope using KBr plates, while ultraviolet absorption spectra were measured by a Hitachi U-3200 Auto-Recording Spectrophotometer using cyclohexane as solvent, a solute concentration of 4.3 mg/100 ml, and an optical path length in the sample of 1 cm.
TABLE 1__________________________________________________________________________Solubilities in silicone oils of the organosilicon compounds obtained inthe examples using a 10 weight % additionof the compounds at room temperaturesilicone oils organosilicon compounds of this invention(viscosity at 25° C.) EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE__________________________________________________________________________ 4octamethylcyclotetrasiloxane homogeneous soln. homogeneous soln. homogeneous soln. homogeneous soln. (transparent) (transparent) (transparent) (transparent)dimethylpolysiloxane homogeneous soln. homogeneous soln. homogeneous soln. homogeneous soln.(viscosity: 10 cs) (transparent) (transparent) (transparent) (transparent)dimethylpolysiloxane homogeneous soln. homogeneous soln. white suspension homogeneous soln.(viscosity: 300 cs) (transparent) (transparent) (transparent)dimethylpolysiloxane homogeneous soln. homogeneous soln. white suspension homogeneous soln.(viscosity: 1,000 cs) (transparent) (transparent) (transparent)dimethylpolysiloxane homogeneous soln. homogeneous soln. white suspension homogeneous soln.(viscosity: 10,000 cs) (transparent) (translucent) (transparent)methylphenylpolysiloxane homogeneous soln. homogeneous soln. homogeneous soln. homogeneous soln.(phenyl group content: (transparent) (transparent) (transparent) (transparent)5 mole %, viscosity: 200 cs)methylphenylpolysiloxane homogeneous soln. white suspension homogeneous soln. homogeneous soln.(phenyl group content: (translucent) (translucent) (translucent)25 mole %, viscosity: 400 cs)methylalkylpolysiloxane*.sup.1 homogeneous soln. white suspension homogeneous soln. homogeneous soln.(viscosity: 100 cs) (transparent) (translucent) (transparent)methyltrifluoropropyl- homogeneous soln. homogeneous soln. white suspension homogeneous solnpolysiloxane (transparent) (transparent) (transparent)(trifluoropropyl group content:15 mole %, viscosity: 36 cs)__________________________________________________________________________ ##STR18##
EXAMPLE 2 ##STR19##
An allyl ether derivative was synthesized using the above reagent III (100 g), toluene (250 g), a 28 weight % solution of sodium methoxide in methanol (107 g) and allyl bromide (89.5 g) according to the same procedure as in Example 1, and 104 g of a distillation fraction was obtained by distillation under reduced pressure (5 mmHg) in the temperature range 204°-210° C. The fraction was recrystallized from 1,000 g of a mixed solvent of toluene and methanol in the proportion (by weight) of 15:85, so as to obtain the allyl derivative represented by the formula: ##STR20##
This consisted of light yellow needle-like crystals of melting point 101°-104° C., yield 74.7 g.
Next, this allyl derivative (10 g) was introduced into a reaction vessel together with toluene (70 g) and a 2 weight % chloroplatinic acid solution in 2-propanol (0.02 g), and after raising the internal temperature to 80° C., 52.8 g of the following methylhydrogenpolysiloxane reagent;
average formula ##STR21## was gradually added by means of a dropping funnel.
After the addition was complete, the resulting mixture was stirred for 8 hours while maintaining the internal temperature at 80°-90° C.
The reaction solution was air-cooled to room temperature, 0.5 g of active carbon was added and stirring was continued for 2 hours. After filtering off the active carbon, the solution was heated to 150° C. under reduced pressure (5 mmHg) for 2 hours to remove solvent, and the desired organosilicon compound was obtained. This consisted of a yellow transparent liquid of viscosity 425 cs at 25° C., yield 58.0 g.
FIG. 3 and FIG. 4 respectively show the infrared and ultraviolet absorption spectra of the product measured as in Example 1, while Table 1 shows its solubility in various silicone oils. The solute concentration of the sample used for measuring ultraviolet absorption spectra was 6.6 mg/100 ml.
EXAMPLE 3 ##STR22##
An allyl ether derivative was synthesized using the above reagent V (80 g), toluene (300 g), a 28 weight % solution of sodium methoxide in methanol (71.6 g) and allyl bromide (45.3 g) according to the same procedure as in Example 1, and 82.0 g of a distillation fraction was obtained by distillation under reduced pressure in the temperature range 243°-246° C. (pressure 5 mmHg). The fraction was recrystallized from 1,750 g of a mixed solvent of toluene and methanol in the proportion (by weight) of 2:33, so as to obtain the allyl derivative respresented by the formula: ##STR23##
This consisted of white crystals of melting point 76°-79° C., yield 64.0 g.
Next, this allyl derivative (15 g) was introduced into a reaction vessel together with toluene (50 g) and a 2 weight % chloroplatinic acid solution in 2-propanol (0.02 g), and using 21.2 g of the following methylhydrogenpolysiloxane reagent; average formula ##STR24## a desired organosilicon compound was obtained as in Example 2. This consisted of a yellow transparent liquid of viscosity 1,110 cs at 25° C., yield 33.4 g.
FIG. 5 and FIG. 6 respectively show the infrared and ultraviolet absorption spectra of the product measured as in Example 1, while Table 1 shows its solubility in various silicone oils.
The solute concentration of the sample used for measuring ultraviolet absorption spectra was 4.2 mg/100 ml.
EXAMPLE 4 ##STR25##
Using the allyl derivative VII (40 g) synthesized in Example 3, toluene (100 g), a 2 weight % solution of chloroplatinic acid in 2-propanol (0.06 g) and the above reagent VIII (49 g), a desired organosilicon compound was obtained as in Example 2. This consisted of a yellow transparent liquid of viscosity 318 cs at 25° C., yield 79.7 g.
FIG. 7 and FIG. 8 respectively show the infrared and ultraviolet absorption spectra of the product measured as in Example 1, while Table 1 shows its solubility in various silicone oils.
The solute concentration of the sample used for measuring ultraviolet spectra was 3.9 mg/100 ml.
EXAMPLE 5 ##STR26##
Using the allyl derivative IX (15 g) synthesized in Example 1, 2-propanol (150 g), a 10 weight % solution of potassium acetate in ethanol (0.3 g), a 2 weight % solution of chloroplatinic acid in 2-propanol (0.03 g) and the above methylphenylhydrogendisiloxane reagent X (15.4 g), a desired organosilicon compound was obtained as in Example 1. This consisted of a yellow translucent liquid of viscosity 895 cs at 25° C., yield 27.0 g.
FIG. 9 and FIG. 10 respectively show the infrared and ultraviolet absorption spectra of the product measured as in Example 1.
The solute concentration of the sample used for measuring ultraviolet absorption spectra was 5.9 mg/100 ml.
Further, when the product was added, in the proportion of 10 weight %, to a methylphenylpolysiloxane containing 25 mole % of phenyl groups and having a viscosity of 400 cs, and a methylphenylpolysiloxane containing 28 mole % of phenyl groups and having a viscosity of 15 cs respectively, it dissolved homogeneously at room temperature to give transparent solutions in both cases.
This confirmed that whereas only minute quantities of benzotriazole type compounds dissolve in silicone oils, the organosilicon compounds obtained in this invention have a very high solubility while also strongly absorbing ultraviolet radiation.
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Organosilicon compounds represented by the general formula: ##EQU1## and preparing process thereof were disclosed; where a lies in the range 1≦a≦3 and b lies in the range 0.001≦b ≦2,
R 1 are identical or dissimilar monovalent saturated or unsaturated hydrocarbons with 1-30 carbon atoms,
R 2 is a monovalent organic group represented by
CR.sup.3.sub.2 CR.sup.3 (H)CR.sup.3.sub.2 --R.sup.3,
R 3 are hydrogen atoms or monovalent saturated hydrocarbon groups with 1-5 carbon atoms.
R 4 are monovalent organic groups represented by the formula: ##STR1## R 5 being identical to said R 1 or halogen atoms, alkoxy groups, carboxyl groups, hydroxyl groups or amino groups, d is an integer from 0 to 4 and c is an integer from 0 to 3.
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BACKGROUND OF THE INVENTION
The present invention is in a process and apparatus for separating liquid ash from an exhaust gas which is formed by the combustion of carbonaceous fuels and is at a temperature of from 1200° to 1800° C. at a pressure of from 1 to 100 bars, preferably from 1 to 30 bars, and has an ash content from 0.1 to 60 g/sm 3 (sm 3 =standard cubic meter).
It is known that small coal particles can be suspended in an oxygen-containing gas and combusted in a combustion chamber so that the inorganic components of the coal become available as ash. In dependence on the the nature of the combustor (consisting, e.g., of a slag tap furnace), the fuel and the oxygen content which is presented, a very high combustion temperature may be achieved so that the exhaust gas formed by the combustion leaves the combustion chamber at a temperature of from 1200° to 1800° C. Under these conditions, the ash which is produced by the combustion may be present in a molten, liquid state.
It is also known that high temperature exhaust gases which are produced by a combustion under pressure can desirably be used to generate electric power because the energy content of these exhaust gases can be converted to electric power by a gas turbine with very high efficiency. The remaining heat content of the combustion exhaust gas leaving the gas turbine can desirably be used to produce steam in a steam boiler. For this reason it is desirable from the aspects of energy and economics to produce combustion exhaust gases which are under pressure and at a temperature which is as high as possible; that temperature lies between 1200° and 1800° C. The production of such a combustion exhaust gas involves the disadvantage that the ash which is formed by the combustion of coal becomes available in a liquid rather than solid state. Before the hot combustion exhaust gas is used in a gas turbine it is necessary to remove substantially all of the liquid ash from the combustion exhaust gas because the gas turbine would otherwise be destroyed by the deposited and solidified ash droplets.
Published German Application 3,720,963 proposes a process wherein ash which is formed by the combustion of coal with air and which is in a pressurized combustion exhaust gas at a temperature from 1200° to 1700° C. is separated from the gas by passing that ash containing gas through at least one porous and gas-permeable ceramic filter element disposed in the combustion chamber. The filter consists mainly of Al 2 O 3 , SiO 2 , MgO and/or ZrO 2 .
It has been found that the life of the ceramic filters is limited particularly treating an exhaust gas from the combustion of relatively high ash content coal. For this reason it is an object of the invention to provide a process which is of the kind described first hereinbefore and which uses simple technical means but which results in a separation at a constant rate for the longest period possible.
SUMMARY OF THE INVENTION
The object underlying the invention is accomplished in that the ash-containing exhaust gas leaving the combustion chamber is directed onto at least one baffle surface. It has surprisingly been found that, in dependence on the design of the baffle separator, at least 70% of the liquid ash which is suspended in the exhaust gas can be separated at high temperatures. In the baffle separator known per se, dust particles or droplets will be separated from a gas stream as the gas stream is deflected whereas the particles, due to their inertia, continue in their original direction and impinge on the obstacle and are there deposited (Ullmanns Enzyklopadie der Technischen Chemie, 3rd Edition, Volume II/2, 1968, page 411).
In accordance with the invention the exhaust gas can pass through a centrifugal separator prior to its impingement on a baffle surface. By that measure, a major part of the liquid ash is separated in the centrifugal separator. A combination of a centrifugal separator and a baffle separator achieves a high degree of purification. The centrifugal separator may consist of a cyclone of any of various types.
It is also contemplated in accordance with the invention that the exhaust gas can pass through a ceramic filter element after the direction of flow of the exhaust gas has been changed by at least one baffle surface. The use of a baffle separator and a succeeding filter separator will also result in a high separation rate.
The object underlying the invention is also accomplished by the provision of an apparatus which consists of a housing in which at least one baffle surface is disposed. The housing is formed with a gas inlet and gas outlet and means, such as a drain, for removing the liquid ash. It has been found that a baffle surface should be oriented substantially transversely to the direction of flow of the exhaust gas. Such an arrangement including an angle of about 90° to the direction of flow may be used to separate droplets of liquid ash, which will effectively be drained from the baffle surface and can be discharged from the baffle separator. The exhaust gas may be directed to the baffle surface e.g., in a horizontal or vertical direction.
If the process includes a centrifugal separation stage and a succeeding baffle separation stage, the process can be carried out in accordance with the invention in an apparatus which consists of a cyclone provided with a dip pipe, and of a succeeding housing, in which at least one baffle surface is disposed at an angle of about 90° with the direction of flow of the exhaust gas. The housing includes a drain or outlet for removal of the liquid ash. Due to the high separation rate of the cyclone, the one or more succeeding baffle surface will be contacted by a gas having a lower ash content so that the life of the baffle separator materials will be prolonged.
In accordance with the invention it has also proven satisfactory to provide an apparatus which consists of a cyclone having a dip pipe and at least one baffle surface disposed in the dip pipe which includes an angle of about 90° with the direction of flow of the exhaust gas through the dip pipe. The length of the dip pipe 15 may be changed subject to the efficiency of the cyclone and the pressure loss in the cyclone. The baffle surface may be provided, e.g., in the vertical portion of the dip pipe. In that apparatus simple technical means may be used to separate the liquid ash almost completely from the exhaust gas.
If the process for separating the liquid ash consists of a baffle separator stage and a succeeding filter separator stage, the process can be carried out in accordance with the invention in an apparatus which consists of a housing in which at least one baffle surface is disposed, which includes an angle of about 90° with the direction of flow of the exhaust gas. The housing also includes an opening or other means for removing the liquid ash. The housing is followed by at least one ceramic filter element. The ceramic filter elements are porous and gas-permeable and consist mainly of Al 2 O 3 , SiO 2 , MgO and/or ZrO 2 . The filter elements have 10 to 1000 pores/cm 2 ; their open pore porosity is between 30 and 90% and the average pore diameter is between 10 and 2000 um.
It is especially preferred to provide an apparatus which is designed in accordance with the invention and in which the ceramic filter element includes a particulate bed formed from ceramic shaped bodies. The ceramic shaped bodies may be, e.g., spherical and consist mainly of Al 2 O 3 , SiO 2 , MgO and/or ZrO 2 . The exhaust gas flows through the particulate bed, e.g., in a vertical direction from top to bottom or from bottom to top. Consequently, the liquid ash particles form relatively coarse drops or liquid layers which are moved substantially by gravity and enter a collecting vessel substantially independently of the gas flow.
In the apparatus designed in accordance with the invention it has proven particularly desirable to coat the baffle surfaces, the inside surfaces of the housing, the dip pipe and the inside surfaces of the cyclone with a refractory ceramic material which is chemically inert to the ash. Such parts have a long life and ensure that a caking of the liquid ash is prevented.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this specification. For a better understanding of the invention, its operating advantages and specific objects obtained by its use, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated and described a preferred embodiment of the invention.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows a baffle separator useful in the invention which is supplied with gas flowing vertically from above;
FIG. 2 shows a cyclone provided with a dip pipe;
FIG. 3 shows a cyclone provided with a dip pipe in which baffle surfaces are disposed;
FIG. 4 shows a separator provided with a ceramic filter element;
FIG. 5 shows a separator which is provided with a particulate bed of ceramic material and is supplied with gas from above; and
FIG. 6 illustrates a process of the invention for separating liquid ash.
DESCRIPTION OF PREFERRED EMBODIMENT
FIG. 1 shows a baffle separator 1, which consists of a housing 12, in which one or more baffle surfaces 13 are disposed and which extend at an angle of approximately, but less than about 90°, preferably 78° to 88°, to the direction of flow of ash-containing exhaust gas 6. The ash-containing exhaust gas 6 is supplied to a baffle separator 1 vertically from top to bottom through inlet 10. As the ash-containing exhaust gas 6 impinges on the baffle surface 13, the droplets of ash are separated and flow down on the slightly inclined baffle surface. The exhaust gas 7, from which most of the droplets of ash have been removed, leaves the baffle separator 1 through outlet 11. The liquid ash 16 is collected in a conical portion of baffle separator 1 and is intermittently withdrawn through valve 9 and line 8.
A combustion exhaust gas which had an ash content of 1.5 g/sm 3 and had in a free cross-section a velocity of flow of 5 m/second and was at a temperature of 1500° C. and under a pressure of 3 bars was passed from top to bottom through a baffle separator, which had six baffle surfaces. After a pressure drop of 8000 Pa, the pure gas leaving the separator had an ash of content of about 50 mg/sm 3 . Similar good results will also be obtained if the exhaust gases flow from bottom to top and particularly if the exhaust gas flows horizontally.
FIG. 2 shows a cyclone 2 which acts as a centrifugal separator and consists of a housing 14, in which a vertical dip pipe 15, which may be movable, is disposed. The ash-containing exhaust gas 6 tangentially enters the cyclone 2 through inlet 10 and is substantially free of ash when it has contacted the wall surfaces. The exhaust gas 7 from which ash has been removed leaves the cyclone 2 through the outlet 11. The liquid ash 16 is collected in the conical portion of the cyclone 2 and is intermittently removed through the valve 9 and the line 8.
A gas which was at a temperature of 1500° C., under a pressure of about 5 bars and which had a liquid ash content of 30 to 40 g/sm 3 and a velocity of flow of about 6 m/sec, passed through a cyclone 2 wherein about 90% of the liquid ash was separated in a single pass therethrough so that the purified exhaust gas 7 had a residual ash content of about 3 g/sm 3 . The gas was subsequently supplied to a baffle separator 1, in which ash was removed to an ash content of about 20 mg/sm 3 .
FIG. 3 shows a cyclone 2 provided with a dip pipe 15, in which six baffle surfaces 13 are disposed. The remaining parts of cyclone 2 of FIG. 3 correspond with those as described in FIG. 2. A combustion exhaust gas which was at a temperature of 1500° C. and under a pressure of about 5 bars and had a velocity of flow of about 6 m/second and an ash content of 30 to 40 g/sm 3 was purified by an apparatus as shown in FIG. 3 to an ash content of about 30 mg/sm 3 .
FIG. 4 shows a filter separator 4, which consists of a housing 17, in which a ceramic filter element 18 is disposed. The filter element 18, consists of porous ZrO 2 foam. The ash-containing exhaust gas 6 enters separator 4 horizontally through inlet 10 and impinges on filter element 18 at right angles thereto. A part of the liquid ash which impinges on the filter element is directly separated on the surface of the filter element and is downwardly drained in a vertical direction into the conical portion of the filter separator 4. Another part of the liquid ash penetrates into the filter element 18 and is drained downwardly in a vertical direction into the conical portion of the filter separator 4. A weir 19 is disposed on the raw-gas side of the filter element 18 and always protrudes into the liquid ash 16 in order to separate the raw-gas space from the pure-gas space. As a result, all of the raw gas must pass through filter element 18. The liquid ash 16 is intermittently withdrawn from the filter separator 4 through valve 9 and line 8. The purified exhaust gas 7 leaves the filter separator 4 through outlet 11.
An exhaust gas which had an ash content of 7 g/sm 3 and was at a temperature of 1500° C. and under a pressure of 3 bars and had a velocity of about 5 m/second, was purified to an ash content of 100 mg/sm 3 by a single pass through a filter element 18. The pressure drop was about 500 Pa.
FIG. 5 shows a separator 5 which contains a particulate bed. The gas flows vertically from top to bottom through the bed. The separator 5 consists of a housing 20, in which a filter element consisting of a particulate layer 21 of ceramic material, is disposed. The particulate layer 21 is of spherical particles of ZrO 2 and is provided on a perforated plate 23. The ash-containing gas 6 flows through inlet 10 into separator 5, which contains a particulate bed and in which the gas flows vertically through the particulate layer 21 from top to bottom. The purified exhaust gas 7 leaves separator 5 through outlet 11. The particulate layer 21 is permeable to gas and to liquid ash. The liquid ash is collected in funnel 22, drained into the conical portion of separator 5, and is intermittently removed from the particulate bed separator 5 through valve 9 and line 8.
A combustion exhaust gas which was at a temperature of about 1500° C., under a pressure of about 6 bars and had a velocity of flow of about 4 m/second and an ash content of about 4 g/sm 3 was purified to a residual ash content of less than 5 mg/sm 3 in a single pass through the particulate bed separator 5.
FIG. 6 is a flow scheme of the process in accordance with the invention, which can be carried out as shown whenever entrained particles of liquid ash must be removed at a relatively high rate from hot combustion exhaust gases.
A coal powder, which may be suspended in air, and air, which may be enriched with oxygen, are supplied through lines 24 and 25, respectively, to a combustion chamber 3 wherein the coal is combusted at a temperature of about 1600° C. and under a pressure of from 15 to 20 bars. The combustion may be effected at under- or overstoichiometric conditions. Liquid ash is produced by the combustion and is removed, in part, in the combustion chamber 3. The remaining liquid ash, which may amount to 30 to 40 g/sm 3 , is suspended in the flue gas (combustion exhaust gas) and is supplied through line 26 to cyclone 2 where up to 90% or more of the liquid ash is separated. The exhaust gas leaving the cyclone 2 through line 27 has a low ash content of less than 5 g/sm 3 , and preferably 2 to 3 g/sm 3 . That exhaust gas enters the baffle separator 1, where 90% of the liquid ash is separated so that the exhaust gas which leaves the baffle separator 1 through line 28 contains less than 500 mg/sm 3 , preferably 20 mg/sm 3 . The exhaust gas out of separator 1 enters the filter separator 4, in which a pure gas with an ash content below 5 mg/sm 3 is produced. The pure gas leaves the filter separator through line 11. The liquid ash 16 which is collected in all units is discharged through line 8.
The use of at least one cyclone 2 will be required whenever a gas with a high ash content must be purified. A cyclone is not required if the exhaust gas has an ash content below about 1 g/sm 3 . The use of a filter separator 4 or 5 will depend on the design and performance of the preceding separators and is acceptable if the pure gas is required to have an extremely low ash content of about 1 mg/sm 3 . The exclusive use of a baffle separator 1 is acceptable if the exhaust gas has an ash content below 5 g/sm 3 and if the ash is suspended in the exhaust gas in the form of relatively large droplets.
To start up the units used in the process, ash-free fuel oil, rather than coal, is supplied to the combustion chamber 3 through line 29. The supply of fuel oil is discontinued when the units have heated up to the exhaust gas temperature. If the filter separator 4 is used, the weir 19 is closed during the start-up operation, i.e., the weir 19 will then be lowered as far as to the bottom of the filter separator 4. To operate the processing units, coal powder is replaced by fuel oil, which is supplied to the combustion chamber 3 through line 29. The combustion of the fuel oil is continued until liquid ash has been removed from all processing units.
The process illustrated in FIG. 6 has been carried out in a troublefree operation for several hundred hours. A gas which had a residual ash content below 5 mg/sm 3 was continuously removed through line 11.
Substances such as chamotte, dead burned fire day, steatite or carburetted stone can be used when it is desirable to coat the baffle surfaces, the inside surfaces of the housing, the dip pipe and the inside surfaces of the cyclone with refractory inert to the ash.
It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
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Disclosed are a process and apparatus for separating liquid ash from an exhaust gas which is formed by the combustion of carbonaceous fuels. The exhaust gas is at a temperature of from 1200° to 1800° C. and under a pressure from 1 to 100 bars and has an ash content, consisting of liquid particles, of 0.1 to 60 g/sm 3 . In the process, the ash-containing exhaust gas leaving the combustion chamber is directed to a housing in which there is at least one baffle surface oriented substantially transversely to the direction of flow of the exhaust gas which may be preceded by a centrifugal separator and/or succeeded by a ceramic filter element.
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FIELD OF THE INVENTION
[0001] The present invention relates to a production of fine dried noodles, specifically to a processing of prepared fine dried noodles and particularly to dry-steamed fine dried noodles and a production device thereof.
BACKGROUND OF THE INVENTION
[0002] In China, the largest country where fine dried noodles are produced and consumed, an industrial production of the fine dried noodles has been realized. At present, a main production process of fine dried noodles is that the raw material is prepared, kneaded, cured, subjected to tabletting, slit, dried, cut off and packaged into finished products by paper packages or plastic packages. Drying fine dried noodles, as a procedure with the highest investment and the highest technology content in a whole production line, refers to dehydrating wet noodles to finally reach a moisture content specified by the production standard. This procedure not only concerns the quality of products, but also has important influence on energy consumption, yield and cost. The occurrence of phenomena during the production, such as noodle rupture, noodle damp and noodle acidification, is basically caused by unreasonable drying equipment and technologies. The difference between drying technologies of fine dried noodles lies in drying temperature and drying time.
[0003] Document Production Formula and Process of Fine Dried Noodles (edited by Shen Qun, Chemical Industry Press, 2008) has described drying of fine dried noodles in Section III of Chapter II (P 107). At present, drying of fine dried noodles includes low-temperature low-speed drying which generally means that, the highest temperature of a primary drying area is below 40° C., and the drying time is 5 h-8 h, wherein there are imported and domestic ropeway-pattern drying chambers; intermediate-temperature intermediate-speed drying which generally means that, the highest temperature of a primary drying area is less than 45° C., and the drying time is 3 h-5 h, wherein based on ropeway-pattern high-temperature drying, the drying tunnel is extended and the drying time is prolonged properly, and the drying temperature is reduced, so that the drying temperature and drying time both are between those of the high-temperature drying and the low-temperature drying; and high-temperature high-speed drying which generally means that, the highest temperature of a primary drying area is greater than 45° C. but less than 50° C., and the drying time is less than 3 h (about 2 h, 40 min fastest).
[0004] After the processes of rolling, curing, drying and the like are performed on fine dried noodles, due to the restriction of the amount of water added for kneading, the structural arrangement of gluten network tissues is not very uniform, the spacing between tissues is large and incompact, and the distribution of starch grains on a gluten film is not uniform. In addition, the fine dried noodles have ordinary taste, are boilproof and are difficult to store, and generation of worms is prone to happening.
SUMMARY OF THE INVENTION
[0005] An object of the present invention is to provide dry-steamed fine dried noodles having good taste, long shelf life and worm resistance, and a production device thereof. The structural arrangement of gluten network tissues of the dry-steamed fine dried noodles is uniform, the spacing between tissues is small and compact, and the distribution of starch grains on a gluten film is uniform. Compared with the noodles as raw material, the maximum load of the dry-steamed fine dried noodles is improved by 10%-200%, and the cooking loss rate is reduced by 0.5%-1.5%.
[0006] To achieve the above object, the present invention employs the following technical solutions.
[0007] Dry-steamed fine dried noodles are provided, which are prepared via the following steps by using fine dried noodles with a moisture content of 10%-16% as raw material:
[0000] (1) heating and dry-steaming: heating and dry-steaming the fine dried noodles, wherein the heating and dry-steaming employs one of the following two solutions:
solution 1: heating the fine dried noodles to 50° C.-80° C., and keeping for 1 h-35 h under a relative humidity of 60%-80%;
solution 2: feeding the fine dried noodles into a dry-steaming device, heating air in the dry-steaming device to 50° C.-90° C., and keeping for 3 h-100 h under a relative humidity of 60%-80%; and
(2) cooling and tempering: cooling the fine dried noodles dry-steamed in step (1) to room temperature by means of controlling a cooling rate to be 2° C./h-30° C./h and keeping the relative humidity at 60%-80%, thus obtaining dry-steamed fine dried noodles with a moisture content of less than or equal to 14.5%.
[0008] Preferably, the maximum load of the dry-steamed fine dried noodles is greater than 0.95 N, and the cooking loss rate is less than 7.5%.
[0009] The dry-steamed fine dried noodles are cut off or packaged by paper packages or plastic packages, and then sold.
[0010] In solution 1 of step (1), the fine dried noodles are heated via microwaves.
[0011] In solution 1 of step (1), the fine dried noodles are heated to 50° C.-80° C., and then are kept for 3 h-24 h under a relative humidity of 60%-80%.
[0012] The room temperature is preferably 20° C.-25° C.
[0013] The fine dried noodles, used as raw material in the present invention, are conventional fine dried noodles in the prior art, and are preferably prepared from wheat flour or composite powder of wheat flour and fruit and vegetable grains, wherein the content of the wheat flour in the composite powder by mass is greater than or equal to 90%.
[0014] The preparation method is as follows: preparing, kneading, curing, tabletting, slitting and drying wheat flour to obtain fine dried noodles with a moisture content of 10%-16%.
[0015] The wheat flour should meet the requirements of the national industry standard (LS/T 3202). The fine dried noodles are suspended fine dried noodles, cut-off fine dried noodles in bulk, paper-packaged fine dried noodles, or plastic-packaged fine dried noodles, preferably, suspended fine dried noodles, i.e., fine dried noodles which are suspended and dried in a drying room.
[0016] In the prior art, preferably, during the main drying process, the moisture content (28%-34%) in the fine dried noodles is reduced to the moisture content requirement (10%-16%) of the product standard at an appropriate temperature (generally below 50° C.), humidity (70%-90%) and wind speed, thereby being suitable for the storage of the fine dried noodles for a long time.
[0017] A device for producing dry-steamed fine dried noodles is provided, including a box body 1 provided with a noodle inlet and a noodle outlet, a heating mechanism disposed in the box body, a humidifier disposed on the box body, a detection mechanism for detecting the temperature and relative humidity of air in the box body, and a control mechanism including a PLC device, the control mechanism being electrically connected to the detection mechanism, the heating mechanism and the humidifier.
[0018] The control mechanism controls the temperature, humidity and working time of air in the box body via the heating mechanism and the humidifier by means of the detection of the detection mechanism.
[0019] The control range of temperature of the control mechanism is 50° C.-90° C., the control range of relative humidity is 60%-80%, and the control range of working time is 3 h-100 h.
[0020] The present invention will be further explained and described as below.
[0021] The dry-steamed fine dried noodles provided by the present invention are prepared via the steps of heating, dry-steaming, cooling and tempering by using the prepared fine dried noodles. The fine dried noodles have a moisture content of less than or equal to 14.5%, do not have obvious changes in color and appearance, and are not warped, nonacid, not crispy, and not sticky. The hardness of the fine dried noodles is enhanced. Compared with the control noodles, the maximum load in texture index is improved by 10%-200%, the gluten network structure is compact, the toughness of the fine dried noodles is enhanced, and the cooking loss rate is reduced by 0.5%-1.5%. The fine dried noodles have good taste, boiling fastness, long shelf life, and good edible quality, cooking performance and commodity effect.
[0022] In a control experiment, wheat flour is directly processed by the method of the present invention, and then placed in an oven for dry-steaming for 16-20 h at 75° C. Then, the dry-steamed wheat flour is processed into noodles. By evaluating and analyzing the noodles, the result shows that it is difficult to process the wheat flour into noodles, and the prepared noodles cannot reach the effects of the dry-steamed fine dried noodles obtained from the finished fine dried noodles product under the same conditions. Meanwhile, potato starch and cassava starch are processed by the method of the present invention, and then 5% and 10% of starch in added into flour and then the mixture processed into fine dried noodles. The result shows that the noodles does not have obvious difference from the control group (starch is not subjected to high-temperature treatment) and cannot reach the effects of the dry-steamed fine dried noodles obtained from the finished fine dried noodles product under the same conditions.
[0023] Compared with the prior art, the present invention has the following advantages:
[0000] (1) by performing high temperature dry-steaming treatment on the prepared fine dried noodles, the present invention, breaking through the conventional modes of thinking, improves the quality of the fine dried noodles and particularly improves the hardness and toughness of the fine dried noodles while achieving sterilization and anti-insect effects, thus improving the quality guarantee period of the product, and avoiding the occurrence of quality problems such as noodle rupture and poor taste during direct high temperature drying;
(2) the structural arrangement of gluten network tissues of the dry-steamed fine dried noodles prepared by the present invention is uniform, the spacing between tissues is small and compact, and the distribution of starch grains on the gluten film is uniform; and
(3) compared with the noodles as raw material, the maximum load of the dry-steamed fine dried noodles prepared by the present invention is improved by 10%-200%, and the cooking loss rate is reduced by 0.5%-1.5%.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a structure diagram of a production device according to the present invention;
[0025] FIG. 2 is a scanning electron microscopic image of common fine dried noodles in embodiment 1; and
[0026] FIG. 3 is a scanning electron microscopic image of suspended fine dried noodles after dry-steaming for 9 h at 85° C. in embodiment 1.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0027] The present invention will be further described as below in combination with accompanying drawings and embodiments. The percentage content in the embodiments refers to percentage content by mass.
Embodiment 1
[0028] Fine dried noodles are prepared by the following steps:
[0029] (1) Production of fine dried noodles: producing fine dried noodles is an industrial process for producing common fine dried noodles, including: processing raw material into fine dried noodles after steps of preparing, kneading, curing, tabletting, slitting and drying, wherein the moisture content of the fine dried noodles is 10%-16%. The fine dried noodles in this embodiment are suspended fine dried noodles, that is, the fine dried noodles are suspended and dried in a drying room, wherein the moisture content is 14%. The raw material in this embodiment is wheat flour.
[0030] It can be seen from FIG. 2 that, although the processes of rolling, curing, drying and the like are performed on common fine dried noodles, the structural arrangement of gluten network tissues of the common fine dried noodles is not uniform, the spacing between tissues is large and incompact and the distribution of starch grains on the gluten film is not uniform due to the restriction of the amount of water added for kneading or the like.
[0031] (2) Dry-steaming: in order to heat the fine dried noodles, the heating and dry-steaming method in this embodiment is as follows: fine dried noodles which have been normally dried in the drying room are suspended and fed into a dry-steaming device, air in the dry-steaming device is heated to 85° C. and kept for 24 h, and the relative humidity is kept at 80%.
[0032] It can be seen from FIG. 1 that, a device for producing dry-steamed fine dried noodles (i.e., a dry-steaming device) includes a box body 1 provided with a noodle inlet 4 and a noodle outlet 6 , a heating mechanism 5 disposed in the box body 1 , a humidifier 7 disposed on the box body 1 , a detection mechanism 2 for detecting the temperature and relative humidity of air in the box body 1 , and a control mechanism 3 including a PLC device, the control mechanism 3 being electrically connected to the detection mechanism 2 , the heating mechanism 5 and the humidifier 7 .
[0033] The control mechanism 3 controls the temperature, humidity and working time of air in the box body 1 via the heating mechanism 5 and the humidifier 7 by means of detection of the detection mechanism 2 .
[0034] The control range of temperature of the control mechanism 3 is 50° C.-90° C., the control range of relative humidity is 60%-80%, and the control range of working time is 3 h-100 h.
[0035] (3) cooling and tempering: the fine dried noodles dry-steamed in step (2) are cooled to room temperature, wherein a cooling rate is 2° C./h-30° C./h, the relative humidity is kept at 60%-80%, and the moisture content of the fine dried noodles is controlled to be less than or equal to 14.5%.
[0036] In this embodiment, the cooling rate is 30° C./h, the relative humidity is kept at 80%, and the moisture content of the fine dried noodles is controlled to be 11.0%.
[0037] The dry-steamed fine dried noodles are prepared via the steps of heating, dry-steaming, cooling and tempering by using the prepared fine dried noodles. The fine dried noodles have a moisture content of less than or equal to 14.5% (11% in this embodiment), do not have obvious changes in color and appearance, and are not warped, nonacid, not crispy, and not sticky. With the increase of dry-steaming time, the maximum load (reflecting hardness of the dry-steamed fine dried noodles) produced by the above process will rise. Compared with the control noodles, the hardness of the fine dried noodles is enhanced, and the maximum load in texture index is improved by 10%-200%. Furthermore, during dry-steaming, the fine dried noodles are further cured, the gluten network structure is compact, the toughness of the fine dried noodles is enhanced prominently, and the cooking loss rate is reduced by 0.5%-1.5% in comparison with the control noodles (refer to the attached table). The fine dried noodles have good taste, boiling fastness, long shelf life, and good edible quality, cooking performance and commodity effect.
[0038] Attached Table shows test data of maximum load in texture index and cooking loss rate of suspended fine dried noodles after dry-steaming at 85° C.
[0000]
Hold time (h)
Maximum load/N
Cooking loss rate (%)
0
0.8552
8.0
(control)
3
0.9568
7.5
6
1.1416
7.3
9
1.3674
7.2
12
1.5258
6.9
20
1.6010
6.8
24
2.0939
6.7
Note:
The texture analyzer is a British TA-PLUS texture analyzer, the number n of the samples to be tested is 3, the thickness is 0.75 mm-0.76 mm, and the value is an average value.
[0039] It can be seen from the attached table that, the maximum load in the texture index is improved by 11.9% (keeping for 3 h) and 144.8% (keeping for 24 h) in comparison with the control noodles, the gluten network structure tends to be compact, the toughness of the fine dried noodles is enhanced prominently, and the cooking loss rate is reduced by 0.5% (keeping for 3 h) and 1.3% (keeping for 24 h) in comparison with the control noodles (refer to the attached table).
[0040] It can be seen from FIG. 3 that, the arrangement of gluten network tissues of the dry-steamed fine dried noodles obtained after dry-steaming treatment becomes regular, the spacing between tissues is small, and the distribution of starch grains on the gluten film is uniform. It can be seen that the dry-steaming treatment has a function of improving the tissue structure of dried noodles, and this is consistent with the test data and the result of sensory evaluation of the texture index and cooking loss rate. The fine dried noodles are cut off, paper-packaged or plastic-packaged as required after dry-steaming treatment.
Embodiment 2
[0041] In step (1) of the present invention, the raw material is composite powder of wheat flour and fruit and vegetable grains, wherein the wheat flour accounts for 92%, while the fruit and vegetable grains (sorghum flour) account for 8%.
[0042] In step (2) of the present invention, the temperature is raised to 70° C. and then kept for 24 h, and the relative humidity is kept at 75%.
[0043] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 12.0%, the maximum load in the texture index is improved by 79.5% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 1.1% in comparison with the control noodles, and the remaining is the same as those in embodiment 1.
Embodiment 3
[0044] In step (1) of the present invention, the raw material is composite powder of wheat flour and fruit and vegetable grains, wherein the wheat flour accounts for 95%, the vegetable powder accounts for 2%, and the soybean meal accounts for 3%.
[0045] In step (2) of the present invention, the temperature is raised to 75° C. and then kept for 6.5 h, and the relative humidity is kept at 78%.
[0046] After the end of dry-steaming, the fine dried noodles are cooled to room temperature, wherein the cooling rate is 25° C./h and the relative humidity is kept at 75% in this embodiment.
[0047] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 12%, the maximum load in the texture index is improved by 34.9% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 0.5% in comparison with the control noodles, and the remaining is the same as those in embodiment 1.
Embodiment 4
[0048] In step (1) of the present invention, the raw material is composite powder of wheat flour and fruit and vegetable grains, wherein the wheat flour accounts for 92%, and the fruit and vegetable grains (buckwheat flour) account for 8%. The fine dried noodles are products after being dried, cut off and packaged with paper shrink films.
[0049] In step (2) of the present invention, the temperature is raised to 80° C. and then kept for 24 h, and the relative humidity is kept at 80%.
[0050] In the present invention, to enable the fine dried noodles to be heated uniformly and ensure the consistence of the quality of the fine dried noodles, the fine dried noodles are placed uniformly in the dry-steaming device.
[0051] After the end of dry-steaming, the fine dried noodles are cooled to room temperature, wherein the cooling rate is 15° C./h and the relative humidity is kept at 70% in this embodiment.
[0052] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 11.8%, the maximum load in the texture index is improved by 21.3% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 0.8% in comparison with the control noodles, and the remaining is the same as those in embodiment 1.
Embodiment 5
[0053] In step (1) of the present invention, the raw material is composite powder of wheat flour and fruit and vegetable grains, wherein the wheat flour accounts for 95%, and the fruit and vegetable grains (green bean powder) account for 5%. The fine dried noodles are products after being dried, cut off and packaged with plastic packages.
[0054] In step (2) of the present invention, the temperature is raised to 50° C. and then kept for 100 h, and the relative humidity is kept at 60%.
[0055] After the end of dry-steaming, the fine dried noodles are cooled to room temperature, wherein the cooling rate is 10° C./h and the relative humidity is kept at 60% in this embodiment.
[0056] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 12.0%, the maximum load in the texture index is improved by 15.3% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 0.5% in comparison with the control noodles, and the remaining is the same as those in embodiment 1 and embodiment 4.
Embodiment 6
[0057] In step (1) of the present invention, the fine dried noodles are cut off and packaged in bulk after being dried.
[0058] In step (2) of the present invention, the temperature is raised to 75° C. and then kept for 30 h, and the relative humidity is kept at 80%.
[0059] After the end of dry-steaming, the fine dried noodles are cooled to room temperature, wherein the cooling rate is 2° C./h and the relative humidity is kept at 80% in this embodiment.
[0060] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 12.5%, the maximum load in the texture index is improved by 35.3% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 1.0% in comparison with the control noodles, the fine dried noodles are paper-packaged or plastic-packaged as required after dry-steamed, and the remaining is the same as those of embodiment 1 and embodiment 4.
Embodiment 7
[0061] In step (1) of the present invention, the fine dried noodles are cut off and packaged in bulk after being dried.
[0062] To improve production efficiency, in step (2) of the present invention, the heating and dry-steaming method is heating the fine dried noodles by microwaves. The fine dried noodles are heated to 50° C.-80° C. (70° C. in this embodiment) and then kept for 1 h-35 h (1 h in this embodiment), and the relative humidity is kept at 60%-80% (75% in this embodiment).
[0063] After the end of dry-steaming, the fine dried noodles are cooled to room temperature, wherein the cooling rate is 2° C./h and the relative humidity is kept at 75% in this embodiment.
[0064] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 12.0%, the maximum load in the texture index is improved by 23.7% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 0.7% in comparison with the control noodles, the fine dried noodles are paper-packaged or plastic-packaged as required after dry-steamed, and the remaining is the same as those of embodiment 1 and embodiment 4.
Embodiment 8
[0065] In step (1) of the present invention, the fine dried noodles are packaged in bulk after being dried and cut off.
[0066] To improve production efficiency and reduce cost, in step (2) of the present invention, the fine dried noodles are heated to 50° C.-80° C. (50° C. in this embodiment) at first, then fed into a dry-steaming device at 50° C.-80° C. (50° C. in this embodiment) and kept for 1 h-35 h (35 h in this embodiment), and the relative humidity is kept at 60%-80% (60% in this embodiment).
[0067] After the end of dry-steaming, the fine dried noodles are cooled to room temperature, wherein the cooling rate is 2° C./h and the relative humidity is kept at 70% in this embodiment.
[0068] By detecting the dry-steamed fine dried noodles, the moisture content of the dry-steamed fine dried noodles is 12.0%, the maximum load in the texture index is improved by 15.4% in comparison with the control noodles, the gluten network structure tends to be compact, the cooking loss rate is reduced by 0.6% in comparison with the control noodles, the fine dried noodles are paper-packaged or plastic-packaged as required after dry-steamed, and the remaining is the same as those of embodiment 1 and embodiment 4.
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The present invention discloses dry-steamed fine dried noodles. The dry-steamed fine dried noodles with a moisture content of less than or equal to 14.5% are prepared via the processes of dry-steaming, cooling and tempering by using fine dried noodles with a moisture content of 10%-16% as raw material. Compared with the control noodles, the maximum load of the dry-steamed fine dried noodles is improved by 10%-200%, and the cooking loss rate is reduced by 0.5%-1.5%. The dry-steamed fine dried noodles have good taste, boiling fastness, long shelf life, and good edible quality and cooking performance. By performing high temperature dry-steaming treatment on the prepared fine dried noodles, the present invention improves the quality of the fine dried noodles and particularly improves the hardness and toughness of the fine dried noodles while achieving sterilization and anti-insect effects, thus improving the quality guarantee period of the product, and avoiding the occurrence of quality problems such as noodle rupture and poor taste during direct high temperature drying.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a CON of Ser. No. 09/268,527 (filed Mar. 12, 1999, now U.S. Pat. No. 6,210,606, which application is a CON of Ser. No. 08/620,618 (filed Mar. 22, 1996, now U.S. Pat. No. 5,932,143), which application claims benefit of Ser. No 60/007,688 (filed Nov. 29, 1995).
This application claims priority from Provisional Application Ser. No. 60/007,688 filed Nov. 29, 1995.
FIELD OF THE INVENTION
The present invention is directed to polycrystalline electrically conductive polymer precursors and polycrystalline conducting polymers having adjustable morphology and properties.
BACKGROUND
Electrically conductive organic polymers emerged in the 1970's as a new class of electronic materials. These materials have the potential of combining the electronic and magnetic properties of metals with the light weight, processing advantages, and physical and mechanical properties characteristic of conventional organic polymers. Examples of electrically conducting polymers arc polyparaphenylene vinylenes, polyparaphenylenes, polyanilines, polythiophenes, polyazines, polyfuranes, polythianaphthenes polypyrroles, polyselenophenes, poly-p-phenylene sulfides, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers and copolymers of the monomers thereof.
These polymers are conjugated systems which are made electrically conducting by doping. The doping reaction can involve an oxidation, a reduction, a protonation, an alkylation, etc. The non-doped or non-conducting form of the polymer is referred to herein as the precursor to the electrically conducting polymer. The doped or conducting form of the polymer is referred to herein as the conducting polymer.
Conducting polymers have potential for a large number of applications in such areas such as electrostatic charge/discharge (ESC/ESD) protection, electromagnetic interference (EMI) shielding, resists, electroplating, corrosion protection of metals, and ultimately metal replacements, i.e. wiring, plastic microcircuits, conducting pastes for various interconnection technologies (solder alternative), etc. Many of the above applications especially those requiring high current capacity have not yet been realized because the conductivity of the processible conducting polymers is not yet adequate for such applications.
To date, polyacetylene exhibits the highest conductivity of all the conducting polymers. The reason for this is that polyacetylene can be synthesized in a highly crystalline form (crystallinity as high as 90% has been achieved) (as reported in Macromolecules, 25, 4106, 1992). This highly crystalline polyacetylene has a conductivity on the order of 10 5 S/cm. Although this conductivity is comparable to that of copper, polyacetylene is not technologically applicable because it is a non-soluble, non-processible, and environmentally unstable polymer.
The polyaniline class of conducting polymers has been shown to be probably the most suited of such materials for commercial applications. Great strides have been made in making the material quite processable. It is environmentally stable and allows chemical flexibility which in turn allows tailoring of its properties. Polyaniline coatings have been developed and commercialized for numerous applications. Devices and batteries have also been constructed with this material. However, the conductivity of this class of polymers is generally on the low end of the metallic regime. The conductivity is on the order of 10 0 S/cm. Some of the other soluble conducting polymers such as the polythiophenes, poly-para-phenylenevinylenes exhibit conductivity on the order of 10 2 S/cm. It is therefore desirable to increase the conductivity of the soluble/processible conducting polymers, in particular the polyaniline materials.
The conductivity (σ)is dependent on the number of carriers (n) set by the doping level, the charge on the carriers (q) and on the interchain and intrachain mobility (μ)of the carriers.
σ=n q μ
Generally, n (the number of carriers) in these systems is maximized and thus, the conductivity is dependent on the mobility of the carriers. To achieve higher conductivity, the mobility in these systems needs to be increased. The mobility, in turn, depends on the morphology of the polymer. The intrachain mobility depends on tile degree of conjugation along the chain, presence of defects, and on the chain conformation. The interchain mobility depends on the interchain interactions, the interchain distance, the degree of crystallinity, etc. Increasing the crystallinity results in increased conductivity as exemplified by polyacetylene. To date, it has proven quite difficult to attain polyaniline in a highly crystalline state. Some crystallinity has been achieved by stretch orientation or mechanical deformation (A.G. MacDiarmid et al in Synth. Met. 55-57, 753). In these stretch-oriented systems, conductivity enhancements have been observed. The conductivity enhancement was generally that measured parallel to tile stretch direction. Therefore, the conductivity in these systems is anisotropic. It is desirable to achieve a method of controlling and tuning the morphology of polyaniline. It is desirable to achieve a method of controlling and tuning the degree of crystallinity and the degree of amorphous regions in polyaniline, which in turn provides a method of tuning the physical, mechanical, and electrical properties of polyaniline. It is further desirable to achieve highly crystalline and crystalline polyaniline and to achieve this in a simple and useful manner in order to increase the mobility of the carriers and, therefore, the conductivity of the polymer. It is also further desirable to achieve isotropic conductivity, that is conductivity not dependent on direction as with stretch-oriented polyanilines.
OBJECTS
It is an object of the present invention to provide a polycrystalline material containing crystallites of an electrically conducting polymer precursor and/or electrically conducting polymer having an adjustable morphology.
It is an object of the present invention to provide a polycrystalline material of an electrically conductive polymer precursor and/or electrically conducting polymer in which the degree of amorphous and crystalline regions is adjustable.
It is an object of the present invention to provide a polycrystalline material of an electrically conducting polymer precursor and/or electrically conducting polymer having adjustable physical, mechanical, and electrical properties.
It is an object of the present invention to provide a crystalline electrically conducting polymer precursor and crystalline conducting polymers.
It is an object of the present invention to provide a highly crystalline electrically conducting polymer precursor and highly crystalline conducting polymers.
It is an object of the present invention to provide a polycrystalline material of an electrically conducting polymer precursor and/or crystalline conducting polymers to provide a highly crystalline material.
It is another object of the present invention to provide an electrically conducting polycrystalline material that exhibits enhanced carrier mobility.
It is another object of the present invention to provide an electrically conducting polycrystalline material which exhibits enhanced conductivity.
It is another object of the present invention to provide an electrically conducting polycrystalline material which exhibits enhanced isotropic conductivity.
It is another object of the present invention to provide a plasticization effect in a polycrystalline electrically conducting polymer precursors and/or electrically conducting polymers.
It is another object of the present invention to provide a polycrystalline material having an antiplasticization effect in electrically conducting polymer precursors and electrically conducting polymers.
It is another object of the present invention to provide a polycrystalline material of a precursor or electrically conducting polymer containing an additive providing mobility.
It is another object of the present invention to provide a polycrystalline material of a precursor or electrically conductive polymer containing an additive to induce all enhanced degree of crystallinity.
It is another object of the present invention to provide a non-stretch oriented polycrystalline film of a precursor or of an electrically conductive polymer which has an enhanced degree of crystallinity.
It is an object of the present invention to provide a polycrystalline material of an electrically conducting polymer precursor and/or electrically conducting polymer having an increased glass transition temperature.
It is an object of the present invention to provide an electrically conducting polymer precursor and electrically conducting polymer having an decreased glass transition temperature.
It is an object of the present invention to provide a polycrystalline material of an electrically conducting polymer precursor and electrically conducting polymer having enhanced mechanical properties.
It is an object of the present invention to provide a polycrystalline material of an electrically conducting polymer precursor and electrically conducting polymer having decrease mechanical properties.
SUMMARY OF THE INVENTION
A broad aspect of the present invention is a polycrystalline material comprising crystallites of a precursor to an electrically conductive polymer and/or an electrical conductive polymer. The intersticial regions between the crystallites contain amorphous material.
In a more particular aspect of the present invention, the amorphous regions of the material contain the additive.
DESCRIPTION OF THE DRAWINGS
Further objects, features, and advantages of the present invention will become apparent from a consideration of the following detailed description of the invention when read in conjunction with the drawings FIG's. in which:
FIG. 1 is a general formula for polyaniline in the non-doped or precursor form.
FIG. 2 is a general formula for a doped conducting polyaniline.
FIG. 3 is a general formula for the polysemiquinone radical cation form of doped conducting polyaniline.
FIG. 4 is a Gel Permeation Chromatograph (GPC) of polyaniline base in NMP (0.1%): GPC shows a trimodal distribution—A very high molecular weight fraction (approx. 12%) and a major peak having lover molecular weight.
Curve 5 ( a ) is a Wide Angle-X-Ray Scattering (WAXS) spectrum for a polyaniline base film processed from NMP. The polymer film is essentially amorphous. Curve 5 ( b ) is a Wide Angle X-Ray Scattering spectrum for a polyaniline base film that has stretch-oriented (l/lo=3.7). This film was derived from a gel. Curve 5 ( c ) is a Wide Angle-X-Ray Scattering spectrum for a polyaniline-base film containing 10% poly-co-dimethyl propylamine siloxane. This film is highly crystalline.
FIG. 6 is a Schematic diagram of a polycrystalline material as taught in present invention having crystalline regions (outlined in (dotted rectangles) with intersticial amorphous regions
FIG. 7 is a Dynamic Mechanical Thermal Analysis (DMTA) plot for polyaniline base film cast from NMP. (First Thermal Scan; under Nitrogen).
FIG. 8 is a DMTA plot which represents the second thermal scan for a polyaniline base film cast from NMP; This same film was previously scanned as shown in FIG. 7 . Film Contains no residual solvent.
FIG. 9 is a DMTA plot for polyaniline base film cast from NMP and containing 5% poly-co-dimethyl aminopropyl siloxane (5% N content). First Thermal Scan.
FIG. 10 is a DMTA plot for polyaniline base film cast from NMP and containing 5% poly-co-dimethyl aminopropyl siloxane (5% N content). Second Thermal Scan (this same film was previously scanned as shown in FIG. 9 ) Film Contains no residual solvent.
FIG. 11 is a GPC for a polyaniline base solution in NMP containing 5% poly-co-dimethyl aminopropyl siloxane by weight to polyaniline. The polyaniline was 0.1% in NMP.
DETAILED DESCRIPTION
The present invention is directed toward electrically conducting polymer precursors and conducting polymers having adjustable morphology and in turn adjustable physical, and electrical properties. The present invention is also directed toward controlling and enhancing the 3-dimensional order or crystallinity of conducting polymer precursors and of conducting polymers. In addition, the present invention is directed towards enhancing the electrical conductivity of conducting polymers. This is done by forming an admixture of an electrically conducting polymer precursor or an electrically conducting polymer with an additive whereby the additive provides local mobility to the molecules so as to allow the conducting polymer precursor or conducting polymer chains to associate with one another and achieve a highly crystalline state. An example of such an additive is a plasticizer. A plasticizer is a substance which when added to a polymer, solvates the polymer and increases its flexibility, deformability, generally decreases the glass transition temperature Tg, and generally reduces the tensile modulus. In certain cases, the addition of a plasticizer may induce antiplasticization, that is an increase in the modulus or stiffness of the polymer, an increase in Tg. Herein the additives can provide a plasticization effect, an antiplasticization effect or both effects.
Examples of polymers which can be used to practice the present invention are of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole, p-phenylene sulfide, azines, selenophenes, furans, thianaphthenes, phenylene vinylene, etc. and the substituted and unsubstituted polymers, polyparaphenylenes, polyparaphenylevevinylenes, polyanilines, polyazines, polythiophenes, poly-p-phenylene sulfides, polyfuranes, polypyrroles, polythianaphthenes, polyselenophenes, polyacctylenes formed from soluble precursors and combinations thereof and copolymers of monomers thereof. The general formula for these polymers can be found in U.S. Pat. No. 5,198,153 to Angelopoulos et al. While the present invention will be described with reference to a preferred embodiment, it is not limited thereto. It will be readily apparent to a person of skill in the art how to extend the teaching herein to other embodiments. One type of polymer which is useful to practice the present invention is a substituted or unsubstituted polyaniline or copolymers of polyaniline having general formula shown in FIG. 1 wherein each R can be H or any organic or inorganic radical; each R can be the same or different; wherein each R 1 can be H or any organic or inorganic radical, each R 1 can be the same or different; x≧1; preferable x≧2 and y has a value from 0 to 1. Examples of organic radicals are alkyl or aryl radicals. Examples of inorganic radicals are Si and Ge. This list is exemplary only and not limiting. The most preferred embodiment is emeraldine base form of the polyaniline wherein y has a value of approximately 0.5. The base form is the non-doped form of the polymer. The non-doped form of polyaniline and the non-doped form of the other conducting polymers is herein referred to as the electrically conducting polymer precursor.
In FIG. 2 , polyaniline is shown doped with a dopant. In this form, the polymer is in the conducting form. If the polyaniline base is exposed to cationic species QA, the nitrogen atoms of the imine (electron rich) part of the polymer becomes substituted with the Q + cation to form an emeraldinie salt as show in FIG. 2 . Q + can be selected from H + and organic or inorganic cations, for example, an alkyl group or a metal.
QA can be a protic acid where Q hydrogen. When a protic acid, HA, is used to dope the polyaniline, the nitrogen atoms of the imine part of the polyaniline are protonated. The emeraldine base form is greatly stalbilized by resonance effects. The charges distribute through the nitrogen atoms and aromatic rings making the imine and amine nitrogens indistinguishable. The actual structure of the doped form is a delocalized polysemiquinone radical cation as shown in FIG. 3 .
The emeraldine base form of polyaniline is soluble in various organic solvents and in various aqueous acid solutions. Examples or organic solvents are dimethylsulfoxide (DMSO), dimethylformamide (DMF) and N-methylpyrrolidinone (NMP), dimethylene propylene urea, tetramethyl urea, etc. This list is exemplary only and not limiting. Examples of aqueous acid solutions is 80% acetic acid and 60-88% formic acid. This list is exemplary only and not limiting.
Polyaniline base is generally processed by dissolving the polymer in NMP. These solutions exhibit a bimodal or trimodal distribution in Gel Permeation Chromatography (GPC) as a result of aggregation induced by internal hydrogen bonding between chains as previously described in U.S. patent application Ser. No. 08/370,128, filed on Jan. 9, 1995, the teaching of which is incorporated herein by reference. The GPC curve for typical polyaniline base in NMP is shown in FIG. 4 .
Polymers in general can be amorphous, crystalline, or partly crystalline. In the latter case, the polymer consists of crystalline phases and amorphous phases. The morphology of a polymer is very important in determining the polymer's physical, mechanical, and electronic properties.
Polyaniline base films processed from NMP either by spin coating or by solution casting techniques are amorphous as can be seen in FIG. 5 a which depicts the Wide Angle X-Ray Scattering (WAXS) spectrum for this material. Amorphous diffuse scattering is observed. Some crystallinity is induced in these films by post processing mechanical deformation especially if these films are derived from gels as described by A.G. MacDiarmid et al in Synth. Met. 55-57, 753 (1993), WAXS of a stretch oriented film having been stretched (l/lo=3.7X) derived from a gel is shown in FIG. 5 b . Some has been induced as compared to the non-stretch oriented films as evidenced by the defined scattering peaks.
Doping the amorphous polyaniline base films (those having structure shown in FIG. 5 a ) with aqueous hydrochloric acid results in isotropic conductivity of 1 S/cm. Such films are not crystalline. Similar doping of stretch oriented films results in anisotropic conductivity where conductivity on the order of 10 2 S/cm is measured parallel to the stretch direction whereas conductivity on the order of 10 0 S/cm is measured perpendicular to the stretch direction. It should also be noted that some level of crystallinity is lost during the doping process in these films.
According to the present invention, the interchain (polymer chain) registration is increased as compared to a stretch oriented film.
FIGS. 7 and 8 show the dynamic mechanical thermal analysis (DMTA) spectrum for a polyaniline base film processed from NMP alone. FIG. 7 is the first scan where a Tg of approx. 118 is observed as a result of the residual NMP which is present in the film. FIG. 8 is the second thermal scan of the same film. This film has no residual solvent and a Tg of ≅251° C. is measured for the polyaniline base polymer.
When an additive such as a plasticizer, such as a poly-co-dimethyl propylamine siloxane, is added to the polyaniline base completely different properties and morphology is observed. The siloxane has a polar amine group which facilitates the miscibility of the polyaniline base and the plasticizer. The DMTA of a polyaniline base film cast from NMP and containing 5% by weight to polyaniline of the poly-co-dimethyl propyl amine siloxane exhibits a lower Tg on the first thermal scan as compared to polyaniline base processed from NMP alone ( FIG. 9 ) as a result of plasticization induced by the siloxane. However, on the second thermal scan of this film ( FIG. 10 ), the polymer exhibits an increase in Tg as compared to polyaniline processed from NMP. When the polysiloxane is added to a solution of polyaniline base, the siloxane due to the polar amine group can interact with the polymer chains and disrupt some of the polyaniline interactions with itself or some of the aggregation. Thus, the polysiloxane first induces some deaggregation. However, the polysiloxane has multiple amine sites and thus, it can itself hydrogen bond with multiple polyaniline base chains and thus, the polysiloxane facilitates the formation of a cross-linked network. This cross-linked network accounts for the increased Tg observed in the DMTA. Tg is characteristic of the amorphous regions of a polymer and in this case the amorphous regions consist of a cross-linked polyaniline/polysiloxane network. Thus, the polysiloxane is inducing an antiplasticization effect in polyaniline base as the Tg is increased. Generally, plasticizers reduce Tg. GPC data ( FIG. 11 ) is consistent with this model. The addition of the poly-amino containing siloxane to a polyaniline base solution in NMP results in a significant increase in the high molecular weight fractions depicting the cross-linked network which forms between polyanilie and the plasticizer.
In addition to the cross-linked network the siloxane induces in the amorphous regions, concomittantly it also is found to induce significant levels of crystallinity in polyaniline base as a result of the local mobility that it provides. FIG. 5 c shows the WAXS for a polyaniline base film processed from NMP containing 10% of the poly amino containing siloxane. As can be seen highly crystalline polyaniline has bee attained. Much higher levels of crystallinity as compared to FIG. 5 b for the stretch oriented films.
Thus polyaniline by the addition of the siloxane forms a structure depicted in FIG. 6 where crystalline regions of highly associated polyaniline chains (outlined by a rectangle) are formed with intersticial amorphous regions. In most cases, the additive resides in the amorphous intersticial sites. The degree of crystallinity (number of crystalline sites) and the size of the crystalline domains as well as the degree of amorphous regions and the nature of the amorphous region (aggregated, i.e. cross-linked or not) can be tuned by the type and amount of additive. In turn, by controlling the above, the properties of the material can also be controlled.
With the poly-co-dimethyl aminopropyl siloxane (5% N content), loadings ranging from 0.001 to 20% by weight gives highly crystalline polyaniline. The highly crystalline polyaniline in turn exhibits increased modulus, stiffness, yield and tensile strengths, hardness, density and softening points. Thus, the siloxane at these loadings is having an antiplasticization effect. Above 20% loading, the crystallinity begins to decrease. As the crystallinity decreases, the modulus, stiffness, Yield and tensile strengths, hardness, density and softening points begin to decrease. Thus, the siloxane at these loadings begins to have a plasticization effect. The siloxane content becomes high enough that it disrupts the polyaniline base interactions in the crystalline regions. With the poly co dimethyl aminopropyl siloxanes having 0.5 and 13% N ratios, similar trends are observed but the particular amount of siloxane needed to have a plasticization effect or an antiplasticization effect varies. Thus, the degree of crystallinity and the degree of amorphous regions and in turn the properties of polyaniline can be tuned by the nature of the additive as well as the amount of additive. Indeed, using the same additive but simply changing the loading dramatically changes the morphology and in turn the properties of polyaniline.
The electronic properties of the polymer are also impacted. The conductivity of a polyaniline base film cast from NMP and containing 1% by weight poly-co-dimethyl aminopropyl siloxane which is doped by aqueous hydrochloric acid is 50 S/cm as compared to 1 S/cm for a polyaniline film with no plasticizer. This is isotropic conductivity. The doped film containing the polysiloxane retains the highly crystalline structure.
The degree of crystallinity and the degree of amorphous regions and in turn the physical, mechanical, and electronic properties can be tuned by the particular additive used and by the amount of additive. For example, the Tg of polyaniline can be increased or decreased by the amount and type of additive. The mechanical properties such as tensile properties, modulus, impact resistance, etc. can be tuned as described above. The additive can range from 0.001 to 90% by weight, more preferably from 0.001 to 50% and most preferably from 0.001 to 25%. A list of plasticizers that can be used to practice the present invention is given in Table 1. The additive can also be removed from the final film structure if so desired by appropriate extraction.
SPECIFIC EXAMPLES
Polyaniline Synthesis Polyaniline is synthesized by the oxidative polymerization of aniline using ammonium peroxydisulfate in aqueous hydrochloric acid. The polyaniline hydrochloride precipitates from solution. The polymer is then neutralized using aquoeous ammonium hydroxide. The neutralized or non-dope polyaniline base is then filtered, washed and dried. Polyaniline can also be made by electrochemical oxidative polymerization as taught by W. Huang, B. Humphrey, and A. G. MacDiarmid, J. Chem. Soc., Faraday Trans. 1, 82, 2385, 1986.
Polyaniline Base in NMP: The polyaniline base powder is readily dissolved in NMP up to 5% solids. Thin films (on the order of a micron) can be formed by spin-coating. Thick films are made by solution casting and drying (70° C. in vacuum oven under a nitrogen purge for 15 hours). These solutions and films have the properties described above.
Polyaniline Base in NMP/Plasticizer
a. Polyaniline Base was first dissolved in NMP to 5% solids and allowed to mix well. A poly-co-dimethyl, aminopropyl siloxane (N content 5% relative to repeat unit) was dissolved to 5% in NMP. The siloxane solution was added to the polyaniline base solution. The resulting admixture was allowed to mix for 12 hours at room temperature. A number of solutions were made having from 0.001% to 50% siloxane content (by weight relative to polyaniline). Thin films were spin-coated onto quartz substrates; Thick films were prepared by solution casting and baking the solutions at 70° C. in a vacuum oven under a Nitrogen purge for 15 hours). The solutions and the films have the properties described above.
b. The same experiment described in (a) was carried out except that the plasticizer was a poly-co-dimethyl, aminopropyl siloxane in which the N content was 13%.
c. The same experiment described in (a) was carried out except that the plasticizer was a poly-co-dimethyl, aminopropyl siloxane in which the N content was 0.5%.
d. The same experiment described in (a) was carried out except that the plasticizer was polyglycol diacid.
e. The same experiment described in (a) was carried out except that the plasticizer was 3,6,9-trioxaundecanedioic acid.
f. The same experiment described in (a) was carried out except that the plasticizer was poly(ethylene glycol) tetrahydro furfuryl ether.
g. The same experiment described in (a) was carried out except that the plasticizer was glycerol triacetate.
h. The same experiment described on (a) was carried out except the plasticizer was epoxidized soy bean oil.
Polyaniline Base in NMP/m-Cresol/Plasticizer
The same experiment as described in (a) was carried out except that polyaniline base and the plasticizer was dissolved in NMP/m-Cresol mixtures in which m-Cresol ranged from 1 to 99%
Polyaniline Base in m-Cresol/Plasticizer
The same experiment as described in (a) was carried out except that the polyaniline base was dissolved in m-Cresol and the plasticizer was dissolved in m-Cresol.
Polyaniline Base in m-Cresol and in NMP/m-Cresol
Polyaniline Base was dissolved in m-Cresol and in NMP/m-Cresol combinations to 5% solids. The m-Cresol in the latter system being the additive ranged from 1 to 99%. Free-Standing films were made by solution casting techniques. With increasing m-cresol content, the polyaniline exhibited a WAXS similar to that shown in FIG. 5 a except that the amorphous scattering peak became somewhat sharper indicative of some crystallinity. However, this was significantly less than observed with the siloxane plasticizer.
Doped Polyanilines
a 1. Hydrochloric Acid and/or Methanesulfonic Acid Doped Films
Polyaniline base films made as described above were doped by aqueous acid solutions of hydrochloric or methanesulfonic acid. The films were immersed in the acid solution for 12 hours for thin films and 36 hours for the thick films. The conductivity of a polyaniline base film processed from NMP and doped with these acid solutions is 1 S/cm The conductivity of a base film processed from NMP and 1% poly-co-dimethyl, amiopropyl siloxane (5% N content) was 50 S/cm.
2. Sulfonic Acid Doped Polyanilines
Polyaniline Base was dissolved in a solvent such as NMP or NMP/m-Cresol combinations, etc. from 1 to 5% solids. To this solution was added a dopant such camphorsulfonic acid or acrylamidopropanesulfonic acid (previously reported in U.S. patent application Ser. No. 595,853 filed on Feb. 2, 1996). These solutions were used to spin-coat or solution cast films. In some experiments, the plasticizer such as the poly-co-dimethyl, aminopropyl siloxane in a solvent was added to the doped polyaniline solution. In certain other experiments, the plasticizer was first added to the pani base solution. The dopant was then added to the polyaniline solution containing the plasticizer.
The teaching of the following U.S. Patent Applications are incorporated herein by reference:
“CROSS-LINKED ELECTRICALLY CONDUCTIVE POLYMERS, PRECURSORS THEREOF AND APPLICATIONS THEREOF”, application Ser. No. 595,853, filed Feb. 2, 1996 now U.S. Pat. 6,193,909;
“METHODS OF FABRICATION OF CROSS-LINKED ELECTRICALLY CONDUCTIVE POLYMERS AND PRECURSORS THEREOF”, application Ser. No. 594,680, filed Feb. 2, 1996 now U.S. Pat. No. 6,030,550
“DEAGGREGATED ELECTRICALLY CONDUCTIVE POLYMERS AND PRECURSORS THEREOF’, application Ser. No. 370,127, filed Jan. 9, 1995 now U.S. Pat. No. 5,804,100; and
“METHODS OF FABRICATION OF DEAGGREGATED ELECTRICALLY CONDUCTIVE POLYMERS AND PRECURSORS THEREOF”, application Ser. No. 370,128, filed Jan. 9, 1995 now U.S. Pat. No. 6,087,472.
While the present invention has been shown and described with respect to a preferred embodiment, it will be understood that numerous changes, modifications, and improvements will occur to those skilled in the art without departing from the spirit and scope of the invention.
TABLE I
PLASTICIZERS
ADIPIC ACID DERIVATIVES
Dicapryl adipate
Di-(2-ethylhexyl) adipate
Di(n-heptyl, n-nonyl) adipate
Diisobutyl adipate
Diisodecyl adipate
Dinomyl adipate
Di-(tridecyl) adipate
AZELAIC ACID DERIVATIVES
Di-(2-ethylheyl azelate)
Diisodecyl azelate
Diisoctyl azelate
Dimethyl azelate
Di-n-hexyl azelate
BENZOIC ACID DERIVATIVES
Diethylene glycol dibenzoate
Dipropylene glycol dibenzoate
Polyethylene glycol 200 dibenzoate
CITRIC ACID DERIVATIVES
Acetyl tri-n-butyl citrate
Acetyl triethyl citrate
Tri-n-butyl citrate
Triethyl citrate
DIMER ACID DERIVATIVES
Bis-(2-hydroxyethyl dimerate)
EPOXY DERIVATIVES
Epoxidized linseed oil
Epoxidized soy bean oil
2-Ethylhexyl epoxytallate
n-Octyl expoxystereate
FUMARIC ACID DERIVATIVES
Dibutyl fumarate
GLYCEROL DERIVATIVES
Glycerol triacetate
ISOBUTYRATE DERIVATIVE
2,2,4-Trimethyl-1,3-pentanediol
Diisobutyrate
ISOPHTHALIC ACID DERIVATIVES
Di-(2-ethylhexyl) isophthalate
Dimethyl isophthalate
Diphenyl isophthalate
LAURIC ACID DERIVATIVES
Methyl laurate
LINOLEIC ACID DERIVATIVE
Methyl linoleate, 75%
MALEIC ACID DERIVATIVES
Di-(2-ethylhexyl) maleate
Di-n-butyl maleate
MELLITATES
Tricapryl trimellitate
Tri-(2-ethylhexyl) trimellitate
Triisodecyl trimellitate
Tri-(n-octyl,n-decyl) trimellitate
MYRISTIC ACID DERIVATIVES
Isopropyl myristate
OLEIC ACID DERIVATIVES
Butyl oleate
Glycerol monooleate
Glycerol trioleate
Methyl oleate
n-Propyl oleate
Tetrahydrofurfuryl oleate
PALMITIC ACID DERIVATIVES
Isopropyl palmitate
Methyl palmitate
PARAFFIN DERIVATIVES
Chloroparaffin, 41% Cl
Chloroparaffin, 50% Cl
Chloroparaffin. 60% Cl
Chloroparaffin, 70% Cl
PHOSPHORIC ACID DERIVATIVES
2-Ethylhexyl diphenyl phosphate
Isodecyl diphenyl phosphate
4-Butylphenyl diphenyl phosphate
Tri-butoxyethyl phosphate
Tributyl phosphate
Tricresyl phosphate
Triphenyl phosphate
PHTHALIC ACID DERIVATIVES
Butyl benzyl phthalate
Butyl octyl phthalate
Dicapryl phthalate
Dicyclohexyl phthalate
Di-(2-ethylhexyl) phthalate
Diethyl phthalate
Dihexyl phthalate
Diisobutyl phthalate
Diisodecyl phthalate
Diisononyl phthalate
Diisooctyl phthalate
Dimethyl phthalate
Ditridecyl phthalate
Diundecyl phthalate
RICINOLEIC ACID DERIVATIVES
Butyl ricinoleate
Glyceryl tri(acetyl) ricinoleate)
Methyl acetyl ricinoleate
Methyl ricinoleate
n-Butyl acetyl ricinoleate
Propylene glycol ricinoleate
SEBACIC ACID DERIVATIVES
Dibutyl sebacate
Di-(2-ethylhexyl) sebacate
Dimethyl sebacate
STEARIC ACID DERIVATIVES
Ethylene glycol monostearate
Glycerol monostearate
Isopropyl isostearate
Methyl stearate
n-Butyl stearate
Propylene glycol monostearate
SUCCINIC ACID DERIVATIVES
Diethyl succinate
SULFONIC ACID DERIVATIVES
N-Ethyl o,p-toluenesulfonamide
o,p-toluenesulfonanamide
Polyesters
adipic acid polyester
Paraplex G-40
adipic acid polyester
Santicizer 334F
azelaic acid polyester
Plastolein 9720)
azelaic acid polyester
Plastolein 9750
sebacic acid polyester
Paraplex G-25
Sucrose derivatives
sucrose acetate-isobutyrate (SAIB)
Tartaric acid derivative
dibutyl tartrate
Terephthalic acid derivative
bis(2-ethylhexyl) terephthalate (DOTP)
Trimellitic acid derivatives
tris(2-ethylhexyl) trimellitate (TOTM)
heptyl nonyl trimellitate
heptyl nonyl undecyl trimellitate
triisodecyl trimellitate
Glycol derivatives
diethylene glycol dipelargonate
triethylene glycol di-2
ethylbutyrate
poly(ethylene glycol) (200) di-2-
ethylhexanoate
Glycolates
methyl phthalyl ethyl glycolate
butyl phthalyl butyl glycolate
Hydrocarbons
hydrogenated terphenyls HB-40
poly(alkyl naphthalene)s Panaflex
aliphatic aromatics Leromoll
chlorinated paraffin (52 wt % Cl),
Cereclor S-52
Terpenes and Derivatives
Camphor
Hydrogenated methyl ester or rosin
Phosphonic Acid Derivatives
Chlorinated Polyphosphanate
Siloxanes
Polydimethyl siloxane
Polyco-dimethyl/propylamine siloxanes with various amount of
propylamine content
Polydiphenylsiloxanes
Polyco-dimethylphenyl siloxanes
Silanol terminated polysiloxanes
Amino terminated polysiloxanes
Epoxy terminated polysiloxanes
Carbirol terminated polysiloxanes
Polysilanes
Glycols
Polyethylene glycol
Poly(ethylene glycol) tetrahydrofurfuryl ether
Poly(ethylene glycol) bis(carboxymethyl) ether
3.6.9-trioxadecanoic acid
3.6.9-trioxaundecanedioic acid
Polyglycol diacid
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Polycrystalline materials containing crystallies of precursors to electrically conductive polymers and electrically conductive polymers are described which have an adjustable high degree of crystallinity. The intersticial regions between the crystallites contains amorphous material containing precursors to electrically conductive polymers and/or electrically conductive polymers. The degree of crystallinity is achieved by preparing the materials under conditions which provide a high degree of mobility to the polymer molecules permitting them to associate with one another to form a crystalline state. This is preferable achieved by including additives, such as plasticizers and diluents, to the solution from which the polycrystalline material is formed. The morphology of the polycrystalline material is adjustable to modify the properties of the material such as the degree of crystallinity, crystal grain size, glass transition temperature, thermal coefficient of expansion and degree of electrical conductivity. High levels of electrical conductivity are achieved in the electrically conductive polycrystalline materials without stretch orienting the material. The enhanced electrical conductivity is isotropic as compared to a stretch oriented film which has isotropic electrical conductivity.
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TECHNICAL FIELD
The present invention relates in general to gable-top containers and the blanks from which they are formed. The invention relates more particularly to such containers which are made from heat-sealable sheet material which is bonded and sealed to various degrees in certain areas of the container closure.
BACKGROUND
Gable-top containers or containers are used widely for packaging milk, juices, and other liquid foods, as well as a variety of other food and non-food products. Such containers are often made from sheet material which is heat-sealable to itself. A typical material for gable-top containers is paper board coated on both sides with polyethylene (typically LDPE) or other heat-sealable material.
Completed gable-top cartons are typically adapted to be resealably opened along a top seal or fin. However, it is not uncommon for the heat seal between the LDPE layers to be stronger than the paper board substrate itself. Often, when the carton is opened, the paper tears away from the LDPE layers, or "delaminates", along the seal area.
Delamination usually occurs on or within the mouth of the spout, which is in or near contact with the contents of the package when the contents are poured out. The fibrous, torn surface of the spout is unsightly, and can be unsanitary if food in the container collects on the torn surface as the container is emptied.
In some gable-top cartons, abhesive areas are provided to reduce area of the heat-sealed surfaces. When abhesives are used, the sealing areas are reduced without requiring the sealing machine to narrowly focus the heat-seals, and delamination is greatly reduced.
One problem with conventional abhesives is that they hinder or prevent the formation of a proper fluid seal. This is of particular importance when the material to be packaged requires an hermetic seal, which reduces the transfer of oxygen and other gases, as well as liquids, through the sealed area. In known packages, a partial heat seal is required in addition to the abhesive seal, in order to affect hermetic sealing. The problem of delamination thus is confined to a smaller area, but not eliminated with conventional abhesives.
The conventional gable-top container also presents other functional or manufacturing problems. To allow proper container sealing, the abhesive areas must be precisely placed to leave a sealable margin. The thickness, viscosity, and choice of the abhesive must also be controlled so the abhesive will be effective within its intended boundaries without migrating and acting outside of those boundaries to any significant degree.
The need for precise application of a partial coating such as an abhesive on a substrate makes the application more expensive and difficult, or subjects the filled containers to a higher than desired seal failure rate. Reduction of the abhesive areas to provide a greater margin for migration and variable application increases the size of the torn heat-sealed surface.
The need for abhesives has also been reduced by confining the heat sealing region closely to parts of the inner surface of the carton, instead of (or in addition to) using the abhesives. Again, however, it is difficult to precisely confine ultrasonic, radiant, or conductive heating with a high degree of accuracy and reproducibility, so either the cost and difficulty of operating such equipment increases or the ability to provide a container with highly reproducible opening characteristics suffers.
If conventional polyethylene-coated heat-sealed containers are sealed in confined areas without using abhesives, the sealing temperature must be maintained within a range of a few degrees Fahrenheit (less than 2° C.) to provide sealing integrity without rendering the sealed container difficult to open or subject to delamination. This narrow temperature range is difficult to maintain in production machinery. Deviations from this range result in over- or under-sealed containers. The containers must be over-sealed to some degree to ensure that all are adequately sealed.
SUMMARY OF THE INVENTION
The present invention provides a solution to the many problems associated with the sealing of gable-top cartons. The present invention is able to accomplish this by providing a gable-top carton and blank having abhesive coating layers at specified locations for the facilitated opening of cartons without delaminating or tearing of any surfaces of the spout.
One aspect of the present invention is a blank adapted to form a closed gable-top vessel. The blank comprises a first outer rib panel, a second outer rib panel, a first inner rib panel, a second inner rib panel and an abhesive coating. The first outer rib panel has an inside surface, a closure side edge, top and bottom edges, and a first sealing region on its inside surface adjacent to its top edge. The second outer rib panel has an inside surface, a closure side edge and top and bottom edges, the inside surface of said second outer rib panel having a second sealing region adjacent to its top edge. The first inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the first outer rib panel, an inner edge, top and bottom edges, a third sealing region disposed on its inside surface, and a fourth sealing region disposed on its outside surface. The second inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the second outer rib panel, an inner edge joined by a crease to the inner edge of the first inner rib panel, top and bottom edges, a fifth sealing region disposed on its inside surface, and a sixth sealing region disposed on its outside surface. The abhesive coating is applied to a sealing region selected from the group consisting of the first sealing region, the second sealing region, the third sealing region, the fourth sealing region, the fifth sealing region, the sixth sealing region and any combination thereof. The abhesive coating may be composed of copolymers of ethylene moieties and at least one other chain component selected from the group consisting of acrylic acid moieties, vinyl alcohol moieties and combinations thereof.
Another aspect of the present invention is a blank formed from sheet material having a heat-sealable inside major surface. The blank is folded to form a closed gable-top vessel. The blank comprises at least one outer rib panel, at least one inner rib panel and an abhesive coating. The at least one outer rib panel has an inside surface, a closure side edge, top and bottom edges, and a first sealing region on its inside surface adjacent to its top edge. The at least one inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the at least one outer rib panel, an inner edge, top and bottom edges, and a second sealing region disposed on its inside surface. The abhesive coating is applied to at least one of the first sealing region and second sealing region for substantially hermetically sealing the first sealing region to the second sealing region when the gable-top vessel is closed. The abhesive coating provides for the facilitated openability of the gable-top vessel and the substantial elimination of delamination when the vessel is open.
The blank may further comprise a second outer rib panel, a second inner rib panel and a second abhesive coating. The second outer rib panel has an inside surface, a closure side edge and top and bottom edges, the inside surface of said second outer rib panel having a third sealing region adjacent to its top edge. The second inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the second outer rib panel, an inner edge joined by a crease to the inner edge of the first inner rib panel, top and bottom edges, and a fourth sealing region disposed on its inside surface. The second abhesive coating is applied to at least one of the third sealing region and fourth sealing region for substantially hermetically sealing the third sealing region to the fourth sealing region when the gable-top vessel is closed. The blank may further comprise a fifth sealing region disposed on the outside surface of the at least one inner rib panel, a sixth sealing region disposed on the outside surface of the second inner rib panel, and a third abhesive coating. The third abhesive coating is applied to at least one of the fifth sealing region and the sixth sealing region for substantially hermetically sealing the fifth sealing region to the sixth sealing region when the gable-top vessel is closed.
The first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer of ethylene and acrylic acid subsequent to drying. More specifically, the first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer of approximately 5 mol % to approximately 50 mol % acrylic acid moieties and approximately 50 mol % to approximately 95 mol % ethylene moieties. The first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer having a melt index of from about 300 to about 3000 subsequent to drying.
Another aspect of the present invention is a filled and sealed gable-top vessel made from sheet material having a heat-sealable inside surface and a gable-top closure. The gable-top closure comprises at least one outer rib panel, at least one inner rib panel and an abhesive coating. The at least one outer rib panel has an inside surface, a closure side edge, top and bottom edges, and a first sealing region on its inside surface adjacent to its top edge. The at least one inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the at least one outer rib panel, an inner edge, top and bottom edges, and a second sealing region disposed on its inside surface. The abhesive coating is applied to at least one of the first sealing region and second sealing region for substantially hermetically sealing the first sealing region to the second sealing region when the gable-top vessel is closed.
The gable-top closure may further comprise a second outer rib panel, a second inner rib panel and a second abhesive coating. The second outer rib panel has an inside surface, a closure side edge and top and bottom edges, the inside surface of said second outer rib panel having a third sealing region adjacent to its top edge. The second inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the second outer rib panel, an inner edge joined by a crease to the inner edge of the first inner rib panel, top and bottom edges, and a fourth sealing region disposed on its inside surface. The second abhesive coating is applied to at least one of the third sealing region and fourth sealing region for substantially hermetically sealing the third sealing region to the fourth sealing region when the gable-top vessel is closed. The gable-top closure may further comprise a fifth sealing region disposed on the outside surface of the at least one inner rib panel, a sixth sealing region disposed on the outside surface of the second inner rib panel, and a third abhesive coating. The third abhesive coating is applied to at least one of the fifth sealing region and the sixth sealing region for substantially hermetically sealing the fifth sealing region to the sixth sealing region when the gable-top vessel is closed.
The first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer of ethylene and acrylic acid. More specifically, the first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer of approximately 5 mol % to approximately 50 mol % acrylic acid moieties and approximately 50 mol % to approximately 95 mol % ethylene moieties. Even more specifically, the first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer of approximately 15 mol % to approximately 25 mol % acrylic acid moieties and approximately 75 mol % to approximately 85 mol % ethylene moieties. The first abhesive coating, second abhesive coating and third abhesive coating may consist essentially of a copolymer having a melt index of from about 300 to about 3000.
Still another aspect of the present invention is a method of assembling a gable-top container. The first step of the method is providing sheet material having a first surface and a second surface, one of which is a heat-sealable inside surface. The next step is cutting and creasing said sheet material to provide a blank. The blank comprises a first outer rib panel, a second outer rib panel, a first inner rib panel, a second inner rib panel and an abhesive coating. The first outer rib panel has an inside surface, a closure side edge, top and bottom edges, and a first sealing region on its inside surface adjacent to its top edge. The second outer rib panel has an inside surface, a closure side edge and top and bottom edges, the inside surface of said second outer rib panel having a second sealing region adjacent to its top edge. The first inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the first outer rib panel, an inner edge, top and bottom edges, a third sealing region disposed on its inside surface, and a fourth sealing region disposed on its outside surface. The second inner rib panel has an inside surface, an outside surface, an outer edge joined by a crease to the closure side edge of the second outer rib panel, an inner edge joined by a crease to the inner edge of the first inner rib panel, top and bottom edges, a fifth sealing region disposed on its inside surface, and a sixth sealing region disposed on its outside surface. The abhesive coating is applied to a sealing region selected from the group consisting of the first sealing region, the second sealing region, the third sealing region, the fourth sealing region, the fifth sealing region, the sixth sealing region and any combination thereof. The abhesive coating may be composed of copolymers of ethylene moieties and at least one other chain component selected from the group consisting of acrylic acid moieties, vinyl alcohol moieties and combinations thereof.
The next step of the method is squaring the blank to partially form the gable-top container with open ends. The next step is forming a bottom rib and a top rib of the gable-top container. The next step is filling the gable-top container with a desired contents such as milk. The final step is forming a second bottom rib and a second top rib of the gable-top container to provide a filled and sealed gable-top container.
Having briefly described the described this invention, the above and further objects, features and advantages thereof will be recognized by those skilled in the pertinent art from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
There is illustrated in FIG. 1 a perspective view of a fully assembled gable-top carton.
There is illustrated in FIG. 2 a view of the bottom of the gable-top carton of FIG. 1.
There is illustrated in FIG. 3 an outside surface plan view of a blank for a gable-top carton.
There is illustrated in FIG. 4 a perspective view of a partially assembled gable-top carton fabricated from the blank of FIG. 3.
There is illustrated in FIG. 5 an inside surface plan view of one embodiment of a top of a container blank according to the present invention.
There is illustrated in FIG. 6 an outside surface plan view of the blank of FIG. 1.
There is illustrated in FIG. 7 a perspective view of a closed gable-top container according to the present invention, with one outside rib panel and one inclined roof panel cut away to show underlying structure.
There is illustrated in FIG. 8 a fragmentary section taken along line 8--8 of FIG. 7.
There is illustrated in FIG. 9 a view similar to FIG. 7, showing the container partly opened.
There is illustrated in FIG. 10 a view similar to FIG. 7, showing the container fully opened, deploying its spout.
There is illustrated in FIG. 11 a fragmentary view similar to FIG. 5, showing a different pattern of application of an abhesive coating.
There is illustrated in FIG. 12 a plot of temperature versus sealing characteristics comparing the sealing performance of a heat-sealing machine when the sealed surfaces are unmodified polyethylene-coated paper board surfaces versus the same type of surfaces coated with an ethylene and acrylic acid copolymer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention pertains to gable-top cartons and the blanks from which the cartons are formed. The construction and parts of such containers and the blanks from which they are formed are described and illustrated, for example, in U.S. Pat. No. 4,744,467, issued to Tetra Pak International AB, and U.S. Pat. No. 4,775,096, issued to AB Tetra Pak. Those entire patents are incorporated by reference here. The present invention builds upon those patents to provide a gable-top carton having abhesive coating layers at specified locations for the facilitated opening of cartons without delaminating or tearing of any surfaces of the spout. The present invention also reduces the necessity for precise placement of sealing materials and precise sealing conditions in a gable-top carton. The present invention further reduces the differences in seal properties which conventionally result from temperature variations in the sealing operation.
There is illustrated in FIG. 1 a perspective view of a fully assembled gable-top carton. There is illustrated in FIG. 2 a view of the bottom of the gable-top carton of FIG. 1. FIG. 1 illustrates a gable top carton 10 including a gable top 12 having a pair of converging gable sides 14, 16. The gable top carton 10 has a bottom surface 18, as shown in FIG. 2. The bottom surface 18 includes a pair of major flaps 20, 20' sealed along a bottom seal 22 that substantially bisects the bottom surface 18.
There is illustrated in FIG. 3 an outside surface plan view of a blank for a gable-top carton. A gable top carton such as that shown in FIG. 1 can be formed using a carton blank 24 of FIG. 3. The blank 24 includes a carton body 26 divided by a plurality of vertical creases 28. The vertical creases 28 extend from the top T to the bottom B of the carton blank, and separate the carton blank 24 into first (30), second (32), third (34), fourth (36), and fifth (38) vertical panels.
A horizontal top crease 40 extends substantially between the sides of the carton blank 24. The top crease 40 intersects with the vertical creases 28 define first (42), second (44), third (46), and fourth (48) top flaps between the horizontal top crease 40 and the top T of the carton blank 24, with the top flaps separated from one another by upper portions U of the vertical creases 28. A horizontal bottom crease 50 extends substantially between the sides of the carton blank 24 at a position between the bottom B of the carton blank 24. The bottom crease 50 intersects with the vertical creases 28 to define first (52), second (54), third (56), and fourth (58) bottom flaps between the horizontal bottom crease 50 and the bottom B of the carton blank 24. The bottom flaps are separated from one another by lower portions L of the vertical creases 28.
A series of top diagonal creases 60 are formed on the second top flap 44 and the fourth top flap 46 of the carton blank 24. The top diagonal creases 60 enable the second and fourth top flaps to be folded inwardly toward one another during carton formation, thus causing the first top flap 42 and third top flap 48 to become the gabled sides of the finished carton.
A series of bottom diagonal creases 62 are formed on the second bottom flap 54 and the fourth bottom flap 58 of the carton blank 24. The bottom diagonal creases 62 enable the second and fourth bottom flaps to be folded inwardly toward one another during carton formation, while the first bottom flap 52 and the third bottom flap 56 become the major flaps that form the bottom exterior surface of the finished carton.
There is illustrated in FIG. 4 a perspective view of a partially assembled gable-top carton fabricated from the blank of FIG. 3. The forming process for the carton blank 24 is schematically illustrated in FIG. 4. Force is applied to the top portion of the partially erected carton blank 24 in the direction of arrows 64 and 66 in such a way as to cause the top flap 44, along with the top flap 48 (not visible in FIG. 4) to fold inwardly toward one another, due to the diagonal creases 60. The top flap 42 and the top flap 46 thus form gable sides of the finished carton, sealed together at a top fin 68.
Force is also applied in the direction of arrows 70 and 72 to the bottom portion of the partially erected carton blank 24, thus causing the bottom flap 54, along with the bottom flap 58 (not visible in FIG. 4) to fold inwardly toward one another, due to the diagonal creases 62. The bottom flap 52 and the bottom flap 56 thus form major flaps of the finished carton, sealed together at a bottom seal 74.
There is illustrated in FIG. 5 an inside surface plan view of one embodiment of a container blank according to the present invention. There is illustrated in FIG. 6 an outside surface plan view of the blank of FIG. 5. As can be seen in FIG. 5, the blank 24 includes the top flaps 42, 44, 46 and 48. A second horizontal top crease 49 further defines the top flaps 42, 44, 46 and 48 into a series of rib panels. The top flap 42 has an outer rib panel 70. The top flap 44 has front inner rib panels 72 and 74. The top flap 46 has an outer rib panel 76. The top flap 48 has rear inner rib panels 78 and 80. Additionally, the top flaps 42 and 46 have top sealing portions 82 and 84 which are divided respectively from outer rib panels 70 and 76 by dividing lines 86 and 88.
Returning to outer rib panel 70, a first inner spout abhesive area 90 is located at a position for optimum sealing with a second inner spout abhesive area 92 located on the inner rib panel 72 while minimizing the use of an abhesive coating layer. The outer rib panel 76 has a third inner spout abhesive area 96 which is located at a position for optimum sealing with a fourth inner spout abhesive area 94 located on the inner rib panel 74 while minimizing the use of an abhesive coating layer. The second and fourth abhesive areas 92 and 94 extend to top edges 102 and 104 for inner rib panels 72 and 74, respectively. However, in this embodiment, the first and third abhesive areas 90 and 96 do not extend to the top edges 106 and 108 for the outer rib panels 70 and 76, respectively. The mating of the first abhesive area 90 with the second abhesive area 92, and the third abhesive area 96 with the fourth abhesive area 94 when the gable-top carton is closed, allows for the use of an abhesive coating layer on only one of each pair of abhesive areas if desired. The abhesive coating layer which may be applied to any of the abhesive areas is further described below.
As shown in FIG. 6, the outer surface elements corresponding to the inner surface elements shown in FIG. 5 have the same numeral designation except that the numeral designations for the outer surface elements are followed by an "A" as demonstrated by the outer surface top flap 42A corresponding to inner surface top flap 42. On the outer surface of the carton blank 24, only the outer surface of the inner rib panels 72A and 74A have abhesive areas which are designated fifth abhesive area 98 and sixth abhesive area 100. When the gable-top carton is closed, the fifth abhesive area 98 is disposed for mating with the sixth abhesive area 100.
The closure or top rib of a gable-top container is formed by overlapping and heat-sealing the side flap 20 on the margin of the side panel 12 and folding the container blank 10 to the configuration shown in FIGS. 7 and 8. Some parts of the container are better shown in FIGS. 9 and 10. As a result, the outer surfaces 72A and 74A of its front inner rib panels 72 and 74, and thus the outer spout abhesive areas 98 and 100 and the top edges 102 and 104, are juxtaposed. The inner surfaces of its outer rib panel 70 and front inner rib panel 72 and the inner surfaces of its front inner and outer rib panels 74 and 76 are also juxtaposed, which causes the inner spout abhesive areas 90 and 92, the inner spout abhesive areas 94 and 96, and the top edges 106 and 108 to be juxtaposed. The top sealing portions 82 and 84 of the outer rib panels 70 and 76 are juxtaposed. The juxtaposed pairs of abhesive areas 90 and 92, 94 and 96, and 98 and 100 can be thought of as merging to form integral abhesive coating layers 110, 112, and 114 as illustrated in FIG. 8. Finally, a fin 116 is created by the heat sealing of top sealing portions 82 and 84 (which may be done by heating, ultrasonic welding, or other means) while the outer rib panels 70 and 76 are urged together to close and seal the top of the package.
The abhesive layers 110, 112, and 114 interposed between portions of the outer and front inner rib panels 70 and 72, the front inner and outer rib panels 74 and 76, and the front inner rib panel outside surfaces 72A and 74A prevent the underlying surfaces from being heat-sealed together at all, or with a full-strength bond. The remaining juxtaposed panels of the gable-top closure, and particularly the parts of the panels 70, 72, 74, and 76 between and above the abhesive areas 90, 92, 94, 96, 98, and 100, are unaffected by the abhesive coating which is applied to these abhesive areas. Their polyethylene or similar thermoplastic surfaces bond together with full strength to seal the container shut. Typically, the abhesive areas 90, 92, 94, 96, 98 and 100 have been subjected to silicone oils or gums, waxes, or other materials before application of the abhesive coating which reduce the bonding strength essentially to nothing.
The container is opened in four stages, illustrated by comparing FIGS. 7, 9, and 10. There is illustrated in FIG. 7 a perspective view of a closed gable-top container according to the present invention, with one outside rib panel and one inclined roof panel cut away to show underlying structure. There is illustrated in FIG. 9 a view similar to FIG. 7, showing the container partly opened. There is illustrated in FIG. 10 a view similar to FIG. 7, showing the container fully opened, deploying its spout. First, the heat-sealed top sealing portions 82 and 84 of one half of the outer rib panels 70 and 76 above the inclined roof panels 64 and 66 must be parted by grasping the two wings defined by the front triangular fold-back panels 64A and 66A and breaking the bond between the top sealing portions 82 and 84 and the bond (if any) between the non-abhesive coated margins of the front inner rib panels 72A and 74A. Second, the two wings defined by the panels 64A and 66A are swung open about 180° or more, as illustrated in FIG. 9. Third, the side creases 28A and 28B are urged together and forward to buckle the pairs of panels 70, 72 and 74, 76, breaking the bonds between them. Fourth, the front triangular fold-back panels 64 and 66 and the front inner triangular end panel 60 are inverted to open a spout having a rhombic horizontal section.
A second embodiment of the invention is shown in FIG. 11, which is like FIG. 5 except for the choice of abhesive application areas. In FIG. 11, the abhesive coating application area is expanded substantially, versus FIG. 5. The areas 90, 92, 94, and 96 are merged to form a single abhesive coating layer which covers the entire panels 72 and 74 and corresponding parts of the panels 70 and 76. The abhesive coating layer also extends above the dividing lines 96 and 98 all the way to the top edges 104 and 108 of the panels 70 and 76. There is no longer any need to provide uncoated side margins between the areas 90 and 92, between the areas 94 and 96, and above the dividing lines 86 and 88 since these areas can be sealed by the abhesive coating layer.
The abhesive coating, subsequent to drying, in each embodiment may consist essentially of a material selected from copolymers of two ethylenically unsaturated monomers, in particular ethylene and at least one other chain component selected from the group consisting of acrylic acid moieties, vinyl alcohol moieties, and combinations thereof. When applied wet, the abhesive coating may consists of a copolymer, ammonia, water and other releasing additives. The abhesive coating layer, for example, may consist essentially of a copolymer of ethylene and acrylic acid subsequent to drying. One contemplated copolymer is from about 5 mol % to about 50 mol %, alternately from about 15 mol % to about 25 mol %, alternately about 20 mol %, acrylic acid moieties and from about 50 mol % to about 95 mol %, alternately from about 75 mol % to about 85 mol %, alternately about 80 mol % ethylene moieties. The preferred abhesives are branched polymeric chains having a melt index of from about 300 to about 3000, which is an indirect measure of their molecular weights. A melt index of about 300 for a 20% acrylic acid copolymer corresponds to a weight average molecular weight of 18,000 and a number average molecular weight of 7000.
Such abhesives are marketed commercially under the registered trademark PRIMACOR by The Dow Chemical Company, Midland, Mich. A specific material in this family which has been found to be useful is PRIMACOR 5990.
Another type of abhesive useful herein is a copolymer of ethylene and vinyl alcohol having similar molar ratios of its constituents and other properties as the ethylene and acrylic acid copolymers identified above. Terpolymers of ethylene, acrylic acid, and vinyl alcohol, in which the proportions of ethylene moieties are as previously stated and the proportions of the acrylic acid and vinyl alcohol moieties, combined, are the same as those of the acrylic acid moieties of the ethylene/acrylic acid copolymers discussed above, are also contemplated for use as the present abhesives.
The abhesives contemplated herein can be formulated with a variety of other materials, within the scope of the present invention. Fillers such as unmodified or amine modified clay, barium sulfate, barytes, carbon black, titanium dioxide, whiting, calcium carbonate, zinc oxide, colloidal silica, or combinations of these materials can be used. Colors, particularly inorganic pigments and organic pigments, can be used. Invisible dyes which can be detected under ultraviolet light can be used to verify the abhesive application areas. Releasing agent additives may also be employed to further enhance the openability of the carton.
Gums and thickeners can be incorporated in the present abhesives. Exemplary materials of this kind include ACRYSOL ASE (sold by Union Carbide), casein, hydroxyethylcellulose, guar gum, Karaya gum, methylcellulose, polyvinyl alcohol, starches, and the like.
Defoamers and lubricants can be used in these abhesive compositions. Exemplary materials of these kinds are colloidal silica, dioctyl phthalate, paraffin or other waxes (directly or as emulsions), ethylene glycol, propylene glycol, trioctyl phosphate, and 2-ethylhexanol.
Other materials which can be added include inorganic or organic alkalis for pH adjustment, melamine-formaldehyde resin, monovalent electrolytes, a styrene maleic half ester, and the sodium salt of styrene maleic acid.
The present abhesives may be dispersed in water to provide, for example, from about 10% to about 70% solids, optionally from about 14% to about 40% solids, in an aqueous solution. The dispersion may be prepared by heating the neat abhesive above its melting point and mixing or emulsifying it with water in the presence of an alkaline agent. If a fugitive alkali is desired, ammonia can be used. An organic or inorganic alkali can also be used, although if a substantial amount of non-volatile alkali remains in the final coating its resistance to penetration by water might be reduced. Other diluents useful herein include water-miscible and water-soluble solvents, for example alcohols, particularly isopropanol. Other organic solvents can be used, but are less preferred in an industrial setting than water or water-soluble materials.
The water dispersion can have the following exemplary properties at a standard temperature, such as 77° F. (25° C.): a solids level of from about 10% to about 50% by weight, a viscosity by Brookfield LVT of from less than about 60 cps (#1 spindle at 60 RPM) to at least 600 cps (#3 spindle at 60 RPM), a Zahn Cup viscosity of from less than 25 seconds (#2 cup) to more than 40 sec (#3 cup); and a pH of from about 7.5 or a little less to about 11.5 or more.
Specific abhesive formulations which are useful herein are sold by Michelman Inc., Cincinnati, Ohio, Mica Corporation, Stratford, Conn., Pierce & Stevens, Varitech Division and Findley Abhesives Inc., Wauwatosa, Wis.
The aqueous abhesive formulation is applied in a very thin layer, for example, less than a mil (0.025 mm. or 25μ) thick, potentially less than 0.1μ thick, on heat-sealable gable-top container stock. Rotogravure, flexographic, or pad application equipment can be used for this purpose. The solvent is allowed to evaporate, which may be accomplished more quickly by heating the abhesive areas, to provide a dry coating. The abhesive may be applied before or after blanks are formed from the stock. The blanks are then used conventionally to make, fill, and seal containers.
EXAMPLE ONE
In independent trials, each of the manufacturers abhesive formulations is coated to a thickness of about 1 mil (25μ), as shown in FIG. 7, on polyethylene-coated paperboard blanks. The containers are fabricated and heat sealed with conventional gable-top container fabricating equipment. As a control, samples of the same container blanks which are not coated with the abhesive are fabricated in the same manner as the abhesive-treated containers. Separate samples of each type of container are heat-sealed at temperatures ranging in ten-degree increments from 270° F. to 450° F. (132° to 232° C.).
FIG. 8 compares the results of sealing treated and untreated containers at various temperatures. The X-axis is sealing temperature and the Y-axis is a qualitative value scale in which the range from 4 to 5 set off in Table I below represents an optimal value. Higher and lower values are deviations from optimal representing a deficient seal (values of 1, 2, or 3) or excessive adhesion (values of 6, 7, 8, 9, or 10). The specific definitions for the value scale are set out in Table I.
The difference between practicing the present invention with and without the present abhesive is shown in FIG. 8. The polyethylene-coated material without the abhesive provides a much stronger seal at any given temperature, but only provides the optimal seal strength values of 4 to 5 in a temperature range of about 3° F. (less than 2° C.)--from about 284 to about 287° F. (140° to 142° C.). An acceptable degree of sealing is difficult to obtain using polyethylene-coated material without the present abhesive or an abhesive, since it is difficult to maintain the sealing temperature within three degrees (less than 2° C.) in commercial equipment.
The abhesive composition according to the present invention, represented by the lower curve, provides optimal sealing in an approximately 30° F. (17° C.) or greater range, from 350° to 380° F. (177 to 193° C.). The sealing temperature can readily be held within this range when the present invention is practiced. Thus, the opening force and tearing can be minimized without producing inadequately sealed containers.
TABLE I______________________________________Sealing Value ScaleVALUE Degree of Seal Ease of Opening Fiber tear______________________________________0 None Easy None1 Slight Easy None2 Partial Easy None3 Almost complete Easy None4 Complete Easy None5 Complete Acceptable None6 Complete Hard None7 Complete Hard Slight8 Complete Hard Partial9 Complete Hard Extensive10 Complete Hard Total______________________________________
From the foregoing it is believed that those skilled in the pertinent art will recognize the meritorious advancement of this invention and will readily understand that while the present invention has been described in association with a preferred embodiment thereof, and other embodiments illustrated in the accompanying drawings, numerous changes, modifications and substitutions of equivalents may be made therein without departing from the spirit and scope of this invention which is intended to be unlimited by the foregoing except as may appear in the following appended claims. Therefore, the embodiments of the invention in which an exclusive property or privilege is claimed are defined in the following appended claims.
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A gable-top vessel made from sheet material having a heat-sealable surface is disclosed. The closure has at least one abhesive layer disposed between and joining the inner surfaces of the first and second outer rib panels to define a pair of joined panels. In one embodiment, the abhesive is applied at least adjacent to the top edges of the outer rib panels which are joined. The abhesive layer can be a copolymer of ethylene and acrylic acid or vinyl alcohol. The abhesive layer substantially hermetically seals the joined panels together whicle reducing the force required to part the joined panels, compared to the force which would be required to part the joined panels if the same panels were heat-sealed directly together in the same sealing regions without the abhesive. A method of assembling a filled and sealed gable-top container is also disclosed. Before or after the sheet material is cut or creased, at least one abhesive layer as described above is applied to at least one of the surfaces which are joined to seal the closure. The blank is then folded, filled and heat sealed to form a closed, essentially hermetically sealed, unitary top rib.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
THIS INVENTION relates to well-cleaning systems.
2. Prior Art
AU-B-39856/93 (655111) (McCASKER) disclose a well-cleaning system particularly suitable for cleaning sewerage pump-station wells.
A common and expensive problem in most sewerage systems is the build-up of fatty residues on the walls and components of sewerage holding wells. If not regularly removed, these residues will adversely affect the efficiency of the sewerage system, causing damage to the expensive pumps and creating an unhealthy and smelly environment.
The well-cleaning system disclosed in AU-B-39856/93 discloses a rotary spray device mounted on a pivoting arm. Mains water is delivered to the device by a solenoid valve. The water travels through the two spray arms to special nozzles which are directed at the well's walls and components. The nozzle mountings are manually adjustable so that the water can be directed to “hard to get at” corners, and the speed of rotation is also manually adjustable. The solenoid valve is operable by a relay in the control board of the well's pump, so that it opens when the pump turns on. Thus, the cleaning process proceeds as the sewage level is dropping. The solenoid closes when the pump stops and so water consumption is kept to a minimum. The mounting bracket allows the washer to pivot back against the wall to allow uninhibited access to the pump(s) and other equipment at the base of the well.
While the well-cleaning systems hereinbefore described have found ready acceptance with civic and public authorities (eg., in Australia) responsible for handling sewage, a number of potential areas for improvement of the systems have been identified.
In some installations, it has been found that frequent well pump-out cycles result in large volumes of water being sprayed into the wells. Not only is this unacceptable from a water conservation aspect, but the water adds to the volume of sewage which must be treated at the sewerage treatment facility.
In normal operation the system only uses water to perform its cleaning function in the well. Wells can often be a source of bad odours and/or corrosive gases. It would be advantageous to inject into the water (a) a deodorant mask to overcome, or minimise, the odours and/or (b) chemical and/or biological additives to improve the quality of well contents.
Hydrogen sulphide (H 2 S) gas is a major problem in sewage. It is toxic, explosive, corrosive and has an extremely offensive odour. It would be advantageous to provide a gas detector in the well to measure the H 2 S gas concentrations, to connect such a detector to a control unit which can operate the well-cleaning system when a predetermined H 2 S gas concentration is reached.
As the pumping-station wells are often located at locations remote from the control centre for the sewerage system, eg., for a city or local government area, it would be advantageous if the well-cleaning system could communicate conditions in the well to the control centre and be controlled therefrom in response to the conditions communicated.
In many countries, including the USA, the work-safety requirements for the man-entry of wells is extremely rigorous, and so man-entry is to be avoided, if possible, for the installation, maintenance, repair or replacement of equipment, eg., pumps, in the wells. It would be advantageous if the well-cleaning system could be installed, or retrieved, without requiring man-entry to the well. It would be further advantageous if the mounting for the well-cleaning system could take advantage of existing equipment installed in the well.
Finally, in some countries, eg., the United Kingdom, the use of reduced pressure zone (RPZ) valves, to prevent the backflow of water from the well-cleaning system to the reticulated mains water supply is not permitted. It is, therefore, necessary to provide a pressurised water supply, for well-cleaning system, which is isolated by an air gap from the mains supply.
SUMMARY OF THE PRESENT INVENTION
It is an object of the present invention to provide a well-cleaning system where the volume of water used during the cleaning operation is minimised.
It is a preferred object to provide a control system for such a system, where the supply of cleaning water to the well-cleaning system is controlled by a computerised control unit, which controls the frequency, and duration of the period, that water is sprayed in the well.
It is a further preferred object to provide such a control system where the conditions in the well can be monitored and chemicals can be selectively injected into the cleaning water to reduce odours and/or improve well conditions.
It is a still further preferred object to provide such a control system which can monitor hydrogen sulphide gas concentrations in the well and operate the system when the concentration reaches a preset limit.
It is a still further preferred object to provide such a control system which can communicate with, or be controlled by, a remote control location.
It is a still further preferred object to provide such a well cleaning system where the mounting arm is mounted on a carriage movable along pump rail(s) in the well and is retrievable without man-entry to the well.
It is a still further preferred object to provide a well-cleaning system with a pressurised cleaning water supply, separate from a mains supply, by an air gap to prevent backflow.
Other preferred objects will become apparent from the following description.
In one aspect, the present invention resides in a control system for a well-cleaning system of the type having a rotary spray device rotatably mounted on a support arm and connectable to a cleaning liquid supply by a selectively operable liquid control valve, the control system including:
a first waste liquid level sensor in the well detecting when waste liquid has been pumped from the well;
a control unit, operably connected to the cleaning liquid control valve; and
a first timer and a second timer operably connected to the control unit;
so arranged that when the first waste liquid level sensor detects that waste liquid has been pumped from the well, the control unit operates the cleaning liquid control valve, to allow cleaning liquid to flow to the rotary spray device to clean the well, with a wash cycle having a duration determined by the second timer, the first timer preventing the control unit initiating a further wash cycle until the elapse of a preset period.
Preferably, the control unit is connected to a liquid waste pump in the well, and is connected to a second waste liquid level sensor in the well, spaced above a first waste liquid sensor, to operate the pump when the waste liquid is detected by the second waste liquid level sensor.
Preferably, the control unit shuts off the pump when the waste liquid level falls to the first liquid level sensor.
Alternatively, the control unit shuts off the pump after the wash cycle is completed.
Preferably, the control system further includes:
a well-condition sensor in the well, connected to the control unit, and operable to cause the control unit to open an additive injection valve to inject deodorant masks, chemicals and/or biological additives, from an additive supply source, into the cleaning liquid during the wash cycle.
Preferably, the control system further includes:
a hydrogen sulphide (H 2 S) gas sensor in the well, connected to the control unit, and operable to cause the control unit to operate the well-cleaning system where H 2 S gas concentration in the well exceeds a preset limit.
Preferably, the control unit is connected to a remote control centre by radio- or microwave link or by a land line.
In a second aspect, the present invention resides in a well-cleaning system incorporating the control system as hereinbefore described.
In a third aspect, the present invention resides in a retrieval system for a well-cleaning system of the type having a rotary spray device rotatably mounted on a support arm and connectable to a cleaning liquid supply by a selectively operable liquid control valve, the retrieval system including:
a carriage at an end of the support arm spaced from the rotary spray device, slidably mounted on at least one pump guide rail in a well; and
flexible retrieval means attached at one end to the support arm and extending from the well to enable the well-cleaning system to be raised or lowered in the well without man-entry to the well.
Preferably, the carriage is slidably mounted on a single pump guide rail or a pair of parallel spaced guide rails; and
the flexible retrieval member is a chain, cable or rope.
In a fourth aspect, the present invention resides in a well-cleaning system incorporating the retrieval system as hereinbefore described.
In a fifth aspect, the present invention resides in a pressurised cleaning liquid supply system for a well-cleaning system of the type as hereinbefore described, the cleaning liquid supply system including:
a cleaning liquid supply line connected to a source of cleaning liquid and having a cleaning liquid flow valve;
a reservoir, spaced from an outlet of the supply line by an air gap; and
a pressure pump in the reservoir operably connected to the rotary spray device;
so arranged that when the well-cleaning system is operating, the cleaning liquid flow valve allows flow of cleaning liquid to the reservoir to replenish the cleaning liquid pumped to the rotary spray device by the pressure pump.
In a sixth aspect, the present invention resides in a well-cleaning system incorporating the cleaning liquid supply system as hereinbefore described.
Other aspects of the present invention will become apparent from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
To enable the invention to be fully understood, preferred embodiments will now be described with reference to the accompanying drawings in which:
FIG. 1 is a schematic side view of the well-cleaning system provided with the control system;
FIG. 2 is a schematic side view of the guide rail mounting system;
FIGS. 3 and 4 are respective side elevational and top plan views of one embodiment of the guide rail mounting system;
FIGS. 5 and 6 are respective side elevational and top plan views of a second embodiment of the guide rail mounting system; and
FIG. 7 is a schematic side elevational view of the well-cleaning system provided with the pressurised water supply system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , the well-cleaning system 10 is generally of the type disclosed in AU-B-39856193 (655111) (McCasker), where a rotary spraying device 11 is rotatably mounted on a mounting arm 12 , and has a pair of radial spray arms 13 . Each spray arm 13 has a spray head 14 with an adjustable spray nozzle 15 . The well-cleaning system 10 is mounted in a sewage-holding well 20 above the sewage pump 21 (and above the highest level 22 of waste liquid in the well 20 ).
A cleaning water line 16 connects the rotary spray device 11 to a cleaning water control valve 17 (eg., a solenoid valve), which is connected to a reticulated mains water supply 18 via a reduced pressure zone (RPZ) valve 19 , which prevents backflow of the water from the well-cleaning system 10 to the mains water supply 18 should the pressure in the latter fall.
The control system 30 has a housing 31 with a display/operation panel 32 .
A computerised master control unit 33 in the housing 31 is connected to a cleaning valve control unit 34 which is operably connected to the cleaning water control valve 17 .
First and second waste liquid sensors 35 , 36 are provided in the well 20 at vertically-spaced locations to monitor when the waste liquid has been pumped out of the well 20 by the pump 21 , and when the waste liquid has reached the highest permitted level 22 , respectively.
A hydrogen sulphide (H 2 S) gas sensor 37 and a well condition sensor 38 are also provided in the well 20 and are connected to the computerised control unit 33 .
The computerised control unit 33 is also connected to the pump 21 .
A washing frequency timer 39 and a washing duration timer 40 are connected to the computerised control unit 33 .
When the second waste liquid sensor 36 detects that the waste liquid has reached the highest permitted level ( 22 ), the computerised control unit 33 switches on the pump 21 to pump out the waste liquid. When the waste liquid level falls to the first liquid level sensor 35 , the computerised control unit switches off the pump 21 . The control unit 33 operates the cleaning valve control unit 34 to cause the cleaning water control valve 17 to open to allow cleaning water from the mains supply 18 to flow to the well-cleaning system 10 , where the nozzles 15 on the rotary spray device 11 spray the wall 24 of the well 20 to wash any residues from the wall 24 . (The control unit 33 can be programmed to allow the pump 21 to also run while the washing is being effected.)
The duration timer 40 controls the period (eg., 3 minutes) during which the cleaning water is sprayed onto the wall 24 of the well 20 .
When the cleaning has been completed, the frequency timer 39 determines the time delay (eg., 3 hours) before the cleaning step may be repeated, even if the pump 21 has been operated to pump out the well 20 a number of times in the intervening period.
Trials have shown that a program of 8 wash cycles in every 24 hours (ie., at 3-hourly intervals), with a cleaning duration time of 3 minutes each, will keep most wells 20 clean. This gives an aggregate of 24 minutes washing per day.
With the existing well-cleaning system of the prior art, where cleaning occurs whenever the pump is operating, there may be, eg., 200 minutes' wash time per day, where the pump does 40 starts per 24 hours with a pump-out time of 5 minutes per start.
By using the control system 30 of the present invention, the cleaning water saving is 88% in the above examples.
When the well-condition sensor 38 detects a build-up of odours and/or corrosive gases, the computerised control unit 33 opens an additive injection valve 50 which enables a deodorant “mask” and/or chemical and/or biological additives to be injected into the cleaning water line 16 from an additive supply tank 51 .
When the H 2 S gas sensor 37 senses a build-up of H 2 S gas in the well 20 , it causes the computerised control unit 33 to operate the well-cleaning system 10 so that the cleaning liquid sprayed in the well 20 will reduce the H 2 S gas concentration therein.
The control system 30 can send information regarding the conditions in the well 20 to a remote manned control centre 60 via a radio (or microwave) link 61 or via a landline 62 . Alternatively, the manned control centre 60 can send instructions to the control system 30 for the operation of the well-cleaning system 10 . For example, the manned control centre 60 could send instructions reprogramming the settings of the frequency timer 39 and/or duration timer 40 .
Referring to FIG. 2 , the well-cleaning system 10 is designed for non-man-entry retrieval from the well 20 , where the mounting arm 12 is mounted for movement along the pump guide rail(s) 25 fixed to the wall 24 of the well 20 . A chain 26 enables the mounting arm 12 to be raised or lowered along the guide rails ( 25 ).
Referring to FIGS. 3 and 4 , the mounting arm 12 has a carriage 70 (of substantially C-shape) slidably mounted on the single pump guide rail 25 and is raised or lowered by a cable or rope 26 a (in substitution for the chain 26 ). In the alternative embodiment in FIGS. 5 and 6 , the mounting arm 12 has a carriage 70 a (of substantially I- or H-shape) slidably mounted on the parallel, spaced, pump guide rails 25 a , 25 b.
As the pump guide rails 25 , 25 a , 25 b are standard installations in the wells 20 (to enable installation/removal of the pumps 21 without man-entry to the well 20 ), the well-cleaning system 10 can be installed without man-entry to the well 20 .
Referring now to FIG. 7 , an alternative pressurised water supply system 80 for the well-cleaning system 10 has a cleaning liquid reservoir 81 separated from the end of a water supply line 80 a by an air gap 82 . A submersible pump 83 in the reservoir 81 supplies pressurised cleaning water to the well-cleaning system 10 on instructions from the computerised control unit 33 (eg., via the cleaning valve control unit 34 ). While the pump 83 is operating, a solenoid valve 84 in the water supply line 80 a is opened to replenish the reservoir 81 .
It will be readily apparent to the skilled addressee that the present invention can enhance the operation of the known well-cleaning system of AU-B-39856/93 in the following areas:
(a) reduced water consumption;
(b) effective control of odours, corrosive gas and/or H 2 S gas concentration; and
(c) installation, maintenance, repair and/or replacement of the well-cleaning system without man-entry to the well.
Various changes and modifications may be made to the embodiments described and illustrated without departing from the present invention.
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A well-cleaning system ( 10 ) is provided with a control system ( 30 ) where waste liquid level sensors ( 35, 36 ) co-operate with timers ( 39, 40 ) to control the frequency and duration of the well-cleaning cycles. Chemicals can be injected into the water on demand from a well-conditioning sensor ( 38 ); and the well-cleaning system ( 10 ) can be operated when high H 2 S gas levels are detected in the well ( 20 ) by a H 2 S gas sensor ( 37 ).
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BACKGROUND
The present invention relates to writing instruments, and in particular to writing instruments utilizing colored inks, pigments, and/or dyes in a suspended fluidic state.
When dealing with writing fluids such as inks, paints, dyes, and/or pigments, subtractive color theory applies, as opposed to additive color theory where a light source passes through colored filters. Subtractive color theory is that of mixing inks, paints, dyes and/or other natural pigments to make colors that absorb and reflect particular wavelengths of light. For example, for printing, cyan, magenta, and yellow are primary colors. Black may be added for various reasons in a four color process, most importantly because cyan, magenta, and yellow do not produce “pure” black but more of a dark gray.
Subtractive color theory is based on what light is absorbed. The amount of any color showing will depend on the amount of each of the three primary colors is in a color mixture. Cyan is the opposite of red. Magenta is the opposite of green. Yellow is the opposite of blue. The amount of blue in the final color mixture is directly related to the amount of yellow ink that is in the color mixture. The same is the case for other primary colors. For example, orange is a common color that is generally equal amounts of red and yellow. Adding more yellow will create a lighter orange. Adding more red will create a red orange. Green color is a combination of cyan and yellow.
The subtractive color theory starts with the presence of all colors of light, usually as white light reflected from a white surface, such as paper. Dyes or inks may be used to subtract some of the reflected light. Understanding subtractive color theory requires an understanding of how colors of light are subtracted. If yellow dye or ink is applied on a white sheet of paper, one may think that color is added to the paper, but the color is already there; the white paper reflects all colors of light approximately equally. The yellow ink, however, reflects only red and green light and absorbs blue light, thereby subtracting it from the white light. Any color of ink, dye or paint subtracts its complementary color of light. Cyan ink on white paper absorbs red light, and allows green and blue to be reflected. Magenta ink subtracts green light, and allows red and blue to reflect. Yellow ink absorbs blue light, allowing red and green to reflect. Cyan, magenta and yellow are the subtractive primary colors, and combined in pairs, they produce the colors red, green and blue. When all three primary colors are subtractively combined, they subtract all colors of light, leaving black, typically a dark gray is the practical result.
When two primary colors are overlaid, they each subtract one color, allowing only the third color to be reflected. For example, if magenta and yellow ink are mixed or applied on white paper, the magenta ink absorbs green light. The yellow ink subtracts blue light. Neither of them absorbs red light, so red light is reflected by white paper, and a viewer sees the color red. In a sense, the colors experienced in a subtractive color mixture are created in the same way they're created with an additive mixture. A combination of red and green light (where the red and green colors each contain light from one-third of the spectrum) will always produce a yellow-colored light (containing light from two-thirds of the spectrum). It doesn't matter whether one starts with white light and subtracts one-third of the spectrum, or starts with no light (black) and adds two thirds of the spectrum. Similarly, green and blue light always combine to produce cyan-colored light, and red and blue light always combine to produce magenta-colored light. Complementary colors work in similar ways for both additive and subtractive mixtures. In additive mixtures for example, yellow and blue light combine to complete the spectrum, producing white light. In subtractive mixtures, however, yellow and blue produce black (yellow and cyan produce green). Yellow ink subtracts one-third of the spectral light, blue ink subtracts the other two-thirds of the light, resulting in a black color. As previously noted, black is difficult to achieve in the subtractive process, and for that reason a four color process may be desired in some situations in order to achieve a true black color.
In summary, the subtractive color system involves colorants and reflected light. Subtractive color starts with an object (often a substrate such as paper or canvas) that reflects light and uses colorants (such as inks, pigments or dyes) to subtract portions of the white light illuminating an object to produce other colors. If an object reflects all the white light back to the viewer, it appears white. If an object absorbs (subtracts) all the light illuminating it, no light is reflected back to the viewer and it appears black.
SUMMARY
A writing instrument may include an elongated body housing a spool valve, fluid reservoirs, and a writing tip secured to the elongated body in selective fluid communication with the fluid reservoirs. The spool valve may be axially moveable relative to the elongated body of the writing instrument.
In one instance an object of writing instrument described herein is to provide a low cost variable color writing instrument capable of full spectrum color.
In another instance an object of the writing instrument described herein is to maximize the words, characters and the like written with the writing instrument before refilling the writing fluid in the fluid reservoirs, and whereby, for example, a user may write in excess of 100 times more words, characters and the like with a given amount of writing fluid, as compared to existing writing instruments.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features, advantages and objects of the present invention are attained can be understood in detail, a more particular description of the invention briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
It is 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.
FIG. 1 is a perspective view of a writing instrument;
FIG. 2 is an exploded perspective view of the writing instrument shown in FIG. 1 ;
FIGS. 3A-3C are perspective views of the spool valve of the writing instrument shown in FIG. 1 ;
FIG. 4 is a section view of the elongated body of the writing instrument shown in FIG. 1 ;
FIG. 5 is a side view of the spool valve of the writing instrument shown in FIG. 1 with hidden lines shown in phantom;
FIG. 6 is a top view of the writing instrument shown in FIG. 1 with hidden lines shown in phantom;
FIGS. 7A-7D are perspective views of the writing instrument shown in FIG. 1 depicting various axial positions of the spool valve relative to the elongated body of the writing instrument;
FIG. 8 is perspective view of a second embodiment of a writing instrument;
FIG. 9 is a side view of spool valve of the writing instrument shown in FIG. 8 depicting a flexible wall of a fluid reservoir pressed against a rigid member mounted on the spool valve;
FIG. 10 is a perspective view of a third embodiment of a writing instrument;
FIG. 11 is a side view of the writing instrument shown in FIG. 10 with hidden lines shown in phantom;
FIG. 12 is a perspective of the elongated body of the writing instrument shown in FIG. 10 with hidden lines shown in phantom;
FIG. 13 is a top plan view of the body of the writing instrument shown in FIG. 12 ;
FIG. 14 is a perspective view of the spool valve of the writing instrument shown in FIG. 9 with hidden lines shown in phantom; and
FIG. 15 is a top plan view of the spool valve shown in FIG. 14 .
DETAILED DESCRIPTION
As used herein the term “fluid” means inks, paints, dyes, pigments, water, alcohol, mixing solutions, surfactants and other flowable fluids suitable for marking on a substrate material, such as paper and the like.
Referring first to FIG. 1 , a writing instrument is generally identified by the reference numeral 100 . For purposes of illustration, but not by way of limitation, the writing instrument 100 is depicted in the drawings as a “fountain pen” and will hereinafter be referred to as a “pen.”
The pen 100 may include a pen barrel 112 , a spool valve 114 , a cap 116 and a writing tip or nib 118 . The spool valve 114 , shown in the exploded view of FIG. 2 , may include an elongated stem 120 , a head 122 and a threaded distal end 126 . The head 122 may include a griping portion 124 , for example a thumb grip. The stem 120 extends downwardly from a lower transverse wall 128 of the head 122 . The stem 120 may be integrally formed with the head 122 or fixedly secured to the head 122 by means known in the art. A lower portion of the stem 120 may include lands 130 and circumferential grooves 132 axially spaced along the lower portion of the stem 120 . O-rings 135 may be concentrically and axially constrained in the grooves 132 . The stem 120 terminates at a lower distal end defined by a transverse wall 133 .
The head 122 of the spool valve 114 may include two or more fluid reservoirs. The pen 100 shown in FIGS. 3A-3C depicts three reservoirs 134 , 136 and 138 , for illustrative purposes only and not by way of limitation. The reservoirs 134 , 136 , 138 are separated by walls 140 and extend from the distal end 126 of the spool valve 114 downward into the head 122 , terminating at a transverse wall 142 depicted in phantom in FIG. 5 .
The reservoirs 134 , 136 , 138 may be sealed by the cap 116 threadedly secured on the distal end 126 of the spool valve 114 . A flexible washer 141 and a rigid washer 142 in the cap 116 ensure an air and liquid tight seal for the reservoirs 134 , 136 , 138 .
Referring now to FIG. 4 , the barrel 112 of the pen 100 may, for illustrative purposes, but not by limitation, include an elongated substantially cylindrical body 150 . The upper end portion of the body 150 includes a box end or receptacle 152 sized and configured to receive the head 122 of the spool valve 114 . A borehole 154 concentric with the vertical axis of the body 150 extends axially downward from the receptacle 152 to a transverse bottom wall 156 . The upper end of the borehole 154 opens to the interior of the receptacle 152 . The borehole 154 is sized and configured to receive the stem 120 of the spool valve 114 . Upon assembly of the barrel 112 with the spool valve 114 , the o-rings 135 seal against the inner surface of the borehole 154 isolating the lands 130 from one another.
The pen barrel 112 may include a conduit 158 establishing a fluid pathway between the borehole 154 and a mixing chamber 160 proximate the lower distal end of the barrel 112 . An axial passage 119 may extend from the mixing chamber 160 to the distal end 121 of the pen barrel 112 . The passage 119 is configured to receive the connector end 123 of the nib 118 . The nib 118 may be screwed or press fit into the passage 119 thereby securing the nib 118 to the lower distal end of the pen barrel 112 . The upper end of the passage 119 is open to the mixing chamber 160 , thereby establishing fluid communication between the mixing chamber 160 and the nib 118 .
Referring now to FIG. 5 , the spool valve 114 may include one or more conduits for establishing fluid communication between the reservoirs 134 , 136 , 138 and the nib 118 . In FIG. 5 , conduits 162 , 164 and 166 are shown offset from the central vertical axis of the stem 120 and extend substantially parallel to the central axis of the stem 120 . The conduits 162 , 164 , 166 terminate at radially and outwardly directed openings 172 , 174 , 176 in the lands 130 . Clearance between the lands 130 and the borehole 154 is sufficient for fluid to flow therebetween. However, it is understood that other configurations, such as a concentric groove, may be provided about the lands 130 to allow circumferential fluid flow (ink or solvent and the like) about the lands 130 .
The pen 100 may be assembled by inserting the stem 120 into the borehole 154 of the barrel 112 . The head 122 may include a helical groove 180 in the outer surface thereof sized to receive a boss 182 projecting inwardly proximate the open distal end of the receptacle 152 . The boss 182 is constrained to move along the helical groove 180 upon rotation of the spool valve 114 relative to the barrel 112 . Rotation moves the spool valve 114 axially relative to the barrel 112 . The thumb grip 124 provides a convenient surface for grasping and rotating the spool valve 114 clock-wise or counter clock-wise to advance or retract the spool valve 114 from the pen barrel 112 . For the configuration of the pen 100 illustrated in FIGS. 1-7 , clock-wise rotation moves the spool valve 114 axially downward relative the barrel 112 . Counter clock-wise rotation moves the spool valve 114 axially upward relative the barrel 112 . It should be noted that the barrel 112 may likewise be rotated by holding the spool valve 114 and rotating the barrel 112 to move it axially relative to the spool valve 114 .
Referring still to FIG. 5 , the spool valve 114 may include a vent duct 184 having a lower distal opening 186 . The vent duct 184 may be concentric with the central vertical axis of the spool valve 114 . The vent duct 184 may extend axially through the spool valve 114 from the opening 186 at the lower distal end of the stem 120 and vent to the atmosphere through radially outwardly directed air vents 188 in the spool valve head 122 , shown in FIG. 6 . The vent duct 184 generally functions as a relief valve to release air that may be compressed in the barrel borehole 154 as the stem 120 advances downward in the borehole 154 . Venting air out of the borehole 154 may avoid air pressure fluctuations that may interfere with fluid flow from the reservoirs 134 , 136 138 into the conduit 158 .
Fluid may be distributed to the pen nib 118 upon alignment of the upper open end 159 of the conduit 158 with openings 172 , 174 , 176 in the stem 120 . As previously noted, rotation of the spool valve 114 moves the stem 120 axially relative to the barrel borehole 124 . FIGS. 7A-7D illustrate the location of the stem 120 relative to the upper open end 159 of the conduit 158 for distributing fluid from the reservoirs 134 , 136 , 138 to the pen nib 118 .
FIG. 7A depicts the pen 100 in the “off” or non-writing mode. In this mode, the spool valve 114 is depicted as being retracted from the pen barrel 112 to a position so that the lowermost land 130 blocks the opening 159 of the conduit 158 . The lowermost land 130 is not in fluid communication with any reservoir and therefore no fluid is distributed to the pen nib 118 .
FIGS. 7B-7D depict the pen stem 120 positioned so that the opening 159 of the conduit 158 aligns with the openings 176 , 174 , 172 in the lands 130 , thereby establishing fluid communication between a respective reservoir 134 , 136 , 138 and the pen nib 118 . A user may actuate the spool valve 114 , as desired to distribute a writing fluid from the fluid reservoirs 134 , 136 , 134 to the mixing chamber 160 of the pen barrel 112 . The user may change the color, shade and hue of the writing fluid applied to the writing surface in an infinite combination of colors and duration of fluids distributed to the mixing chamber 160 from the fluid reservoirs 134 , 136 , 138 .
The writing instrument, as noted above, depicted in the drawings is a fountain type pen for illustrative purposes only. It is understood that the writing instrument described herein may include, but is not limited to, ball point pens with viscous ink (considered paste), pens with generally decreasing ink viscosity ranging from tempura pens, gel pens, roller ball pens, brush tip pens, fountain pens, stylus pens, and/or felt tip pens, of both water or alcohol base and the like.
The pen 100 may be suitable for a wide range of uses such as a simple novelty item to being able to continuously and smoothly cause a transition of colors while creating a drawing, sketch and the like, and where no two sketches or drawings are identical, even with identical pen motions, because of the somewhat turbulent flow and the complex nature of the physics of a flowing fluid. Viscosity alone is a complex and somewhat chaotic factor to consider, as well as the dynamics of the spool valve or other valves, such as disk valves or pinch valves.
The subtractive color system, described in greater detail hereinabove, applies to the pen 100 . The full color spectrum may be possible with the ink colors magenta, yellow, and cyan. Generally, pen 100 may be considered a “color shifting pen” utilizing three reservoirs (or three cartridge) of compatible or mixable inks. Color shifting pens may be controlled with the spool valve described hereinabove. The pen 100 may be used for various purposes, such as, notarizing documents or dealing with legal matters, or even writing a diary. The chronological order of the written words, characters and the like may be determined by the ink color. If insertions occur out of sequence, the color of such insertions provides an indication as to the general time period, based upon the ink color, that such insertions were made. In this respect, the use of color may greatly assist in the prevention of fraud and forgeries. Note that it would be very difficult to re-blend the identical ink color. Forensic document examination may also be greatly facilitated. The reader will note that the chronological order is not actually a function of time, but rather a function of the number of words, characters and the like the pen has written. Furthermore, in addition to ink, fluorescent dyes which fluoresce under ultraviolet light may be introduced into one or more of the reservoirs, for example, in order to introduce unique graduations which would only be visible under UV light.
Continuing again with ink mixtures, the ink colors throughout a sketch, drawing or writing are a smooth transition of many colors, hues, and shades. A user may create the sketch or drawing while controlling and anticipating the colors being mixed and/or blended and delivered to the writing tip. For example, while shades of yellow are being delivered to the writing tip, the sun or yellow objects may be sketched, and as the user introduces green blended ink, then plants and/or green objects may be sketched. Furthermore, during color mixing, and particularly when utilizing fountain pens, it should be noted that the quantity of ink colors available in the market is high, and the user may elect to deviate from the three subtractive primary colors discussed above and select non-primary colors which, for example, may result in mixtures of pastel colors. Alternatively, scarlet, purple and/or green ink may be included in at least one of the reservoirs to emphasize a particular mixable range of colors. Also, for steady delivery of a mixed color or shade, positioning the spool valve to a predetermined intermediate position between two fluid reservoirs, both in the “on” mode in some portion (throttling), steady state mixing action may occur while writing.
All colors are possible with the three reservoir configuration of the pen 100 where the primary subtractive colors are provided. With regard to secondary colors, if the primary subtractive colors of yellow, cyan, and magenta are provided, then a secondary color such as red, green or blue may be mixed and delivered to the pen mixing chamber, and once such a color is in the mixing chamber, a new primary color may be introduced resulting in colors such as violet, rose, orange, chartreuse green, spring green, and azure to be mixed within the pen mixing chamber and thereafter delivered to the writing tip. Further variations when combining tertiary and secondary colors, or tertiary and tertiary colors, or any combination of the above colors are also possible, thus enabling a remarkably wide variation of the number of colors, shades and hues which may be gradually mixed within the pen mixing chamber during the act of writing.
Directing attention now to FIGS. 8 and 9 , a second embodiment of a spool valve pen is generally identified by the reference numeral 200 . As evidenced by the use of common reference numerals, the pen 200 is similar to the pen 100 described above with the exception that the pen 200 may include a dual reservoir system where one or the other of the two reservoirs is always in the “on” or open mode. That is, a fluid reservoir is always in fluid communication with the pen nib 118 . The pen 200 does not include an “off” mode.
In FIG. 8 , the water reservoir 285 of the pen 200 is set to the “on” mode and the ink reservoir 275 is in the “off” mode. A spool valve 214 is received in the pen barrel 220 in the same manner as the spool valve 114 is received in the pen 100 . The ink reservoir 275 is relatively small compared to the relatively large water reservoir 285 . The ink reservoir 275 and water reservoir 285 are mounted on the spool valve 214 on opposite sides of a rigid stanchion wall 280 . Both reservoirs 275 , 285 may be fabricated of flexible material that facilitates quick and convenient refilling of the reservoirs 275 , 285 . The reservoirs 275 , 285 may be refilled by pressing the flexible side of either reservoir 275 , 285 against the rigid stanchion wall 280 , as illustrated in FIG. 9 , much like squeezing the bulb of an eye dropper, and thereby expelling any air in the reservoir. The nib 118 may then be submerged into water or ink and the like. Release of the pressure on the side of the reservoirs draws the fluid into the reservoirs. Prior to refilling a reservoir of the pen 200 , a small amount of diluted writing mixture may be retained in the pen mixing chamber 160 to facilitate efficient refilling of the reservoir. The pen 200 may include additional ink reservoirs as desired, all generally being flexible reservoirs that lend themselves to the vacuum filling method described above.
The pen 200 is typically used with the water reservoir 285 in the “on” position operating as a “dilution pen” or in the “dilution” mode. The pen 200 may be operated with alcohol based inks, in which case the smaller reservoir 275 may contain alcohol ink, and the larger reservoir 285 may contain alcohol and/or a mixing solution. Additional reservoirs may be included as desired, for example, water, alcohol, and a mixing solution in separate reservoirs. Cartridges or converters known in the art may be substituted for the flexible reservoirs if desired. The selection of proper O-rings for water or alcohol use is understood, and silicon O-rings may generally suffice. An unillustrated cap or sleeve may be provided to cover the reservoirs 275 , 285 . Rotation of the spool valve 214 counter clockwise relative to the pen barrel 220 , engages the boss 221 with helical groove 238 , thereby causing the spool valve 214 to be raised and the ink reservoir 275 moved to the “on” position.
With regard to ink dilution, a user may change a color shade, or economize ink consumption. The darkness of 100× diluted ink may in many cases be as dark as lead pencil on paper, and easily reproducible with computer copiers and scanners and the like. When economizing the use of ink, and having once filled the ink reservoir 275 of the pen 200 with standard dark (nearly saturated) fountain pen ink, the user may write a hundred times more words, characters and the like with the dilution pen 200 than with use of ink alone. Ink cost savings would be notable, and the pen 200 would also be more environmentally friendly than any other pen available on the market currently.
By some estimates, when writing with a prior art medium point fountain pen with 1 cc (one cc=one ml) typical ink capacity, for example, a user may expect to write 5-15 pages of sketches or words per one cc of ink alone. With one cc of standard dark fountain pen ink in the ink reservoir 275 of the pen 200 , and considering a 100 x factor of dilution, the user may expect to write 500 to 1500 pages of sketches or written words with the dilution pen 200 , which is a remarkable extension of writing. An entire book may be written without refilling the ink reservoir 275 . It may also be noted that an additional advantage to diluting ink is that diluted ink dries significantly faster than a nearly saturated ink.
For further refinement of the use of a fountain pen, a user may introduce surfactants and lubricants, in powder or liquid form, to one or more pen reservoirs, at any time while using the pen. Generally, when economizing ink by providing a pen with a water reservoir, use of water soluble inks is recommended. Fountain pen inks are typically an aqueous solution and generally 92+% water, adding water is inherently compatible. If notable diminished flow or lubrication properties are evident, a drop of clear dish detergent in the water reservoir may solve flow problems and a drop of pure vegetable glycerin may solve lubrication problems. Kodak PhotoFlo may also be used as a surfactant to aid ink/water flow. TritonX-100 may be another suitable surfactant. The Triton pure chemical is concentrated and should be diluted to create a working solution, where a “working solution” of Triton X-100 may be prepared at a 1:200 dilution, and a drop of the working solution is sufficient for one fountain pen water reservoir. Use of too much surfactant may inhibit the ink/water flow. In a fountain pen, the writing fluid should optimally spread along the underside of the nib and fill in the combs in the collector. Too much surfactant and the ink solution may drip out of the nib. Use of distilled water may result in optimum results.
For use of tempera inks, where the ink viscosity is relatively thick (like honey), the spool valve may be proportionally greater in size, and have larger ink passageways and/or orifices and/or clearances. When using alcohol based inks, note that one of the pen reservoirs may be filled only with alcohol, or filled only with a “mixing solution”, and the other reservoirs may be filled with alcohol based inks. Ethanol (Ethyl alcohol) is a preferred alcohol ink base.
Directing attention now to FIGS. 10-15 , a third embodiment of a spool pen generally identified by the reference numeral 300 is shown. The pen 300 is similar to the pens 100 and 200 described above with the exception that the pen 300 includes reservoirs 331 , 332 , 333 , shown in FIG. 13 , and reservoir passageways 361 , 362 , 363 , shown in FIG. 12 , integrally formed with the pen barrel 320 . The pen 300 may include seven O-rings 325 on the stem 365 , best shown in FIGS. 11 and 13 . O-rings 325 are concentrically constrained within recesses 370 of the stem 365 . The lower distal ends of the passageways 361 , 362 , 363 are redirected radially inward at openings 352 , 353 , 354 , respectively. An axial center passageway 377 concentric with the longitudinal axis of the stem 365 provides a conduit for the distribution of fluid, such as ink or solvent and the like, to the fluid mixing chamber 360 , shown in phantom lines in the drawings, upon alignment of the stem inlet openings 380 with the passageways 361 , 362 , 363 . Boss 321 is constrained to move along helical groove 338 thereby causing the pen barrel 320 to move axially relative to the spool valve 330 as one rotates relative to the other. Reservoirs 331 , 332 , 333 are isolated from each other by walls 340 . An agitator such as a small metal ball may be included within each reservoir to maintain ink suspension. The blind end of the stem 365 may be vented in a similar manner as described hereinabove with reference to pens 100 , 200 .
The nib 318 may be screwed or press fit into a borehole 319 at the lower distal end of the spool valve 330 . The upper end of the borehole 319 is open to the mixing chamber 360 , shown in phantom lines in the drawings, thereby establishing fluid communication between the mixing chamber 360 and the nib 318 .
While various embodiments of the invention have been shown and described herein, 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 which follow.
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A writing instrument includes an elongated body housing a spool valve and a writing tip secured to a distal end of the elongated body. Two or more fluid reservoirs in selective fluid communication with the writing tip. Axial movement of the spool valve relative to the elongated body of the writing instrument alternately establishes fluid flow paths between the fluid reservoirs and the writing tip.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to European Patent Application No. 05425550.0 filed Jul. 27, 2005.
FIELD OF THE INVENTION
[0002] The present invention relates to an improved valve assembly, in particular for use in household coffee machine water circulation conduits.
BACKGROUND OF THE INVENTION
[0003] Valve assemblies are known, as described for example in Patent WOO2088580, which comprise a casing defining a fluid flow cavity; and a valve housed inside the casing to separate a first and a second environment of the flow cavity hermetically when the pressure in the first environment exceeds the pressure in the second environment by an amount above a predetermined threshold value.
[0004] More specifically, the valve substantially comprises a disk-shaped base member having an opening to permit fluid flow between the first and the second environment separated by the base member; and an elastically deformable ring cooperating with the base member to fix the base member hermetically inside the cavity. The valve also comprises a flexible shutter having, on the side facing the first environment, a membrane portion which, by virtue of fluid pressure, cooperates elastically with the opening to separate the first and second environment hermetically.
[0005] As stated, valve assemblies of the above type permit fluid flow between the first and second environment when the difference in pressure between the first and second environments is less than or equal to the predetermined threshold value.
[0006] To this end, the base member also comprises, on the side facing the first environment, a recess communicating with the opening and selectively engageable by the membrane portion to permit fluid flow through the base member for pressure difference threshold values depending on the geometry of the recess.
[0007] Though efficient and reliable, valves of the above type still leave room for improvement. In particular, a need is felt to reduce the number of component parts, so as to reduce the number of moving parts and simplify component machining and assembly.
SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to provide a valve assembly designed to satisfy the aforementioned need in a straightforward, low-cost manner.
[0009] According to the present invention, there is provided a valve assembly as claimed in the attached Claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] A preferred, non-limiting embodiment of the present invention will be described by way of example with reference to the accompanying drawings, in which:
[0011] FIG. 1 shows an axial section of a valve assembly in accordance with the present invention and in the closed position;
[0012] FIG. 2 shows a section along line II-II in FIG. 1 ;
[0013] FIG. 3 shows an axial section of a further embodiment of the FIG. 1 valve assembly in the closed position;
[0014] FIG. 4 shows a section along IV-IV in FIG. 3 ;
[0015] FIG. 5 shows a top plan view of a detail in FIG. 1 ;
[0016] FIG. 6 shows a side view of the FIG. 5 detail.
DETAILED DESCRIPTION OF THE INVENTION
[0017] With reference to FIGS. 1 and 2 , number 1 indicates as a whole a valve assembly in accordance with the present invention, and particularly suitable for use in household coffee machine water circulation conduits.
[0018] Valve assembly 1 comprises a casing 2 defining a fluid flow cavity 3 ; and a valve 4 housed hermetically inside cavity 3 to control flow between two separate environments 5 , 6 of cavity 3 separated by valve 4 .
[0019] More specifically, casing 2 has an axis A, and comprises a body 7 and a body 8 , which extend axially on opposite sides towards environments 5 and 6 respectively.
[0020] Body 7 comprises an axial fluid conduit 9 ; and an axial end portion 10 larger radially than conduit 9 and connected to conduit 9 by a radial wall 11 .
[0021] Similarly, body 8 comprises an axial fluid conduit 12 extending on the opposite side to conduit 9 ; and an axial end portion 13 , which is larger radially than conduit 12 , is fixed to portion 10 of body 7 in a manner not shown, and is connected to conduit 12 by a radial wall 14 .
[0022] Valve 4 , shown in more detail in FIGS. 5 and 6 , is housed coaxially inside casing 2 , and comprises a portion 15 which cooperates hermetically with portion 10 of body 7 and permits fluid flow between environments 5 and 6 .
[0023] More specifically, at its radially outer end, portion 15 comprises a toroidal portion 18 cooperating radially and hermetically with portion 10 ; and an annular portion 16 no larger axially than portion 18 , and connected at its radial ends to portion 18 .
[0024] At the join between portion 16 and portion 18 , portion 15 also comprises a number of—in the example shown, four—axially through openings 23 permitting passage between environments 5 and 6 .
[0025] More specifically, openings 23 are equally spaced angularly about axis A, and each comprise a contour defined by two radially opposite circumferential portions 31 connected by two angularly opposite radial portions 32 .
[0026] Portion 15 is bounded axially towards environments 5 and 6 by respective end surfaces 20 and 21 . More specifically, end surface 21 cooperates with a number of—in the example shown, three—appendixes 22 equally spaced angularly and projecting axially from wall 14 towards valve 4 to hold valve 4 in position axially.
[0027] Valve 4 also comprises a portion 19 varying in configuration to permit/prevent communication between environments 5 and 6 .
[0028] Portion 19 advantageously also cooperates hermetically with casing 2 , on the side facing environment 5 , to prevent environments 5 and 6 from communicating fluidically through openings 23 .
[0029] More specifically, at portion 16 , portion 19 extends from portion 15 towards environment 5 to define, with body 7 , a cavity 30 which is cut off fluidically from openings 23 when the pressure in environment 6 exceeds the pressure in environment 5 by an amount above a predetermined threshold value P. Conversely, cavity 30 is connected fluidically to openings 23 , to permit fluid flow through openings 23 , when the pressure in environment 6 exceeds the pressure in environment 5 by an amount below predetermined threshold value P.
[0030] More specifically, portion 19 comprises a radially outer, truncated-cone-shaped profile 24 connected to portion 16 on the opposite side to environment 5 ; a radially inner, concave profile 25 ; and a circular axial end 26 cooperating hermetically with wall 11 of body 7 .
[0031] More specifically, profile 24 diverges towards environment 5 , and, together with profile 25 , defines end 26 on the environment 5 side.
[0032] Profile 25 comprises a curved portion 27 at portion 16 ; and a truncated-cone-shaped portion 28 interposed axially between portion 27 and end 26 , and diverging towards environment 5 .
[0033] More specifically, profiles 24 and 25 are shaped so that portion 19 has an axial section tapering from portion 15 to end 26 .
[0034] Cavity 30 is therefore bounded by profile 25 of portion 19 and by wall 11 , and is open at conduit 9 .
[0035] Portions 19 and 15 are defined integrally by one body and made of flexible material. More specifically, portions 19 and 15 are preferably made of an organic polymer compatible with use in contact with food products, e.g. silicone.
[0036] In actual use, when the pressure in environment 6 exceeds the pressure in environment 5 by an amount above threshold value P, end 26 adheres to wall 11 of body 7 , so that cavity 30 is cut off fluidically from openings 23 to separate environments 5 and 6 in fluidtight manner.
[0037] Conversely, when the difference in pressure between environments 6 and 5 is less than or equal to threshold value P, the fluid in cavity 30 detaches end 26 from wall 11 , so that cavity 30 is connected fluidically to openings 23 to allow fluid flow between environments 6 and 5 ; which characteristic may be used to prevent fluid stagnating in environment 5 when the pressure in environment 5 falls as a result, for example, of a delivery pump connected to cavity 3 being turned off.
[0038] Threshold value P, corresponding to the maximum pressure difference value at which fluid flows both ways through cavity 3 , may obviously be varied by varying the shape of portion 19 .
[0039] With no change in the shape of portion 19 , threshold value P may obviously also be varied by varying the axial position of wall 11 with respect to end 26 .
[0040] More specifically, moving wall 11 axially away from end 26 reduces threshold value P, eventually to zero; in which latter case, valve assembly 1 permits flow from environment 6 to environment 5 for any pressure difference between environments 6 and 5 .
[0041] Conversely, moving wall 11 axially towards end 26 increases threshold value P.
[0042] The FIG. 3 embodiment shows a valve assembly 1 ′ similar to valve assembly 1 , and the component parts of which are indicated, where possible, using the same reference numbers as for the corresponding parts of valve assembly 1 .
[0043] Valve assembly 1 ′ differs from valve assembly 1 by wall 11 comprising a groove 35 , which imparts an undulated shape to wall 11 . Groove 35 cooperates with end 26 to separate environments 5 and 6 hermetically, when the pressure in environment 6 exceeds the pressure in environment 5 by an amount above threshold value P, and is disengaged by end 26 , to permit fluid flow, when the pressure difference between environments 6 and 5 is below threshold value P.
[0044] More specifically, groove 35 comprises a number of—in the example shown, three—contiguous lobes 36 equally spaced angularly and lying in a plane set back towards environment 5 with respect to wall 11 .
[0045] With particular reference to FIG. 3 , when the pressure in environment 6 exceeds the pressure in environment 5 by an amount above threshold value P, end 26 of portion 19 adheres to groove 35 , at each lobe 36 , so that cavity 30 is cut off fluidically from openings 23 to separate environments 5 and 6 in fluidtight manner.
[0046] Conversely, when the pressure difference between environments 6 and 5 is less than or equal to threshold value P, end 26 does not adhere to groove 35 , so that cavity 30 is connected fluidically to openings 23 to permit fluid flow between environments 6 and 5 .
[0047] Threshold value P therefore depends, not only on the shape of portion 19 and the axial position of wall 11 with respect to portion 19 , but also on the shape of groove 35 .
[0048] The advantages of valve assembly 1 , 1 ′ according to the present invention will be clear from the foregoing description.
[0049] In particular, valve assembly 1 , 1 ′ is formed in two parts, thus reducing the number of moving parts and relative machining and assembly costs.
[0050] Clearly, changes may be made to valve assemblies 1 , 1 ′ according to the present invention without, however, departing from the protective scope of the accompanying Claims.
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There is described a valve assembly having a casing defining a cavity for passage of a fluid; and a valve housed in the cavity; the valve has first sealing means cooperating with the casing to divide the cavity into a first and a second environment; at least one opening permitting flow of the fluid between the first and second environment; and second sealing means varying in configuration to permit/prevent communication between the first and second environment through the opening; and the second sealing means also cooperate with the casing, on the side facing the second environment, to prevent the first and second environment from communicating fluidically through the opening.
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REFERENCE TO PROVISIONAL APPLICATION
[0001] This application is a continuation of Provisional Application (Application Serial No. 60/418,428, filed Oct. 15, 2002, and applicant claim priority therefrom.
FIELD OF THE INVENTION
[0002] This invention relates to a walking or hiking stick or pole that can provide greater balance, support, thrust, and other aid, and in particular a hiking stick or pole configured to dispense particles such as birdseed, planting seed, fertilizer, insecticides, and the like.
PRIOR ART
[0003] Walking and hiking poles are well known in the art, frequently such apparatus include enhanced features such as telescoping shafts and adjustable handles, Also there has also been a variety of dispensers for bird seed and the like are well known.
BRIEF DESCRIPTION OF THE INVENTION
[0004] The invention is based on the recognition that a load dispensing system located at the distal end of a length of hollow tubing provides for a convenient location of a refill port and load activation control while providing for a walking support as well.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] [0005]FIG. 1 is a cross sectional view of the apparatus with the principles of this invention.
[0006] [0006]FIGS. 2 and 3 are enlarged cross sections of the apparatus as FIG. 1 showing the particle load section of the device.
[0007] [0007]FIG. 4 shows the dispenser in the particle retaining position.
[0008] [0008]FIG. 5 shows the dispenser in the particle dispensing position.
DETAILED DESCRIPTION OF THE INVENTION
[0009] [0009]FIG. 1 shows a load dispenser, shown upright and including a bottom or proximal and a top or distal end. A load dispenser is located at the proximal end and the distal end serves as a refill port as well becomes clear from the following explanation in connection with FIGS. 2, 3, 4 and 5 .
[0010] [0010]FIGS. 2 and 3 show a tubular shaft 1 , with a load funnel 2 having a particle 4 entry opening 5 , affixed onto the tubular shaft 1 . A removable cap 3 , is on top of the open wide neck of the load funnel 2 to seal funnel back-flow. With the cap 3 removed, and the internal area open 5 , particles 4 , may be loaded through opening 5 , into the hollow inner length of the tubular shaft 1 and load funnel 2 . An anti-slip handgrip 6 is affixed onto tubular shaft 1 .
[0011] [0011]FIGS. 4 and 5 show an adjustable, spring-loaded, particle dose dispenser comprised of an inner load body 8 , with the bottom 9 being closed. The center 10 of the load body 8 is open, as well as a slot-like opening (s) 11 , protruding through the inner wall 12 , and outer wall 13 . Affixed to the bottom of the closed end 9 , of the load body 8 , is a flow stop seal 14 that is larger in circumference than the bottom 9 of the load body 8 . The flow stop seal 14 has a slot like opening (s) 15 , which extends from the bottom edge 9 of the load body 8 to the outer edge 17 of the flow stop seal 14 . With the flow stop seal 14 is resting against the release body's flanged surface 16 particle 4 flow stops as shown in FIG. 3, and particles 4 can only be released when the particle dose dispenser is in the particles release position 4 . The upper end of the load body 8 has an annular flange 18 to seat the compression spring 19 . The release housing 20 has an inwardly protruding annular flange 21 to seat the compression spring 19 . The compression spring 19 rests between the outer wall 22 of the load body 8 and the inner wall 23 of the release housing 20 , a slip fit clearance allows the compression spring 19 to have movement. The mating surfaces 24 of the load body 7 , and the release housing 20 are slip fit. The load body 8 and the compression spring 19 are placed into the release housing 20 , and made captive by the affixing of the flow stop seal 14 to the bottom 9 of the load body 8 . The compression spring 19 maintains pressure, forcing the load body 8 in one direction and the outer release housing 20 in an opposing direction, stopping the release of particles 4 . Surfaces 26 , the inner wall of the release housing 20 and the outer wall of the tubular shaft 1 , are a slip fit to each other. The upper, outer wall of the load body 8 is affixed 7 to the inner bottom wall of the tubular shaft 1 . The release housing 20 has a circumflexing anti-slip cap 27 affixed to the periphery of the bottom outer wall of the release housing 20 , with the cap open to the extent of the bottom inner wall of the load body 8 . Spaced above the release housing 20 and affixed to the tubular shaft is inner ring 29 . The outer wall of the inner ring 29 is threaded 30 . The outer ring 31 has an internal thread matched to the thread 30 on the outer wall of the inner ring 29 . The outer ring 31 when screwed against the release housing 20 forces the release housing 20 away from the inner ring 29 , compressing the compression spring 19 , limiting the particle dose. At the bottom of the anti-slip cap 27 and detachably affixed 33 to the lower inner wall of the release housing 20 is a spiked button 32 , used as a walking or hiking balance aid. In addition the spiked button may be replaced with other accessory devices such as garden picking, turning, and planting devices. While the forms of apparatus herein described constitute the preferred embodiments of this invention, it is to be understood that the invention is not limited to these precise forms of apparatus, and that changes may be made without departing from the scope of the invention.
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A load dispenser located at the distal end of an elongated hollow tube allows for convenient refilling of the dispenser from the proximal end of the load release mechanism. The length of the tube is dimensioned to serve as a walking stick as well.
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BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates in general to equipment for recovering refrigerant, and in particular to equipment for recovering large quantities of refrigerant.
2. Description of the Prior Art:
In the past, large quantities of CFC refrigerants were vented to the atmosphere when the unit utilizing the refrigerants needed to be repaired or decommissioned. Subsequently, it was learned that the refrigerants lead to depletion of the ozone layer. Now it is prohibited to vent refrigerants to atmosphere.
Recovery units currently in use normally have a compressor, evaporator and a condenser. Vapor refrigerant is drawn into the compressor, which pressurizes the vapor and forwards it to the condenser. The vapor condenses into a liquid in the condenser, and from there it passes to the storage bottle. Liquid refrigerant withdrawn from the system passes through an expansion valve which drops the pressure, causing it to vaporize. The vaporized cold refrigerant passes through an evaporator which removes heat, and from there the vapor passes to the suction side of the compressor.
While these systems work well enough for small quantities of refrigerant removal, they normally will not handle very high flow rates. Consequently in large commercial air conditioning or refrigeration units, removing the refrigerant is very time consuming. The small units are not be able to accommodate the necessary heat exchange during the evaporating and condensing steps.
SUMMARY OF THE INVENTION
The apparatus of this invention is particularly useful for removing large quantities of refrigerant quickly. The apparatus includes a suction unit which may be wheeled or rolled into a building for positioning next to the refrigeration unit. The assembly also includes a truck-mounted unit remotely connected to the suction unit by hoses.
The suction unit has a suction compressor which draws vapor from the refrigerant system. The suction unit also has a liquid pump which will pump out liquid refrigerant. The suction compressor and liquid pump transmit the liquid and vapor refrigerant over lines to a bath of chilled liquid in the truck.
A condenser is immersed in the bath for condensing refrigerant vapor flowing from the suction compressor. A heat exchanger is also located in the bath in communication with the liquid pump for cooling the liquid refrigerant. The refrigerant passes from the glycol bath into a storage tank.
Also, a feedback line leads from the vapor port of the tank to a feedback compressor located in the truck unit. When the tank pressure is above a selected level, the feedback compressor withdraws vapor from the upper portion of the tank and applies it back to the condenser for further condensation. If the tank pressure is below the selected level, a valve directs part of the outlet of the suction compressor through a bypass line to the inlet of the feedback compressor. The compressors act in tandem when the tank pressure is below the selected level.
The system has a drawdown line and valves which will allow the feedback compressor to evacuate all of the lines and equipment from the recovery unit after the recovery has been completed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view illustrating a suction unit constructed in accordance with this invention.
FIG. 2 is a schematic view illustrating a truck-mounted unit for use with the suction unit of FIG. 1 and constructed in accordance with this invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIGS. 1, suction unit 11 will be mounted on a cart so that it can be rolled into a building for positioning next to a refrigeration unit. Suction unit 11 has a low pressure intake 13 and a high pressure intake 15. Intakes 13, 15 comprise connections that will connect into the refrigeration unit at points for receiving vapor and liquid refrigerant, respectively, contained in the refrigeration system. Valves 17, 19 will selectively open and close the lines leading from the low pressure intake 13 and high pressure intake 15. A filter or strainer 23 will filter the refrigerant vapor. The vapor is drawn in low pressure intake 13 by means of a suction compressor 25 connected downstream of filter 23.
A filter 27 connects to the high pressure intake 15. Liquid refrigerant flows through a valve 29 to a positive displacement liquid pump 31. Liquid will flow out a liquid conduit 33. Valve 29 can be switched to direct flow from high pressure port 15 to suction compressor 25 rather than liquid pump 31 when all of the liquid refrigerant has been withdrawn.
Compressor 25 has conventional pressure switches 35, 37 which are connected with compressor 25 for cutting off compressor 25 in the event of excessively high or low pressure. The vapor flows from the outlet of compressor 25 through an oil separator 38 for removing oil droplets contained in the refrigerant vapor. The vapor flows from oil separator 38 optionally through a precooler 39. Precooler 39 is similar in configuration to a serpentine condenser, although it does not normally condense any vapor. An electric fan 41 blows air through the coils of precooler 39 to assist in removing heat from the compressed refrigerant vapor. A valve 43 when closed forces all of the vapor through precooler 39. In the event of low ambient temperature, valve 43 may be opened, allowing vapor to bypass precooler 39. The refrigerant leaves precooler 39 as a warm vapor, flowing through a vapor conduit 45.
Conduits 33 and 45 are flexible hoses which lead to a truck mounted unit 47, illustrated in FIG. 2. Suction unit 11 will be located remote from truck mounted unit 47, possibly several hundred feet away and connected only by the conduits 33, 45.
Truck mounted unit 47 has a heat exchanger 49 connected to the liquid conduit 33. Heat exchanger 49 is a helical coil located within a bath 51 of chilled liquid, such as glycol. The liquid refrigerant in heat exchanger 49 will be cooled by the glycol in bath 51. A check valve 53 connects to the downstream side of heat exchanger 49, allowing refrigerant to flow out into a liquid line 55. The refrigerant flows through a normally open liquid valve 57 and into a liquid port 56 in a storage tank 59.
The vapor flowing through vapor conduit 45 passes through a check valve 61 and from there to a parallel flow condenser 63. Condenser 63 is also immersed in the glycol bath 51. Condenser 63 has parallel headers 63a connected by a plurality of tubes 63b, which are parallel to each other and perpendicular to headers 63a. The refrigerant is condensed in the condenser 63 and flows through a check valve 65 into the liquid line 55. A recirculating pump 67 located in he glycol bath 51 will circulate and discharge glycol through the fins (not shown) mounted to tubes 63b of the condenser 63 to facilitate heat exchange.
A bypass line 69 joins vapor conduit 45 at the upstream side of condenser 63 and extends to the inlet line 73 of a feedback compressor 81. A normally closed bypass valve 71 blocks flow through bypass line 69 unless open. Feedback compressor 81 is a conventional refrigerant compressor, having protective low and high pressure switches 83, 85. When bypass valve is open, some of the refrigerant vapor from vapor conduit 45 passes directly to the inlet line 73 of feedback compressor 81. Feedback compressor 81 further increases the pressure, and passes the vapor through a drawdown valve 87 and a check valve 91 to the condenser 63.
The inlet line 73 of feedback compressor 81 has a normally open vapor port valve 77. Inlet line 73 joins a vapor port or line 75. Vapor port 75 extends into the upper portion of tank 59. A pressure switch 79 is located in the vapor port 75 to monitor the vapor pressure in the upper portion of the tank 59. Switch 79 electrically controls bypass valve 71 and vapor port valve 77 through electrical line 80. A drawdown valve 82 locates between switch 79 and valve 77.
When the pressure sensed by switch 79 is below a selected level, vapor port valve 77 is closed, blocking flow out of vapor port 75. Bypass valve 71 will be open when the pressure is below the selected level. A preferred selected level is 10 to 20 psi. When the pressure is above the selected level, switch 79 positions vapor port valve 77 in the open position, connecting vapor port 75 to the inlet line 73 of feedback compressor 81. When at or above the selected level, switch 79 positions bypass valve 71 in the closed position.
Tank 59 has a conventional float valve 93 which will monitor the level of liquid. Float valve 93 will close liquid valve 57 when tank 59 is full.
After the refrigeration system has been evacuated, it will be necessary to withdraw refrigerant from the various lines and components of the suction unit 11 and truck mounted unit 47. The drawdown components include a pressure drawdown line 95 which leads from drawdown valve 87. Valve 87 has one position which directs the output of compressor 81 through pressure drawdown line 95 and back into the vapor line 75. Drawdown valve 82, which locates at the junction of pressure drawdown line 95 and vapor port 75, has one position that directs flow from drawdown line 95 back into vapor port 75. The other position of drawdown valve 82 directs the flow of vapor out of vapor port 75 to the inlet line 73 of feedback compressor 81. A drawdown suction line 97 extends from the liquid port 56 of tank 59 to line 73 at the intake of feedback compressor 81. A normally closed drawdown valve 99 will open drawdown suction line 97 during the drawdown procedure.
In operation, the operator will place suction unit 11 adjacent the refrigeration system. The operator will connect the low pressure intake 13 to a point in the refrigeration system for receiving vapor, such as the inlet of the refrigeration system compressor. The high pressure intake 15 will be connected to a point in the refrigeration system for receiving liquid, such as at the receiver of the refrigeration system. The operator connects the liquid and vapor conduits 33, 45 from the suction unit 11 to the truck mounted unit 47. All of the lines and components of the suction unit 11 and truck mounted unit 47 will be initially evacuated.
Initially, the operator will withdraw the liquid refrigerant from the system by turning on liquid pump 31. Valve 29 will be in the position shown. The liquid will flow through filter 27 and through the liquid conduit 33. Referring to FIG. 2, the liquid flows through the heat exchanger 49, cooling the liquid. The liquid flows through liquid line 55 and into the liquid port 56 of storage tank 59.
Once the liquid refrigerant has been withdrawn, the operator will then turn on suction compressor 25 to withdraw vapor and pass it through the precooler 39 and out the vapor conduit 45 as a warm, high-pressure vapor. The operator may switch valve 29 to the opposite position shown, so as to withdraw through liquid intake 15 any vapor left in the high pressure side of the refrigeration system. The vapor flows through vapor conduit 45 to truck mounted unit 47.
Referring to FIG. 2, vapor from vapor conduit 45 will flow through condenser 63 where it condenses and flows as a liquid into liquid line 55. The condensed liquid flows into tank 59. Feedback compressor 81 will be continuously running. Initially the vapor pressure in tank 59 will likely be above the selected level because of vaporization of some of the liquid refrigerant that has been stored in tank 59. If so, bypass valve 71 will be closed and vapor port valve 77 will be open. Vapor will flow from tank 59 to the inlet line 73 of feedback compressor 81, which compresses the vapor and transmits it through valves 87, 91 to condenser 63. Condenser 63 condenses the vapor, which flows into liquid line 55 and tank 59.
The vapor pressure in tank 59 may drop below the selected level due to the suction of feedback compressor 81. If below the selected level, pressure switch 79 will cause vapor port valve 77 to close and bypass valve 71 to open. Some of the vapor flowing from conduit 45 will now flow through bypass line 69 to inlet line 73 of feedback compressor 81, which now acts in tandem with suction compressor 25, further increasing the pressure. The vapor flows through the outlet through valve 87 and into condenser 63, where it will be condensed into a liquid. The condensed liquid flows through check valve 65, liquid line 55 and into liquid port 56. The vapor pressure in tank 59 may be above and below the selected level several times during a recovery process. Feedback compressor 81 when withdrawing vapor from tank 59 prevents excessive pressure in tank 59, which otherwise would restrict the flow rate of liquid into liquid port 56.
Once all of the refrigerant has been withdrawn, the system will be placed in a drawdown mode to evacuate its lines and components of refrigerant. This is handled by opening drawdown valve 99, closing liquid valve 57, switching drawdown valve 82 to the opposite position shown, and switching drawdown valve 87 to the opposite position shown. Feedback compressor 81 will be running. Vapor in the conduits 33, 45, condenser 63, heat exchanger 49 and the various other components, will pass through liquid line 55 as a vapor and be drawn through the valve 99 to the inlet line 73 of feedback compressor 81. Feedback compressor 81 will compress the vapor and pass it through drawdown line 95 and valve 82 into the vapor port 75. Once all of the lines have been evacuated, valves 99, 87, and 82 will be moved back to the positions shown and feedback compressor 81 turned off.
The invention has significant advantages. The submersion of the heat exchanger and condenser in a glycol bath greatly facilitates the flow rate. The feedback compressor reduces pressure due to vapor in the tank, to allow a high flow rate of liquid into the tank to be maintained. The drawdown components allow the recovery unit itself to be evacuated of refrigerant.
While the invention has been shown in only one 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.
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A refrigerant recovery unit for large refrigerant systems has a suction compressor which withdraws vapor and a liquid pump which withdraws liquid refrigerant. The compressor and liquid pump pass the fluids to a heat exchanger and a condenser, both located within a bath of chilled liquid. The vapor condenses into a liquid and combines with the liquid refrigerant. The liquid passes to a storage tank. A feedback compressor withdraws vapor from the upper portion of the tank if the pressure is above a selected level and passes it to the condenser for further condensation. A bypass line directs refrigerant vapor to the inlet of the feedback compressor if the tank vapor pressure is below the selected level. A drawdown line allows the feedback compressor to draw all of the refrigerant from the recovery unit after the recovery unit has recovered the refrigerant from the refrigeration system.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to the following 5 U.S. provisional patent applications:
[0002] Using Resistance Equivalent to Estimate Temperature of a Fuel-Injector Heater, invented by Perry Czimmek, Mike Hornby, and Doug Cosby, filed on the same day as this provisional patent application, and identified by Attorney Docket Number 2012P01913US.
[0003] Tuned Power Amplifier With Loaded Choke For Inductively Heated Fuel Injector, invented by Perry Czimmek, filed on the same day as this provisional patent application, and identified by Attorney Docket Number 2012P01914US.
[0004] Tuned Power Amplifier with Multiple Loaded Chokes for Inductively Heated Fuel Injectors, invented by Perry Czimmek, filed on the same day as this provisional patent application, and identified by Attorney Docket Number 2012P01915US.
[0005] Resistance Determination For Temperature Control Of Heated Automotive Components, invented by Perry Czimmek, filed on the same day as this provisional patent application, and identified by Attorney Docket Number 2012P02175US.
[0006] Resistance Determination with Increased Sensitivity for Temperature Control of Heated Automotive Component, invented by Perry Czimmek, filed on the same day as this provisional patent application, and identified by Attorney Docket Number 2012P02176US.
BACKGROUND
[0007] Embodiments of the invention relate generally to power electronics for exhaust after-treatment component heaters and more particularly to power electronics for control and monitoring of electronic catalysts and decomposition elements associated with reductant delivery exhaust after-treatment.
[0008] There is a continued need for improving the emissions quality of internal combustion engines. At the same time, there is pressure to have improved emissions while having a maximum of fuel economy. Those pressures apply to engines fueled with gasoline, diesel, natural gas, or with any other alternative fuels such as hydrogen, ethanol, or additional bio-fuels.
[0009] Dividing the types of components into three distinct categories serves to simplify the explanation of the locations for an exhaust after-treatment heater. The three types of components are: the 3-way catalyst, the particulate filter, and the reductant decomposition tube. The 3-way catalyst combines the undesirable hydrocarbon and carbon monoxide emissions with excess oxygen in the exhaust stream and catalyzes an oxidation reaction where water and carbon dioxide are the output. Further, a reduction reaction occurs where nitrogen oxides, or NOx emissions, are reduced to nitrogen and oxygen. Historical 3-way catalyst systems enrich the combustion such that the combustion continues at a low level inside the exhaust system to more quickly raise the temperature of the catalyst, typically referred to as “catalyst light-off.”
[0010] The particulate filter, for diesels is the Diesel Particulate Filter (“DPF”). This component is a filter that traps carbon particulates or soot. The filter “loads up” with the particles that are being trapped because the filter's pores are smaller than the particles. Eventually, the back-pressure caused by a loaded filter flags the regeneration of this filter. The regeneration is accomplished by heating the filter material, typically ceramic, to such a high temperature that the carbon particulates burn off in the presence of excess oxygen. This heating is typically accomplished by enriching the exhaust with unburned fuel that then burns at the filter, thereby heating it.
[0011] The reductant decomposition tube is where urea-water solution is added by a Reductant Delivery Unit (“RDU”) to the exhaust stream. This urea-water solution aids in Selective Catalyst Reduction (“SCR”) by decomposition of the urea into ammonia and water. This ammonia then reduces nitrogen oxides into diatomic nitrogen and water. Typically, hot exhaust gas is expected to decompose the urea into ammonia and water inside the decomposition tube. This is, however, not always efficient as urea decomposes over a narrow temperature range into ammonia and water, and more frequently decomposes in additional reactions to deposits that do not contribute to SCR.
[0012] During engine cold start, the enrichment necessary to accomplish the start leaves an off-stoichiometric fueling that materializes as high tail-pipe hydrocarbon emissions, due, at least in part, to cold exhaust after-treatment components. The worst emissions are during the first few minutes of engine operation, after which the catalyst, other exhaust components and engine approach operating temperature.
[0013] A number of pre-heating methods have been proposed, most of which involve additional combustion products to be made. The fastest method to heat a catalyst, decomposition element, or particulate filter is directly with electrical power. Electrical energy is converted to heat inside a component suitable in geometry and material to be heated by the Joule or Ohm losses that are caused by the flow of current through that component. As such, it is desirable to know the temperature of the heater and to control that temperature.
[0014] Because the heating technique uses an electrical current, the system includes electronics for providing an appropriate excitation to the component in the exhaust system. This excitation may include controlling the electrical energy and determining when that electrical energy is applied.
[0015] Conventional resistive heating is accomplished open-loop, or without control of electrical energy based on a temperature. A remote thermostat or computational model may be incorporated to provide some control to prevent a runaway temperature event and some level of control. More sophisticated methods may monitor the current through the heater to estimate the temperature or direct thermocouple, positive/negative temperature coefficient sensor, or other means for determining the temperature for a more precise regulation of component temperature.
[0016] The metallic component that is heated will have a positive temperature coefficient of resistance to electrical current (i.e., its electrical resistance will increase as its temperature increases). Ideally, knowing the initial resistance and final resistance would allow the temperature of the component to be known with some degree of precision. The best metals for resistive heaters usually have very small positive temperature coefficients and therefore measurement of the change in resistance by only monitoring current will be desensitized by harness resistance and aging of numerous interconnecting components. Additionally, electronic catalysts, or E-cats, are made of stainless steel and also suffer from a small temperature coefficient of the material. Therefore, it becomes difficult to distinguish a change in resistance of the heater component from a change in resistance of other components connected in series.
[0017] It would be advantageous to more precisely know the resistance change of the heater component such that control of the temperature may be accomplished.
BRIEF SUMMARY
[0018] A temperature of a heated component is determined for control and monitoring. The heater driver, upon receipt of a turn-on signal, generates a current within a component of an electronic catalyst or exhaust after-treatment component, wherein the current through the component generates an appropriate loss to generate heat for facilitation of an exhaust after-treatment process. The heater driver regulates the energy to the heated component based on the electrical resistance of that component as a function of temperature and a predetermined reference value for that temperature.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 depicts a system in accordance with embodiments of the invention.
DETAILED DESCRIPTION
[0020] Embodiments of the invention are directed to determining a temperature of a heater component in an exhaust after-treatment component. Current may be measured by precisely measuring a voltage drop across a small value precision resistor inside an electronics assembly, or “current-sense resistor.” This voltage drop is directly proportional to the current flowing through the resistor. Knowledge of this current may then be expanded upon by a precise measurement of voltage across the heater component. With the current through the heater known and the voltage across the heater known, from Ohm's Law, the resistance may be calculated in accordance with the well-known formula R=V/I, where R is resistance, V is voltage, and I is current. Embodiments of the invention use this resistance knowledge to estimate a temperature of the heated component and to regulate the temperature of the heated component based on this estimate.
[0021] Referring to FIG. 1 , an electronic catalyst (“E-Cat”) heater 110 references the heated component of which a resistance, as a function of temperature, is to be determined. An I-sense resistor differential voltage, also referred to as heater current signal 120 , represents the electrical current through the I-sense resistor 122 and, therefore, through the E-Cat heater 110 . A current measurement circuit 127 comprises the I-sense resistor 122 and a differential voltage operational amplifier 126 . A current sense resistor may be used either on the high side or the low side of the power switch or the load. Current measurement may be done with a hall sensor or with other types of magnetic sensors, such as sense coils.
[0022] A differential voltage across the E-Cat heater, also referred to as heater voltage signal 108 , represents the excitation voltage directly related to the current flowing through the E-Cat heater. The two differential voltages are solved for Ohm's Law relation, R=V/I, using an analog or digital division equivalent 113 , to provide a result as a voltage-equivalent heater resistance signal 112 . The analog or digital division equivalent 113 may be implemented in accordance with conventional techniques, which are known in the art, by combining operations and components including, but not limited to: summing and shift registers in digital solutions; and logarithmic, sum or difference, and antilogarithm amplification in analog solutions. The change in resistance differential amplifier 118 then finds a difference between the voltage-equivalent heater resistance signal 112 and a resistance reference value, R-ref 124 . This generates a delta, or change in resistance, or error, signal that may be brought in as an equivalent temperature rise signal 123 to a temperature control module 130 . This equivalent temperature rise signal 123 may be integrated over time, which may be performed computationally or through an analog conversion to perform the integration function, and may be compared to a temperature reference, T-ref 128 . The temperature control module 130 may use this comparison to determine if power should be removed from the E-Cat heater by turning off the power switch 116 , represented by a MOSFET in FIG. 1 for this example. The temperature control module 130 may be: a microcontroller, a digital “thermostat”, a PID (Proportional Integral Derivative) controller, or any interface that uses the change in temperature (that is represented by the equivalent temperature rise signal) integrated and compared to a target change in temperature, absolute temperature, or some other temperature reference. If the equivalent temperature rise signal 123 is too high, the temperature change is too great, so the power switch 116 may be de-energized thereby turning off the E-Cat heater 110 . A cool-down model may then be used to determine when to turn the heater on again. Or if a continuous set point control strategy is used, then the power switch may be turned on and off rapidly (or operated in a linear region like an analog audio amplifier) to regulate the temperature to a target temperature by repeatedly adjusting heater power.
[0023] The differential voltage across the E-Cat heater 110 may be obtained by a differential voltage measurement circuit 109 , which may comprise a differential voltage operational amplifier 114 and a pair of Kelvin connections 104 - 1 and 104 - 2 to the heater as close to the actual heater electrical connections as possible. The pair of Kelvin connections refers to the junction where force and sense connections are made. The force component is a high current carrying conductor and the sense component is a parallel wire for obtaining a voltage potential at that connection. There are two Kelvin connections such that one conductor pair carries the current of the E-Cat heater, and the other conductor pair is used for obtaining the voltage potential. The two pairs of wires may be of different size, with the current carrying pair of an appropriate size to minimize loss, and the voltage potential pair any reasonably small size for the measurement. In this way, these two pairs of wires may be used, in accordance with embodiments of the invention, to perform a four wire measurement.
[0024] To measure the differential voltage, the load or heater may be one leg of a
[0025] Wheatstone bridge that is balanced. And then any change in the load would result in an unbalance of the Wheatstone bridge, and, therefore, a different voltage across the load. Or a resistance divider may be located locally at the heater or load. And then the voltage from the resistance divider may be brought back to the electronics for interpretation.
[0026] In sum, in accordance with embodiments of the invention, heater resistance may be determined by dividing differential voltage across the heater, measured close to the heater, by the current through the heater. And the equivalent resistance value may be used to control the heater temperature based on a resistance change due to temperature.
[0027] The foregoing detailed description is to be understood as being in every respect illustrative and exemplary, but not restrictive, and the scope of the invention disclosed herein is not to be determined from the description of the invention, but rather from the claims as interpreted according to the full breadth permitted by the patent laws. For example, while FIG. 1 depicts a low side semiconductor switch and a low side current sense resistor, other embodiments may use a high side semiconductor switch or high side current sense resistor or any combination thereof as understood by those skilled in the art. It is to be understood that the embodiments shown and described herein are only illustrative of embodiments of the invention and that various modifications may be implemented by those skilled in the art without departing from the scope and spirit of the invention.
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A temperature of a heated component is determined for control and monitoring. The heater driver, upon receipt of a turn-on signal, generates a current within a component of an electronic catalyst or exhaust after-treatment component, wherein the current through the component generates an appropriate loss to generate heat for facilitation of an exhaust after-treatment process. The heater driver regulates the energy to the heated component based on the electrical resistance of that component as a function of temperature and a predetermined reference value for that temperature.
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BACKGROUND OF THE INVENTION
The present invention relates to a scroll-type hydraulic machine.
Before describing the present invention, the basic principles of a scroll-type hydraulic machine will be briefly explained.
FIGS. 1A to 1D show fundamental components of a scroll-type compressor, which is one application of a scroll-type hydraulic machine, and the operations thereof in successive angular positions. In these figures, the compressor is composed of a stationary scroll 1, having a fixed center O, and an orbiting scroll 2, which performs an orbiting motion around a fixed point O'. Compression chambers 4 are formed between the stationary scroll 1 and the orbiting scroll 2, and a discharge port 3 is formed around a center portion of the stationary scroll 1. The scrolls 1 and 2 take the form of spiral arms, each of which may be in the form of an involute or a combination of involutes and arcs. The arms are complementary in shape. The stationary scroll 1 and the orbiting scroll 2 are interleaved as shown.
In operation, the orbiting scroll 2 orbits continuously with respect to the stationary scroll 1 from a starting position (0°) shown in FIG. 1A through operating cycle phase positions of 90° (FIG. 1B), 180° (FIG. 1C) and 270° (FIG. 1D), without changing its angular orientation with respect to the stationary scroll 1. With such orbital movement of the orbiting scroll 2, the volumes of the compression chambers 4 are cyclically reduced, and thus fluid introduced therein is compressed. The compressed fluid is finally discharged from the discharge port 3. During this operation the distance between the center O and the fixed point O', which is maintained constant, can be represented by: ##EQU1## where p corresponds to a distance between wraps and t is the wall thickness of each wrap.
In order to minimize the thrust force of a scroll-type hydraulic machine or compressor having a large capacity, a structure has been proposed in which the orbiting scrolls are arranged in a back-to-back relationship to cancel out the thrust forces. Examples of such structures are disclosed in U.S. Pat. Nos. 801,182, 3,011,694 and 4,192,152. In order to facilitate an understanding of the background of the present invention, the structure having the back-to-back arranged orbiting scrolls will be described briefly with reference to FIG. 2, which shows schematically an example of such a structure as disclosed in U.S. Pat. No. 4,192,152.
In FIG. 2, a pair of stationary scrolls 1 have complementary-shaped wraps 5. The scrolls 1 are fixedly secured to each other by bolts 4 with the scroll wraps facing one another with a space therebetween. An orbiting scroll 2 is provided on opposite surfaces of a center plate with complementary-shaped orbiting scroll wraps 6. The orbiting scroll 2 is disposed in the space between the stationary scrolls forming a plurality of compression chambers 4 between the stationary scroll wraps 5 and the orbiting scroll wraps 6. Discharge ports 3 for the compressed fluid are formed at center portions of the stationary scrolls 1 to which respective discharge tubes 15 are connected. An intake port 16 is formed at a suitable peripheral position of one of the stationary scrolls 1 to which an intake pipe 17 is connected. Near the intake port 16 in the space between the stationary scrolls 1 is formed a suction chamber 18. A crankshaft 7 having an eccentric portion is supported by bearings 9, 10 and 11 provided in the stationary scrolls 1 and is driven through a coupling 12 by a drive source 13. The eccentric portion of the crankshaft 7 is supported by a bearing 8 provided in the orbiting scroll 2. A balance weight 19 is attached to the eccentric portion of the crankshaft 7 to balance a centrifugal force acting on the orbiting scroll 2 during the operation of the machine.
In operation, the crankshaft 7 is rotated by the drive source 13, which may be electric motor, internal combustion engine, turbine or the like. Upon the rotation of the crankshaft 7, an orbiting force is imparted to the orbiting scroll 2 via the bearing 8 by the eccentric rotation of the eccentric portion of the crankshaft. Compression then occurs on both sides of the orbiting scroll as described above. The pressure in the compression chambers 4 increases as the chambers 4 move towards the center portion of the machine and pressurized fluid is discharged through the discharge ports 3 and hence through the discharge tubes 15. At the same time, fluid intake occurs through the suction tube 17 and the intake port 16 to the intake chamber 18, which feeds the fluid to the compression chamber 4. The centrifugal force acting on the orbiting scroll 2 which is generated during the operation thereof is statically as well as dynamically balanced by the balance weight 19 shown in FIG. 2.
Since the compression chambers 4 are formed symmetrically around the orbiting scroll 2, the pressure distribution of the compression chambers 4 on both sides of the orbiting scroll 2 are similar, and thus there are no thrust forces acting on the orbiting scroll 2 as a whole. This construction is particularly effective when the operating speed of the orbiting scroll is low and the thrust load is large because, in such a case, it is very difficult to use a thrust bearing.
Although this conventional structure is advantageous due to the fact that no thrust force is produced, there are still problems in actual practice. Specifically, it is impossible as a practical matter to manufacture the orbiting scroll 2 having the complementary scroll wraps 6 on the opposite sides thereof with a high precision, and it is very difficult to assemble the orbiting scroll with the stationary scroll 1 with precisely controlled radial gaps between the orbiting scroll wraps 6 and the stationary scroll wraps 5 on both sides of the orbiting scroll. Particularly, the relative position of one stationary scroll to the other is determined by the relative positions of the bearings mounted in the stationary scrolls 1, and the relative position of the orbiting scroll 2 to the stationary scrolls 1 is determined by the coupling provided by the crankshaft 7. Thus, very precise adjustment of the radial gaps between the orbiting scroll and the stationary scrolls is impossible as a practical matter. Once these factors are taken into account, the conventional scroll-type machine constructed as described above has not been entirely satisfactory.
Another important problem relates to the driving system for the orbiting scroll. In FIG. 2, a single crank mechanism is used. In a case where a plurality of crank mechanisms are arranged equiangularly, the eccentric centers of the respective crankshafts 7 of the mechanisms must be highly precisely determined, otherwise a normal operation of the machine itself cannot be expected.
A more important problem resides in that, due to the fact that the drive system is disposed at the periphery of the orbiting scroll 2, the diameter of the orbiting scroll 2 is necessarily large, and due to a large mass resulting from such a large diameter of the orbiting scroll, the bearing load due to centrifugal forces is not negligible. Furthermore, the diameter of the stationary scrolls 1 is necessarily also large, which makes it necessary to make the walls of the stationary scrolls quite thick.
SUMMARY OF THE INVENTION
Overcoming these drawbacks, the present invention provides a scroll-type hydraulic machine having a pair of stationary scroll wraps and orbiting scroll wraps assembled together in which thrust loads acting on the orbiting scroll are cancelled by constructing the machine so that the thrust forces act on opposite sides of the eccentric shaft. Further in accordance with the invention, the mechanical reliability of the machine is improved by minimizing the relative movement between the orbiting scroll and the eccentric shaft.
Furthermore, the invention provides a scroll-type hydraulic machine having orbiting scrolls which are easily assembled with the stationary scrolls and the gaps between the orbiting scrolls and the stationary scrolls are easily sealed.
More specifically, the present invention, provides a scroll-type hydraulic machine including a first stationary scroll having a first scroll wrap, a first orbiting scroll having a second scroll wrap interleaved with the first scroll wrap such that the interleaved first and second scroll wraps compress and discharge introduced fluid when the second scroll wrap is orbited with respect to the first scroll wrap; a first orbiting scroll shaft provided on the orbiting scroll opposite the second scroll wrap, a second stationary scroll having a third scroll wrap, a second orbiting scroll having a fourth scroll wrap interleaved with the third scroll wrap such that the interleaved third and fourth scroll wraps compress and discharge introduced fluid when the fourth scroll wrap is orbited with respect to the third scroll wrap, a second orbiting scroll shaft provided on the second orbiting scroll opposite the fourth scroll wrap, and a crank mechanism. The crank mechanism includes a crankshaft having an eccentric through-hole and which is rotated by driving means, an eccentric shaft supported in the eccentric through-hole of the crankshaft through bearings, a first driven eccentric ring mechanism, and a second driven eccentric ring mechanism. The first orbiting scroll shaft is disposed at one end of the eccentric shaft and is engaged therewith through the first driven eccentric ring mechanism rotatable with respect to the eccentric shaft to orbit the first orbiting scroll shaft. Similarly, the second orbiting scroll shaft is disposed at the other end of the eccentric shaft and is engaged therewith through the second driven eccentric ring mechanism rotatable with respect to the eccentric shaft. The crank mechanism further includes a pair of discrete, driven eccentric ring mechanisms, disposed on opposite sides of the eccentric shaft, through which the orbiting scroll shafts are driven.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A to 1D are cross-sectional views showing a scroll-type hydraulic machine in successive operational steps used for an explanation of the operating principles thereof;
FIG. 2 is a cross-sectional view of a conventional scroll-type hydraulic machine;
FIG. 3 is a cross-sectional view of a scroll-type hydraulic machine constructed according to the present invention;
FIG. 4 is an enlarged view of a portion of the machine of FIG. 3 in a disassembled state;
FIGS. 5A-5D through 7 illustrate a driven eccentric ring mechanism in successive operational positions;
FIG. 8 illustrates forces acting on the orbiting scroll;
FIG. 9 is a perspective view of a large-scale version of the preferred embodiment of the present invention; and
FIG. 10 is a front view of the machine of FIG. 9.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 3, which is a cross-sectional view of a preferred embodiment of a scroll-type hydraulic machine according to the present invention, and in FIG. 4, which is an enlarged perspective view of a portion of the machine of FIG. 3 in a disassembled state with important portions exaggerated, a crankshaft 20 is provided with an eccentric through-hole 21 in which an eccentric shaft 22 is rotatably supported through bearings 23. The crankshaft 20, the bearing 23, the eccentric shaft 22, and the driven eccentric ring mechanisms constitute a crank mechanism. The crankshaft 20 and the eccentric shaft 22 have rotational centers 24 and 25 (FIG. 4), respectively. The eccentric shaft 22 has at one end thereof an enlarged portion 26 formed with a center recess 27 in which a driven eccentric ring mechanism 28 is rotatably received. An orbiting scroll shaft 30 of an orbiting scroll 29 is rotatably fitted in the driven eccentric ring mechanism 28. The driven eccentric ring mechanism 28 is composed of an eccentric ring 31, an eccentric ring bearing 32 supporting the eccentric ring 31 rotatably with respect to the enlarged portion 26 of the eccentric shaft 22, and an orbiting scroll bearing 33 supporting the eccentric ring 31 rotatably with respect to the orbiting scroll shaft 30. The orbiting scroll shaft 30 has a center of rotation O 2 (34) separated from the center of rotation O 1 (24) of the crankshaft 20 by a predetermined crank radius r (see also FIG. 5A). The eccentric ring 31 has a center of rotation O 3 (35) which lies at a point substantially on a straight line connecting the center of rotation 24 and the center of rotation 34 of the orbiting scroll shaft 30 and on an opposite side to the center of rotation 24 with respect to the point 34. The positions of the points O 1 , O 2 and O 3 are shown in FIG. 5A and will be described in more detail later. In this embodiment, the center 25 of the eccentric shaft 22 coincides with the center 35 of the eccentric ring 31.
An Oldham coupling 36 (FIG. 4) of a known construction is used to maintain the angular position of the orbiting scroll 29. The Oldham coupling 36 includes a ring member, a pair of lower protrusions 39 formed opposite each other on a lower surface of the ring member, and a pair of upper protrusions 41 formed opposite each other and orthogonally to the lower protrusions on the upper surface of the ring member. The protrusions 39 are slidably engaged with an Oldham coupling groove 38 formed on a housing 37, and the protrusions 41 are slidably engaged with an Oldham coupling claw 40 formed on the orbiting scroll 29. The scroll 29 has on a lower surface thereof a shaft 30 and on an upper surface thereof an orbiting scroll wrap 42 interleaved with a wrap 44 of a stationary scroll 43. Scroll 43 is fastened by bolts 45 to the housing 37. The wraps establish an angular relationship as shown in FIG. 1.
An intake port 46 is formed in the stationary scroll 43 to which an inlet pipe 47 is connected. When the orbiting scroll 29 orbits with respect to the stationary scroll 43, the fluid to be compressed is sucked through the intake pipe 47 to a suction chamber 48 and, after being compressed in the compression chambers 49, is discharged via a discharge port 50 through the discharge pipe 51.
The crankshaft 20 is supported by crankshaft bearings 52 provided in the housing 37. A driven gear mechanism 53 is keyed to the outer periphery of the crankshaft 20 to drive the latter. A balance weight 55 is attached to the driven gear mechanism 53 to balance the centrifugal force produced by the operation of the machine and acting on the orbiting scroll.
The other end of the eccentric shaft 22 is formed with an enlarged diameter portion 126 which is similar to the upper enlarged portion 26 and has a center recess similar to the recess 27 of the upper enlarged diameter portion 26. The enlarged diameter portion 126 is coupled with a shaft 130 of a lower orbiting scroll 129. Housing 37 and scroll 129 are coupled through an Oldham coupling similar to that associated with the upper obiting scroll 29 but having a complementary configuration.
The driven gear mechanism 53 is driven by a driving gear 56 keyed to a drive shaft 57. A gear box 59 houses a plurality of drive shaft bearings 60 by which the drive shaft 57 is rotatably supported. A hole through which the drive shaft 57 extends outwardly is provided with a sealing member 61 with which the gear box is sealed and is prevented from being contaminated by dust.
A lubricating oil tank 62 is provided below the gear box 59 and a pump 64 is incorporated therein. The pump 64, when operated, feeds lubricating oil 63 from the tank 62 through an oil supply hole 65 to lubricate the drive shaft bearings 60. The oil then passes to the housing 37. After lubricating the various sliding portions including bearings in the housing 37, the oil is returned through an oil return hole 66 to the tank 62 as indicated by arrows in FIG. 2. In order to protect the pump 64, a filter 68 is provided at an inlet portion of an intake pipe 67 of the pump 64. Members depicted by reference numerals 69 (FIG. 3), 70 (FIG. 4) and 71 (FIG. 4) are oil throwers, thrust bearings and oil supply grooves, respectively.
In operation, the scroll-type hydraulic machine, here assumed to be a compressor, starts when the drive shaft 57 is driven by a driving source such as an electric motor, internal combustion engine, turbine, etc. (not shown). When the drive shaft 57 rotates, the driving gear 56 engaged with the drive shaft 57 is rotated to rotate the driven gear 53 meshed with the driving gear 56. Since the driven gear 53 is coupled to the crankshaft 20, the latter, which is supported by the crankshaft bearings 62 in the housing 37, also rotates about its center 24.
The eccentric shaft 22, having the center 25 and supported by the bearings 23 in the eccentric through-hole 21 of the crankshaft 20, is rotated about the center of rotation 24 with the distance corresponding to the crank radius r being maintained between the center 25 and the center of rotation 24.
As mentioned previously, the enlarged diameter portions 26 and 126 provided at the opposite ends of the eccentric shaft 22 and associated components are similar but complementary in shape. Therefore, only the enlarged diameter portion 26 and the elements associated therewith will be described in detail. The circular recess 27 formed in the enlarged diameter portion, having the center of rotation 25, rotatably receives therein the driven eccentric ring mechanism 28. The driven eccentric ring mechanism 28 functions to seal the radial gap between the stationary scroll wrap 44 of the stationary scroll 43 and the orbiting scroll wrap 42 of the orbiting scroll 29 during the operation of the machine. The operating principles thereof will be described with reference to FIGS. 5A through 7.
In FIGS. 5A through 5D, the center of rotation O 1 (24) of the crankshaft 20 is assumed to be at the origin of the indicated coordinate system. A, B and C indicate fixed points on the orbiting scroll shaft 30, the eccentric ring 31, and the enlarged diameter portion 56, respectively. FIGS. 5A through 5D illustrate relative positions of these elements when the machine is at operating cycle phase angles of 0°, 90°, 180° and 270°, respectively. When the crankshaft 20 rotates around the center of rotation O 1 , the center O 3 of the eccentric shaft 22 also rotates around the center of rotation O 1 . Therefore, the center O 2 of the orbiting scroll shaft 30 rotates around O 1 with O 1 O 2 =r. Thus O 1 , O 2 and O 3 are arranged substantially on a straight line which rotates at the same rotational speed as the crankshaft 20. At this time, the point A on the orbiting scroll shaft 30 does not perform rotation relative to the center O 2 due to the restriction imposed by the Oldham coupling 36, and lines connecting the center O 2 to the point A in the respective states shown in FIGS. 5B, 5C and 5D are always parallel to the line between the center O 2 and the point A in the state shown in FIG. 5A.
As to the fixed point C on the thrust bearing 70 and hence the increased diameter portion 26, there is a slight relative movement between the thrust bearing 70 and the orbiting scroll 29. Therefore, the point C tends to rotate about O 3 with a rotational radius of O 2 O 3 . However, since, as will be described later, the distance O 1 O 2 increases when the point C rotates in either direction, the wrap 42 of the orbiting scroll 29 contacts the wrap 44 of the stationary scroll 43. Therefore, the range of movement of the center of rotation O 2 is on the order of the width of the gap between the wraps 44 and 42, and thus the range of relative movement between the center O 3 and the point C is of the same order as above. Thus, a line connecting the center O 3 and the point C is substantially parallel to that shown in FIG. 5A through the entire rotational cycle, as shown in FIGS. 5A through 5D. Accordingly, the fixed point B on the eccentric ring 31 always falls on a line connecting the centers O 1 , O 2 and O 3 and performs relative movement with respect to O 2 . As will be clear from the foregoing, since the eccentric ring 31 undergoes movement relative to the orbiting scroll shaft 30 and the increased diameter portion 26 and hence the eccentric shaft 22, the orbiting scroll bearing 33 and the eccentric ring bearing 32 are provided.
The relative movement between the thrust bearing 70 and the orbiting scroll 29 is a circular movement with a radius O 2 O 3 and, if O 2 O 3 =e is made small enough, it is possible to make the relative speed quite small.
The way in which radial sealing of the driven eccentric ring mechanism 28 is achieved will now be described with reference to FIGS. 6 and 7. It has been well known that when the compression operation is started, a force F.sub.θ, which is tangential to the rotational direction D, and a radial force F r , due mainly to the centrifugal force of the orbiting scroll 29, act on the center of rotation O 2 of the orbiting scroll shaft 30, and hence produce a load on the driving source. This is shown in FIG. 6. When the force component F.sub.θ acts on the center of rotation O 2 , a moment F.sub.θ ·e is produced around the center of rotation O 3 of the eccentric ring 31. At this time, since the force component F r acts on a straight line connecting the centers O 2 and O 3 , there is no moment produced around O 3 . In some cases, there may be a minute gap ε present between the wraps 44 and 42 of the stationary scroll 43 and the orbiting scroll 29, even if the distance between the centers O 1 and O 2 is maintained at the predetermined crank radius ##EQU2## Further, it has been empirically determined that the width of such gap is on the order of several microns to several tens of microns. It has been also known that if the wraps 44 and 42 are shaped as involutes of a circle having radius a, the gaps ε fall along straight lines which are parallel to each other and symmetric about the vector force component F r and spaced a distance a therefrom.
When the moment F.sub.θ ·e acts about the center of rotation O 3 of the eccentric ring as described, the center of rotation O 2 of the orbiting scroll shaft 30 tends to rotate around O 3 and the wrap 42 of the orbiting scroll 29 approaches the wrap 44 of the stationary scroll until the minute gap ε disappears. This state is shown in FIG. 7. The center of rotation O 2 of the orbiting scroll shaft 30 rotates about the center O 3 through a minute angle Δθ and reaches a point O 12 . At this time, the distance between O 1 and O 2 increases to be the same as that between the points O 1 and O 12 , causing the minute radial gap ε to disappear. As shown in FIG. 7, a sealing force f is thus produced between the wraps 44 and 42, and hence the distance e between O 2 and O 3 can be obtained from the equation representing the balance of moments, namely, 2f·a=F.sub.θ ·e, where ε and hence the angle Δθ, are assumed as being negligible. From this, the sealing force f can be calculated as ##EQU3##
Accordingly, it can be understood that sealing of the radial gap between the scroll wraps 44 and 42 is realized and leakage of compressed fluid therethrough during the operation of the machine is hence minimized.
A specific feature of the driven eccentric ring mechanism 28 is that the sealing force f is a function of only the tangential force component F.sub.θ, which is a function only of the pressure in the compressor, and is not substantially influenced by the speed (r.p.m.) of the machine. In this manner, the driven eccentric ring mechanism 28, received in the circular recess 27 of the eccentric shaft 22, seals the radial gap between the stationary scroll wrap 44 and the orbiting scroll wrap 42.
When the eccentric shaft 22 is driven by the crankshaft 20, the orbiting scroll 29 is driven through the driven eccentric crank mechanism 28. In order to perform compression according to the principles illustrated in FIGS. 1A through 1B, the Oldham coupling 36 engages with the Oldham coupling grooves 38 formed on the housing 37 and with the Oldham coupling claws 31 of the orbiting scroll 29. The Oldham coupling 36 performs a straight reciprocal movement with respect to the housing 37 and also performs a relative straight reciprocal movement with respect to the orbiting scroll 29 (see FIG. 4).
When the orbiting scroll 29 is driven by the eccentric shaft 22 through the driven eccentric ring mechanism 28 and the Oldham coupling 36, the compression of fluid occurs according to the principles illustrated by FIGS. 1A through 1D and the force F is exerted on the orbiting scroll 29 as shown in FIG. 8. In FIG. 8, a component F t of the force F is the thrust load (axial load), and a component F r θ is the radial load. As is clear from FIG. 7, the radial load F r θ is a composite force of the tangential force F.sub.θ and the radial force F r , and hence can be represented by ##EQU4##
As shown in FIG. 5, the relative movement of the point A on the orbiting scroll shaft 30 to the point C on the eccentric shaft 22 is small, and thus the thrust bearings 70 provided in the orbiting scroll 29 and the eccentric shaft 22 undergo only a very small relative movement. In more detail, the circular movement has a radius equal to the distance e between O 2 and O 3 ; the smaller the distance e, the smaller the amount of relative movement. Further, there is a relative movement caused by the driven eccentric ring mechanism 28 when rotated through the minute angle Δθ indicated in FIG. 7. However, this relative movement is very small, and thus the relative movements of the orbiting scroll 29 and the eccentric shaft 22 are very small. Therefore, the thrust force F t indicated in FIG. 8 is transmitted through the outer periphery of the lower surface of the orbiting scroll 29 to the thrust bearing 70 of the eccentric shaft 22. The small relative movement between the outer periphery of the lower surface of the orbiting scroll 29 and the thrust bearing 70 as mentioned above is one of the important features of the present invention. Further, since the eccentric shaft 22 is provided at the opposed ends thereof with complementarily configured structures including the stationary scroll and the orbiting scroll, the thrust forces F t acting on the orbiting scrolls 29 and 120 cancel one another and no force is exerted on the eccentric shaft 22 (see FIG. 3).
In order to dynamically stabilize the orbiting scroll 29, as shown in FIG. 8, the vector of the composite force F must be inside the outer diameter of the thrust bearing 70. In order to achieve this, the outer diameter D of the thrust bearing 70 should be as close as possible to the outer diameter of the orbiting scroll 29.
When the orbiting scroll 29 operates stably as shown in FIG. 8, gas to be compressed is introduced through the intake pipe 47 connected to the intake port 46 to the suction chamber 48 and then to the compression chambers 49 where it is compressed. After being compressed, it is discharged through the discharge port 50 and the discharge pipe 51, at which point the compression cycle is complete.
Lubricating oil 63 is sucked by the pump 64 through the filter 68 and the suction pipe 67 and supplied through the oil supply port 66 to the various sliding components of the machine. The lubricating oil, after lubricating the sliding components within the housing 37, is returned through the return oil port 45 formed in the gear box 59 to the oil tank 62. The oil throwers 69 provided in the housing 37 function to prevent excess amounts of lubricating oil from being fed to the suction chamber 48.
Although, in the above described embodiment, the crankshaft 20 is driven through a gearing arrangement, it is possible to drive the crankshaft 20 directly from an electric motor mounted in the housing of the compressor. That is, instead of the driven gears 53, the rotor of the electric motor is arranged in the same location and the stator is secured to the housing 37. Upon supplying electric power to the motor, the rotor rotates the crankshaft to perform the compression operation. In such case, it may be possible to make the compressor itself smaller because the motor is provided in the housing.
FIGS. 9 and 10 show two respective further embodiments of the present invention, each of which is composed of a plurality of hydraulic machines, each having a stationary scroll and an orbiting scroll arranged relative to the crankshaft as shown in FIG. 3 to thereby increase the capacity of the scroll-type hydraulic machine. In FIG. 9, a pair of machine units are arranged around the driving gear 56 equiangularly and simultaneously driven by the driving gear 56, which is in turn driven by the driving source 72. In FIG. 10, four machine units are arranged around the driving gear 56 equiangularly and driven simultaneously by the driving gear 56.
It is possible to further increase the capacity of the hydraulic machine by mounting a plurality of driving gears 56 on the driving shaft 57 and driving plural machine units with each of them. Alternatively, it is possible to increase the capacity by providing driving shafts 57 on both sides of the driving source 72 and providing a driving gear 56 on each of the driving shafts.
As described in detail hereinbefore, the present invention provides a scroll-type hydraulic machine in which the thrust forces F t acting on the orbiting scrolls act on opposite sides of the eccentric shaft and to thus cancel one another. Further, the relative movement between the orbiting scroll and the eccentric shaft is minimized, resulting in an improvement of the mechanical reliability of the hydraulic machine. Furthermore, since the orbiting scrolls are arranged at the opposed ends of the eccentric shaft and driven individually through respective driven eccentric ring mechanisms, the orbiting scroll can be easily assembled with the stationary scroll. Also, good sealing of the radial gap between the orbiting scroll and the stationary scroll is obtained.
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A scroll-type hydraulic machine having a first stationary scroll with a first scroll wrap, a first orbiting scroll with a second scroll wrap on one surface thereof interleaved with the first scroll wrap, a first orbiting scroll shaft on the other surface of the first orbiting scroll, a second stationary scroll having a third scroll wrap, a second orbiting scroll having a fourth scroll wrap on one surface interleaved with the third scroll wrap, a second orbiting scroll shaft provided on the other surface of the second orbiting scroll, and a crank mechanism. The crank mechanism includes a rotatably driven crankshaft having an eccentric through-hole extending lengthwise therethrough, an eccentric shaft rotatably supported by bearings in the eccentric through-hole, and first and second eccentric ring mechanisms. Each eccentric ring mechanism is provided at one end of the eccentric shaft and is rotatable with respect thereto. The orbiting scroll shafts are driven in an orbital pattern through the respective eccentric ring mechanisms.
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FIELD OF THE INVENTION
[0001] The present invention relates to heat exchange generally and more particularly to sterilization of food products using highly efficient heat exchangers.
BACKGROUND OF THE INVENTION
[0002] The following U.S. Pat. Nos. of the applicant are related to the subject matter of the present invention: 6,158,504; 5,928,699, 5,670,198 and 5,768,472.
SUMMARY OF THE INVENTION
[0003] The present invention seeks to provide an improved heat exchanger and improved pasteurized and sterilized food products realized by use of the improved heat exchanger.
[0004] There is thus provided, in accordance with a preferred embodiment of the present inventions a vacuum heat exchange system including:
[0005] a container partially filled with a liquid and maintained under a vacuum;
[0006] a first heat exchanger disposed in the liquid in the container, the first heat exchanger receiving, a first fluid material, heating the liquid and thereby cooling the first fluid material; and
[0007] a second heat exchanger disposed outside of the liquid in the container, the second heat exchanger receiving a second fluid material and being heated by vapors of the liquid, thereby heating the second fluid material,
[0008] at least one of the first and second heat exchangers including an agitator for agitating, the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0009] Preferably, the first heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Alternatively, the second heat exchanger includes an agitator for agitating the second fluid material passing therethrough to enhance heat exchange generally throughout the second fluid material. Additionally or alternatively, both of the first and second heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0010] In accordance with a preferred embodiment of the present invention, at least one of the first and second heat exchangers includes a scraped surface heat exchanger.
[0011] Additionally, the vacuum heat exchange system also includes an electroheater for heating the first fluid material prior to receipt thereof by the first heat exchanger. Alternatively, the vacuum heat exchange system also includes an electroheater for receiving the second fluid material from the second heat exchanger.
[0012] In accordance with a preferred embodiment of the present invention, the first and second fluid materials are the same material at different temperatures and the vacuum heat exchange system also includes an electroheater for heating the first fluid material prior to receipt thereof by the first heat exchanger and the first fluid material is received by the electroheater from the second heat exchanger.
[0013] There is also provided, in accordance with a preferred embodiment of the present invention, a material treatment system including:
[0014] an electroheater operative to rapidly heat a first fluid material; and
[0015] a vacuum heat exchange subsystem operative to rapidly cool the first fluid material following electroheating thereof, the vacuum heat exchange subsystem including:
[0016] a container partially filled with a liquid and maintained under a vacuum;
[0017] a first heat exchanger disposed in the liquid in the container, the first heat exchanger receiving the first fluid material, heating the liquid and thereby cooling the first fluid material; and
[0018] a second heat exchanger disposed outside of the liquid in the container, the second heat exchanger receiving a second fluid material and being heated by vapors of the liquid, thereby heating the second fluid material,
[0019] at least one of the first and second heat exchangers including an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0020] Preferably, the first heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Alternatively, the second heat exchanger includes an agitator for agitating the second fluid material passing therethrough to enhance heat exchange generally throughout the second fluid material Additionally or alternatively, both of the first and second heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0021] In accordance with a preferred embodiment of the present invention, at least one of the first and second heat exchangers includes a scraped surface heat exchanger.
[0022] In another preferred embodiment of the present invention the electroheater supplies the first fluid material to a holding tank, prior to receipt of the first fluid material by the first heat exchanger. Alternatively or additionally, the electroheater receives the second fluid material from the second heat exchanger.
[0023] In accordance with still another preferred embodiment of the present invention, the first and second fluid materials are the same material at different temperatures and the electroheater heats the first fluid material prior to receipt thereof by the first heat exchanger and the first fluid material is received by the electroheater from the second heat exchanger.
[0024] There is additionally provided, in accordance with a preferred embodiment of the present invention, a material treatment system including:
[0025] electroheater operative to rapidly heat a first fluid material;
[0026] a first vacuum heat exchange subsystem operative to rapidly cool the first fluid material following electroheating thereof, the first vacuum heat exchange subsystem including:
[0027] a container partially filled with a liquid and maintained under a vacuum;
[0028] a first heat exchanger disposed in the liquid in the container, the first heat exchanger receiving the first fluid material, heating the liquid and thereby cooling the first fluid material; and
[0029] a second heat exchanger disposed outside of the liquid in the container, the second heat exchanger receiving a second fluid material and being heated by vapors of the liquid, thereby heating the second fluid material,
[0030] at least one of the first and second heat exchangers including an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material; and
[0031] a second vacuum heat exchange subsystem operative to preheat the first fluid material prior to electroheating thereof, the second vacuum heat exchange subsystem including:
[0032] a container partially filled with a liquid and maintained under a vacuum;
[0033] a third heat exchanger disposed in the liquid in the container, the third heat exchanger receiving a third fluid material, heating the liquid and thereby cooling the third fluid material; and
[0034] a fourth heat exchanger disposed outside of the liquid in the container, the fourth heat exchanger receiving the first fluid material and being heated by vapors of the liquid, thereby heating the first fluid material,
[0035] at least one of the third and fourth heat exchangers including an agitator for agitating, the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0036] Preferably, the first heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Alternatively, the second heat exchanger includes an agitator for agitating the second fluid material passing therethrough to enhance heat exchange generally throughout the second fluid material. Additionally or alternatively, both of the first and second heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0037] In accordance with a preferred embodiment of the present invention, the third heat exchanger includes an agitator for agitating the third fluid material passing therethrough to enhance heat exchange generally throughout the third fluid material. Alternatively, the fourth heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Additionally or alternatively, both of the third and fourth heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0038] In accordance with a preferred embodiment of the present invention, at least one of the first and second heat exchangers includes a scraped surface heat exchanger. Additionally or alternatively, at least one of the third and fourth heat exchangers includes a scraped surface heat exchanger.
[0039] In another preferred embodiment of the present invention, the electroheater supplies the first fluid material to a holding tank, prior to receipt of the first fluid material by the first heat exchanger.
[0040] There is further provided, in accordance with a preferred embodiment of the present invention, a packaged food product characterized in:
[0041] having a viscosity exceeding approximately 5,000 centipoise;
[0042] being sterilized; and
[0043] being aseptically packaged.
[0044] Preferably, the packaged food product has a pH exceeding approximately 4.5.
[0045] There is yet further provided, in accordance with a preferred embodiment of the present invention, a packaged humus food product characterized in:
[0046] being sterilized; and
[0047] being aseptically packaged.
[0048] There is still further provided, in accordance with a preferred embodiment of the present invention, a packaged egg food product characterized in:
[0049] being sterilized; and
[0050] being aseptically packaged.
[0051] There is additionally provided, in accordance with a preferred embodiment of the present invention, a packaged egg food product characterized in:
[0052] being sterilized; and
[0053] being aseptically filled and sealed following sterilization and cooling thereof.
[0054] Preferably, the packaged egg food product is coagulated.
[0055] There is further provided, in accordance with a preferred embodiment of the present invention, a packaged egg food product characterized in:
[0056] being pasteurized to at least 75 degrees Centigrade;
[0057] being aseptically filled and sealed following pasteurization and cooling thereof; and
[0058] being liquid.
[0059] There is also provided, in accordance with a preferred embodiment of the present invention, a vacuum heat exchange method including:
[0060] partially filling a container maintained under a vacuum with a liquid;
[0061] receiving a first fluid material in a first heat exchanger disposed in the liquid in the container, heating the liquid and thereby cooling the first fluid material; and
[0062] receiving a second fluid material in a second heat exchanger disposed outside of the liquid in the container, heating the second heat exchanger by vapors of the liquid, thereby heating the second fluid material,
[0063] where at least one of the first and second heat exchangers includes an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0064] Preferably, the first heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Alternatively, the second heat exchanger includes an agitator for agitating the second fluid material passing therethrough to enhance heat exchange generally throughout the second fluid material. Additionally or alternatively, both of the first and second heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0065] In accordance with a preferred embodiment of the present invention, at least one of the first and second heat exchangers includes a scraped surface heat exchanger.
[0066] In another preferred embodiment of the present invention, the vacuum heat exchange method also includes heating the first fluid material in an electroheater prior to receipt thereof by the first heat exchanger. Additionally or alternatively, the vacuum heat exchange method also includes receiving the second fluid material into an electroheater from the second heat exchanger.
[0067] In yet another preferred embodiment of the present invention, the first and second fluid materials are the same material at different temperatures and the vacuum heat exchange method also includes:
[0068] receiving the first fluid material from the second heat exchanger; and
[0069] heating the first fluid material using an electroheater prior to receipt thereof by the first heat exchanger.
[0070] There is further provided, in accordance with a preferred embodiment of the present invention, a material treatment method including:
[0071] rapidly heating a first fluid material using an electroheater; and
[0072] rapidly cooling the first fluid material following electroheating thereof by:
[0073] partially filling a container maintained under a vacuum with a liquid;
[0074] receiving, the first fluid material in a first heat exchanger disposed in the liquid in the container, heating the liquid and thereby cooling the first fluid material; and
[0075] receiving a second fluid material in a second heat exchanger disposed outside of the liquid in the container, heating the second heat exchanger by vapors of the liquid, thereby heating the second fluid material,
[0076] where at least one of the first and second heat exchangers includes an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0077] Preferably, the first heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Alternatively, the second heat exchanger includes an agitator for agitating the second fluid material passing therethrough to enhance heat exchange generally throughout the second fluid material. Additionally or alternatively, both of the first and second heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0078] In accordance with a preferred embodiment of the present invention, at least one of the first and second heat exchangers includes a scraped surface heat exchanger.
[0079] In another preferred embodiment of the present invention, the vacuum heat exchange method also includes supplying the first fluid material to a holding tank from the electroheater prior to receiving the first fluid material in the first heat exchanger. Additionally or alternatively, the vacuum heat exchange method also includes receiving the second fluid material into the electroheater from the second heat exchanger.
[0080] In still another preferred embodiment of the present invention, the first and second fluid materials are the same material at different temperatures and the vacuum heat exchange method also includes:
[0081] receiving the first fluid material by the electroheater from the second heat exchanger; and
[0082] heating the first fluid material in the electroheater prior to receipt thereof by the first heat exchanger.
[0083] There is yet further provided, in accordance with a preferred embodiment of the present invention, a material treatment method including:
[0084] rapidly heating a first fluid material using an electroheater; and
[0085] rapidly cooling the first fluid material following electroheating thereof by:
[0086] partially filling a container maintained under a vacuum with a liquid;
[0087] receiving a first fluid material in a first heat exchanger disposed in the liquid in the container, heating the liquid and thereby cooling the first fluid material; and
[0088] receiving a second fluid material in a second heat exchanger disposed outside of the liquid in the container, heating the second heat exchanger by vapors of the liquid, thereby heating the second fluid material,
[0089] where at least one of the first and second heat exchangers includes an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material; and
[0090] preheating the first fluid material prior to electroheating thereof by:
[0091] partially filling a container maintained under a vacuum with a liquid;
[0092] receiving a third fluid material in a third heat exchanger disposed in the liquid in the container, heating the liquid and thereby cooling the third fluid material; and
[0093] receiving the first fluid material in a fourth heat exchanger disposed outside of the liquid in the container, heating the fourth heat exchanger by vapors of the liquid, thereby heating the first fluid material,
[0094] where at least one of the third and fourth heat exchangers includes an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0095] Preferably, the first heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material. Alternatively, the second heat exchanger includes an agitator for agitating the second fluid material passing therethrough to enhance heat exchange generally throughout the second fluid material. Additionally or alternatively, both of the first and second heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0096] In accordance with a preferred embodiment of the present invention, the third heat exchanger includes an agitator for agitating the third fluid material passing therethrough to enhance heat exchange generally throughout the third fluid material. Alternatively, the fourth heat exchanger includes an agitator for agitating the first fluid material passing therethrough to enhance heat exchange generally throughout the first fluid material Additionally or alternatively, both of the third and fourth heat exchangers include an agitator for agitating the fluid material passing therethrough to enhance heat exchange generally throughout the fluid material.
[0097] Preferably, at least one of the first and second heat exchangers includes a scraped surface heat exchanger. Additionally or alternatively, at least one of the third and fourth heat exchangers includes a scraped surface heat exchanger.
[0098] In another preferred embodiment of the present invention, the material treatment method includes supplying the first fluid material to a holding tank from the electroheater prior to receiving, the first fluid material in the first heat exchanger.
[0099] There is additionally provided, in accordance with a preferred embodiment of the present invention, a method of preparing a packaged food product including:
[0100] producing a food product having a viscosity exceeding approximately 5,000 centipoise;
[0101] sterilizing the food product; and
[0102] aseptically packaging the food product.
[0103] Preferably, the packaged food product has a pH exceeding approximately 4.5.
[0104] There is further provided, in accordance with a preferred embodiment of the present invention, a method of preparing a packaged humus food product including:
[0105] sterilizing the humus food product; and
[0106] aseptically packaging the humus food product.
[0107] There is still further provided, in accordance with a preferred embodiment of the present invention, a method of preparing a packaged egg food product including:
[0108] sterilizing the egg food product; and
[0109] aseptically packaging the egg food product.
[0110] There is yet further provided, in accordance with a preferred embodiment of the present invention, a method of preparing a packaged egg food product including:
[0111] sterilizing the egg food product;
[0112] cooling the egg food product; and
[0113] aseptically filling and sealing the egg food product in a package.
[0114] Preferably, the egg food product is coagulated.
[0115] There is additionally provided, in accordance with a preferred embodiment of the present invention, a method of preparing a packaged liquid egg food product including:
[0116] pasteurizing the liquid egg food product to at least 75 degrees Centigrade;
[0117] cooling the liquid egg food product; and
[0118] aseptically filling and sealing the liquid egg food product in a package.
BRIEF DESCRIPTION OF THE DRAWINGS
[0119] The present invention will be understood and appreciated more fully from the following detailed description, taken in conjunction with the drawings in which:
[0120] [0120]FIG. 1A is a simplified sectional illustration of a vacuum heat exchange system constructed and operative in accordance with a preferred embodiment of the present invention;
[0121] [0121]FIG. 1B is a sectional illustration of a portion of an agitator operative in accordance with a preferred embodiment of the present invention;
[0122] [0122]FIG. 2 is a simplified sectional illustration of a vacuum heat exchange system constructed and operative in accordance with another preferred embodiment of the present invention;
[0123] [0123]FIG. 3 is a simplified sectional illustration of a vacuum heat exchange system constructed and operative in accordance with still another preferred embodiment of the present invention;
[0124] [0124]FIG. 4 is a simplified sectional illustration of a material treatment system and methodology constructed and operative in accordance with a preferred embodiment of the present invention;
[0125] [0125]FIG. 5 is a simplified sectional illustration of a material treatment system and methodology constructed and operative in accordance with another preferred embodiment of the present invention;
[0126] [0126]FIG. 6 is a temperature-time graph illustrating aspects of operation of embodiments of the present invention;
[0127] [0127]FIG. 7 is a simplified illustration of an electroheating system useful with highly viscous materials and products containing particles; and
[0128] [0128]FIG. 8 is a simplified sectional illustration of a material treatment system and methodology constructed and operative in accordance with yet another preferred embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0129] Reference is now made to FIGS. 1A and 1B, which are simplified sectional illustrations of a vacuum heat exchange system constructed and operative in accordance with a preferred embodiment of the present invention As seen in FIG. 1A, the vacuum heat exchange system preferably includes a thermally insulated enclosure 100 , the interior of which communicates with the ambient atmosphere via a vacuum pump 102 , which preferably maintains the interior of enclosure 100 at subatmospheric pressure, typically about 29″ of mercury.
[0130] Enclosure 100 is partially filled with a cooling liquid 104 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 100 . A heated fluid material 106 , such as a heated food product which has undergone electroheating, is preferably supplied to a conduit 108 which extends through the liquid 104 . As the heated fluid material 106 passes through the conduit 108 , in thermal contact with the walls thereof, it becomes cooled by evaporating the liquid 104 . The cooled fluid material then flows from the conduit 108 .
[0131] In accordance with a preferred embodiment of the present invention, an agitator 110 , typically in the form of an elongate shaft 112 , having outwardly extending vanes 114 , is disposed in conduit 108 , and rotated therein about an axis 116 , as by a motor 118 , to provide enhanced uniformity of thermal contact between the heated fluid material 106 and the walls of the conduit 108 . A preferred type of conduit 108 and agitator 110 are together known as a scraped surface heat exchanger.
[0132] In accordance with a preferred embodiment of the present invention a cooling liquid 120 , preferably water, is caused to pass through a conduit 122 , preferably a coil, which extends through enclosure 100 , above the level of the cooling liquid 104 . The temperature of the cooling liquid 120 is preferably sufficiently low as to cause vapors of the cooling, liquid 104 to condense upon contact with the outer walls of conduit 122 and to fall downward into cooling liquid 104 , as drops 124 .
[0133] Reference is now made to FIG. 2, which is a simplified sectional illustration of a vacuum heat exchange system constructed and operative in accordance with another preferred embodiment of the present invention. As seen in FIG. 2, the vacuum heat exchange system preferably includes a thermally insulated enclosure 200 , the interior of which communicates with the ambient atmosphere via a vacuum pump 202 , which preferably maintains the interior of enclosure 200 at subatmospheric pressure, typically about 29″ of mercury.
[0134] Enclosure 200 is partially filled with a cooling liquid 204 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 200 . A heated liquid 206 , such as heated water, is preferably supplied to a conduit 208 , preferably a coil, which extends through the liquid 204 . As the heated liquid 206 passes through the conduit 208 , in thermal contact with the walls thereof, it heats the liquid 204 , generating heated vapor 214 .
[0135] In accordance with a preferred embodiment of the present invention, a cool fluid material 210 is caused to pass through a conduit 212 , which extends through enclosure 200 , above the level of the cooling liquid 204 . As the cool fluid material 210 passes through the conduit 212 , in thermal contact with the walls thereof, it becomes heated by the heated vapor 214 from liquid 204 . The heated fluid material then flows from the conduit 212 .
[0136] In accordance with a preferred embodiment of the present invention, an agitator 220 , typically in the form of an elongate shaft 222 , having outwardly extending vanes 224 , is disposed in conduit 212 , and rotated therein about an axis 226 , as by a motor 228 , to provide enhanced uniformity of thermal contact between the cool fluid material 210 and the walls of the conduit 212 . A preferred type of conduit 212 and agitator 220 are together known as a scraped surface heat exchanger.
[0137] Reference is now made to FIG. 3, which is a simplified sectional illustration of a vacuum heat exchange system constructed and operative in accordance with still another preferred embodiment of the present invention. As seen in FIG. 3, the vacuum heat exchange system preferably includes a thermally insulated enclosure 300 , the interior of which communicates with the ambient atmosphere via a vacuum pump 302 , which preferably maintains the interior of enclosure 300 at subatmospheric pressure, typically about 29″ of mercury.
[0138] Enclosure 300 is partially filled with a cooling liquid 304 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 300 . A heated fluid material 306 , such as a heated food product which has undergone electroheating, is preferably supplied to a conduit 308 , which extends through the liquid 304 . As the heated fluid material 306 passes through the conduit 308 , in thermal contact with the walls thereof, it becomes cooled by evaporating the liquid 304 , thereby heating the liquid 304 , generating heated vapor 309 . The cooled fluid material then flows from the conduit 308 .
[0139] In accordance with a preferred embodiment of the present invention, an agitator 310 , typically in the form of an elongate shaft 312 , having outwardly extending vanes 314 , is disposed in conduit 308 , and rotated therein about an axis 316 , as by a motor 318 , to provide enhanced uniformity of thermal contact between the heated fluid material 306 and the walls of the conduit 308 . A preferred type of conduit 308 and agitator 310 are together known as a scraped surface heat exchanger.
[0140] In accordance with a preferred embodiment of the present invention a cool fluid material 320 , such as a food product which is to be electroheated, is caused to pass through a conduit 322 , which extends through enclosure 300 , above the level of the cooling liquid 304 . The temperature of the cool fluid material 320 is preferably sufficiently low as to cause vapors of the cooling liquid 304 to condense upon contact with the outer walls of conduit 322 and to fall downward into cooling liquid 304 , as drops 324 . As the cool fluid material 320 passes through the conduit 322 , in thermal contact with the walls thereof, it becomes heated by the heated vapor 309 from liquid 304 . The heated fluid material then flows from the conduit 322 .
[0141] In accordance with a preferred embodiment of the present invention, an agitator 330 , typically in the form of an elongate shaft 332 , having outwardly extending vanes 334 , is disposed in conduit 322 , and rotated therein about an axis 336 , as by a motor 338 , to provide enhanced uniformity of thermal contact between the cool fluid material 320 and the walls of the conduit 322 . A preferred type of conduit 322 and agitator 330 are together known as a scraped surface heat exchanger.
[0142] Reference is now made to FIG. 4, which is a simplified sectional illustration of a material treatment system and methodology constructed and operative in accordance with a preferred embodiment of the present invention. As seen in FIG. 4, the system and methodology of FIG. 4 typically comprises a preheating subsystem 400 , such as that shown in FIG. 2 and described hereinabove, which receives a fluid material, such as a food product, to be preheated and preheats it to a desired temperature, an electroheater 402 , which heats the preheated fluid material to a predetermined temperature for a predetermined time and a cooling subsystem 404 , such as that shown in FIG. 1A and described hereinabove, which receives the electroheated fluid material, typically from a holding tank 406 , cools the fluid material and supplies it to an aseptic filling mechanism 408 after it has been further cooled in conventional cooler 409 , thereby producing a packaged product having new and superior characteristics.
[0143] Pre-heating, subsystem 400 preferably comprises a thermally insulated enclosure 410 , the interior of which communicates with the ambient atmosphere via a vacuum pump 412 , which preferably maintains the interior of enclosure 410 at subatmospheric pressure, typically about 29″ of mercury.
[0144] Enclosure 410 is partially filled with a liquid 414 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 410 . A heated liquid 416 , such as heated water, is preferably supplied to a conduit 418 , preferably a coil, which extends through the liquid 414 . As the heated liquid 416 passes through the conduit 418 , in thermal contact with the walls thereof, it heats the liquid 414 , generating heated vapor 419 .
[0145] In accordance with a preferred embodiment of the present invention a cool fluid material to be preheated 420 , such as a food product, is caused to pass through a conduit 422 , which extends through enclosure 410 , above the level of the cooling liquid 414 . As the cool fluid material 420 passes through the conduit 422 , in thermal contact with the walls thereof, it becomes heated by the heated vapor 419 from liquid 414 . The heated fluid material then flows from the conduit 422 .
[0146] In accordance with a preferred embodiment of the present invention, an agitator 430 , typically in the form of an elongate shaft 432 , having outwardly extending vanes 434 , is disposed in conduit 422 , and rotated therein about an axis 436 , as by a motor 438 , to provide enhanced uniformity of thermal contact between the fluid material 420 and the walls of the conduit 422 . A preferred type of conduit 422 and agitator 430 are together known as a scraped surface heat exchanger.
[0147] The pre-heated output of the scraped surface heat exchanger is preferably supplied to electroheater 402 , which is operative to heat the pre-heated fluid material to an elevated temperature in a very short time. Suitable electroheaters are described in applicant's U.S. Pat. Nos. 6,304,718, 6,088,509; 5,863,580; 5,768,472; 5,636,317; 5,609,900; 5,607,613; 5,583,960; 5,415,882; 5,290,583 and 4,739,140, the disclosures of which are hereby incorporated by reference. A preferred embodiment of an electroheater is described hereinbelow with reference to FIG. 7.
[0148] The heated output of electroheater 402 is preferably supplied via a holding tank 406 to cooling subsystem 404 . Cooling subsystem 404 preferably comprises a thermally insulated enclosure 440 , the interior of which communicates with the ambient atmosphere via a vacuum pump 442 , which preferably maintains the interior of enclosure 440 at subatmospheric pressure, typically about 29″ of mercury.
[0149] Enclosure 440 is partially filled with a cooling liquid 444 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 440 . The electroheated fluid material 446 is preferably supplied to a conduit 448 , which extends through the liquid 444 . As the electroheated fluid material 446 passes through the conduit 448 , in thermal contact with the walls thereof it becomes cooled by evaporating the liquid 444 .
[0150] In accordance with a preferred embodiment of the present invention, an agitator 450 , typically in the form of an elongate shaft 452 , having outwardly extending vanes 454 , is disposed in conduit 448 , and rotated therein about an axis 456 , as by a motor 458 , to provide enhanced uniformity of thermal contact between the electroheated fluid material 446 and the walls of the conduit 448 . A preferred type of conduit 448 and agitator 450 are together known as a scraped surface heat exchanger.
[0151] In accordance with a preferred embodiment of the present invention a cooling liquid 460 , preferably water, is caused to pass through a conduit 462 , preferably a coil, which extends through enclosure 440 , above the level of the cooling liquid 444 . The temperature of the cooling liquid 460 is preferably sufficiently low as to cause vapors of the cooling liquid 444 to condense upon contact with the outer walls of conduit 462 and to fall downward into cooling liquid 444 , as drops 464 .
[0152] The cooled output of cooling subsystem 404 is preferably supplied to conventional cooler 409 for further cooling prior to being sent to aseptic filling mechanism 408 which produces a packaged product having enhanced shelf life and storage temperature insensitivity.
[0153] Reference is now made to FIG. 5, which is a simplified sectional illustration of a material treatment system and methodology constructed and operative in accordance with another preferred embodiment of the present invention. As seen in FIG. 5, the system and methodology of FIG. 5 typically comprises a preheating and cooling vacuum heat exchange subsystem 500 , such as that shown in FIG. 3 and described hereinabove which receives a fluid material, such as a food product, to be preheated and preheats it to a desired temperature, an electroheater 502 , which rapidly heats the fluid material to a predetermined temperature for a predetermined time and then supplies it to a holding tank 504 and thence back to subsystem 500 for rapid cooling thereof, and an aseptic filling mechanism 506 , which receives the cold fluid material via a conventional cooler 508 and produces a packaged product having new and superior characteristics of shelf life and temperature insensitivity.
[0154] As seen in FIG. 5, the vacuum heat exchange system preferably includes a thermally insulated enclosure 510 , the interior of which communicates with the ambient atmosphere via a vacuum pump 512 , which preferably maintains the interior of enclosure 510 at subatmospheric pressure, typically about 29″ of mercury.
[0155] Enclosure 510 is partially filled with a cooling liquid 514 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 510 .
[0156] In accordance with a preferred embodiment of the present invention a fluid material 520 , such as a food product which is to be electroheated, is caused to pass through a conduit 522 , which extends through enclosure 510 , above the level of the cooling liquid 514 . The temperature of the fluid material 520 is preferably sufficiently low as to cause vapors of the cooling liquid 514 to condense upon contact with the outer walls of conduit 522 and to fall downward into cooling liquid 514 , as drops 524 . As the cool fluid material 520 passes through the conduit 522 , in thermal contact with the walls thereof, it becomes heated by the heated vapor 526 from liquid 514 . The heated fluid material then flows from the conduit 522 .
[0157] In accordance with a preferred embodiment of the present invention, an agitator 530 , typically in the form of an elongate shaft 532 , having outwardly extending vanes 534 , is disposed in conduit 522 , and rotated therein about an axis 536 , as by a motor 538 , to provide enhanced uniformity of thermal contact between the fluid material 520 and the walls of the conduit 522 . A preferred type of conduit 522 and agitator 530 are together known as a scraped surface heat exchanger.
[0158] The preheated output of conduit 522 is preferably supplied to electroheater 502 , which is operative to heat the pre-heated fluid material to an elevated temperature in a very short time. Suitable electroheaters are described in applicant's U.S. Pat. Nos. 6,304,718; 6,088,509; 5,863,580; 5,768,472; 5,636,317; 5,609,900; 5,607,613; 5,583,960; 5,415,882; 5,290,583 and 4,739,140, the disclosures of which are hereby incorporated by reference. A preferred embodiment of an electroheater is described hereinbelow with reference to FIG. 7.
[0159] The heated output of electroheater 502 is preferably supplied via holding tank 504 and a pump 540 to a conduit 542 , which extends through the liquid 514 . As the heated fluid material passes through the conduit 542 , in thermal contact with the walls thereof, it becomes cooled by evaporating the liquid 514 .
[0160] In accordance with a preferred embodiment of the present invention, an agitator 550 , typically in the form of an elongate shaft 552 , having outwardly extending vanes 554 , is disposed in conduit 542 , and rotated therein about an axis 556 , as by a motor 558 , to provide enhanced uniformity of thermal contact between the heated fluid material and the walls of the conduit 542 . A preferred type of conduit 542 and agitator 550 are together known as a scraped surface heat exchanger.
[0161] Aseptic filling mechanism 506 receives the cooled fluid material from conduit 542 after it has been further cooled in conventional cooler 508 and produces a packaged product having new and superior characteristics of shelf life and temperature insensitivity.
[0162] Reference is now made to FIG. 6, which is a temperature-time graph illustrating operation of the present invention for processing food products, such as humus, in accordance with preferred embodiments of the present invention, such as those shown and described hereinabove with particular reference to FIGS. 4 and 5.
[0163] As seen in FIG. 6, the food product is rapidly preheated by the first heat exchanger, such as heat exchanger 400 (FIG. 4) or 500 (FIG. 5), typically from a temperature of 40 degrees C. to a temperature of 85 degrees C. in approximately 40 seconds. Thereafter, the food product is heated to about 130 degrees C. by the electroheater, such as electroheater 402 (FIG. 4) or 502 (FIG. 5), in a fraction of a second. It is then cooled to a temperature of 85 degrees C. by the vacuum heat exchanger, such as heat exchanger 404 (FIG. 4) or 500 (FIG. 5), in approximately 40 seconds, after being held for a period of time in a holding tank at 130 degrees C. It is then preferably cooled further from a temperature of 85 degrees C. to approximately 40 degrees C. or below before being aseptically packaged.
[0164] It has been found by the applicant that humus which has been sterilized by rapid heating and cooling as described hereinabove is characterized by having extremely long shelf life without requiring refrigeration and by having substantial tolerance to temperature abuse.
[0165] It has also been found by the applicant that liquid egg which has been pasteurized by rapid heating, typically to temperatures in the range of 75-85 degrees C., and cooling, similar to that described hereinabove, is characterized by having extremely long refrigerated shelf life and by having tolerance to temperature abuse.
[0166] Reference is now made to FIG. 7, which is a simplified illustration of an electroheater which is particularly suitable for use with viscous products, such as humus. As seen in FIG. 7, a viscous product, such as humus, typically having a viscosity in the range of 20,000 centipoise is supplied at a high rate, typically in the range of 1,500 to 5,000 liters/hour through an electrically insulative conduit 700 , in the direction indicated by arrows 702 .
[0167] Three conductive electrodes, 704 , 706 and 708 are preferably arranged in spaced mutual arrangement along conduit 700 . Each electrode preferably includes a hollow disc, the interior of which communicates with the interior of conduit 700 by means of a plurality of downstreamly directed angled openings 710 . A relatively small quantity of a conductive fluid, typically 1 to 5 liters/hour per electrode, is supplied to conduit 700 from supply conduits 712 , 714 and 716 , which output to respective electrodes 704 , 706 and 708 and thence via openings 710 to conduit 700 . It is seen that preferably electrodes 704 and 708 are grounded, while electrode 706 receives AC current at high voltage, preferably at mains frequencies.
[0168] The arrangement of FIG. 7 is preferred for electroheating of relatively viscous materials, since it generally prevents physical contact between the viscous materials and electrodes 704 , 706 and 708 . Also, there are no obstacles to flow and no change of diameter, so the velocity is high and uniform.
[0169] Reference is now made to FIG. 8, which is a simplified sectional illustration of a material treatment system and methodology constructed and operative in accordance with yet another preferred embodiment of the present invention.
[0170] As seen in FIG. 8, the material treatment system and methodology of FIG. 8 employs a thermally insulated enclosure 800 , the interior of which is in communication with the ambient atmosphere via a vacuum pump 802 , which preferably maintains the interior of enclosure 800 at subatmospheric pressure, typically about 29″ of mercury.
[0171] Enclosure 800 is partially filled with a cooling liquid 804 , preferably water, which boils at room temperature at the subatmospheric pressure of 29″ of mercury within enclosure 800 . A scraped surface heat exchanger 806 is disposed in enclosure 800 and includes a conduit 808 , part of which extends through the liquid 804 . Heated fluid material 810 , such as an electroheated food product, passes through the conduit 808 , in thermal contact with the walls thereof, and becomes cooled by evaporating the liquid 804 .
[0172] In accordance with a preferred embodiment of the present invention, an agitator 812 , typically in the form of an elongate shaft 814 , having outwardly extending vanes 816 , is disposed in conduit 808 , and rotated therein about an axis 818 , as by a motor 820 , to provide enhanced uniformity of thermal contact between the heated fluid material 810 and the walls of the conduit 808 .
[0173] Disposed inside enclosure 800 above the level of the cooling liquid 804 is a condensing coil 822 . A coolant, such as water, preferably passes through condensing coil 822 .
[0174] The system of FIG. 8 also preferably comprises a reservoir 824 in fluid communication with the interior of enclosure 800 , such as by means of a flexible tube 826 . Reservoir 824 preferably contains cooling liquid 804 which can flow into the interior of enclosure 800 via flexible tube 826 . Another flexible tube 828 is preferably provided to ensure that the vacuum maintained inside enclosure 800 is also maintained inside reservoir 824 . Reservoir 824 is preferably mounted onto a vertical track (not shown) for selectable vertical positioning relative to enclosure 800 , thereby to enable ease of selection of the level of cooling liquid 804 in enclosure 800 . This level effectively controls the amount of cooling produced by the system by determining how much of the scraped surface heat exchanger 806 is disposed in the liquid 804 .
[0175] It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention includes both combinations and subcombinations of the various features described hereinabove as well as variations and modifications which would occur to persons skilled in the art upon reading the specification and which are not in the prior art.
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An improved heat exchange system and methodology, and an improved material treatment system and methodology, based on that heat exchange system, for providing improved pasteurized and sterilized packaged food products is disclosed. Improved pasteurized and sterilized packaged food products produced thereby are also disclosed.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a web butt-joining apparatus and method, and particularly relates to a web butt-joining apparatus and method for joining end portions of a new and an old rolls of thin band-shaped sheet materials (hereinafter, called “web”) of plastic, paper, metal foil and the like in a butted state.
[0003] 2. Description of the Related Art
[0004] In order to join a tail end of an old web and a tip end of a new web in a butted state with high accuracy at the time of joining the webs, the conventional web butt-joining apparatus joins the webs after stopping the line of a coater and a treatment machine having joining apparatuses, or by bringing a web feeding part into a stopping or low-speed state by using an accumulator of the web, namely, by slowing down the web feeding part. However, stopping or slowing down the line each time webs are joined causes the problem of significant reduction in manufacturing efficiency.
[0005] When webs are to be joined while being conveyed without stopping or slowing down the line, the web conveyance is performed at a high speed (100 m/minute or higher), and therefore, when the conventional web butt-joining apparatus is to be caused to respond to the high-speed conveyance of the webs, rapid rise in the speed of the new roll is required, and there is the disadvantage of requiring use of a large-sized motor, and occurrence of weaving to the new roll due to abrupt torque.
[0006] In order to solve this, the present applicant proposes an apparatus corresponding to increase in the speed of web conveyance (for example, see Japanese Patent Application Laid-Open No. 6-171806).
[0007] The web butt-joining apparatus disclosed in Japanese Patent Application Laid-Open No. 6-171806 is a three drum type apparatus including a cutting blade and a member for drawing out a web tip end portion of a new roll, and constituted of a cutting drum capable of rotating at the same speed as the conveyance speed of the web, a cutting and joining drum capable of rotating at the same speed as the conveyance speed of the web, and a joining drum which separably holds the bonding tape and is rotatable at the same speed as the conveyance speed of the web, and is characterized by performing cutting and joining of the web while pinching the tail end of the old roll and the tip end of the new roll with the respective drums, and is described to be capable of solving the above described problem.
SUMMARY OF THE INVENTION
[0008] However, the problems that are not solved in the conventional web butt-joining apparatuses of Japanese Patent Application Laid-Open No. 6-171806 and the like still remain. As the first problem, the construction in which the web is cut by an instant operation by the cutting blade of substantially the same length as the width of the wide web is adopted in the conventional device, and such cutting has the disadvantage of decreasing joining accuracy.
[0009] As the second problem, the conventional apparatuses have the disadvantage of causing chips at the time of cutting the webs. The webs of TAC (Triacetyl Cellulose) and the like are easily torn, and easily cause chips of the webs.
[0010] As the third problem, in the conventional apparatuses, a replacement operation due to wear and breakage (broken blade) of the cutting blades frequently takes place, and there is the disadvantage of reduction in productivity, increase in cost of consumables and the like.
[0011] As the fourth problem, in the conventional apparatuses, the adjusting operation of cutting blades or the like when the thickness, material and the like of the webs change is complicated, and there is the disadvantage of reduction in productivity or the like.
[0012] The present invention is made in view of the above circumstances, and has an object to provide a web butt-joining apparatus and method for butt-joining webs capable of joining an old web and a new web, simplifying a mechanism of the apparatus, enhancing joining accuracy and quality, and reducing cost of consumables, cost of the apparatus, and down time.
[0013] In order to attain the above-described object, the present invention provides a web butt-joining apparatus, characterized by including a turret device that supports an old roll and a new roll on which band-shaped flexible base materials are wound to be capable of being unwound, and is rotatable at every predetermined angle, a cutting drum including a cutting member, which is provided at a cylindrical portion of a peripheral surface with its tip end protruded, forms an inclined angle of 0.5 degrees to 5 degrees with respect to an axial direction of the cylindrical portion, and has substantially the same length as a width of the band-shaped flexible base material, and a holding device that holds a tip end portion of the band-shaped flexible base material of the new roll, and capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, a cutting and joining drum which includes a cutting receiving member of substantially the same length as the width of the band-shaped flexible base material, and a holding device which holds a portion in the vicinity of a tail end portion of the band-shaped flexible base material of the old roll, and is capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base material, and a joining drum which holds a bonding tape to be separable and is capable of rotating at the same speed as the conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, and characterized in that while conveying the band-shaped flexible base material, the web butt-joining apparatus performs cutting and butt-joining of the tail end of the band-shaped flexible base material of the old roll and the tip end of the band-shaped flexible base material of the new roll.
[0014] For this purpose, the present invention provides, in a web butt-joining method for performing cutting and butt-joining of a tail end of a band-shaped flexible base material of an old roll and a tip end of a band-shaped flexible base material wound around a new roll while causing the band-shaped base material wound around the old roll to travel, a web butt-joining method characterized by including the steps of: winding the band-shaped flexible base material of the new roll on a cutting drum, and holding a tip end portion of the band-shaped flexible base material of the new roll by a new web holding device of the cutting drum; winding the band-shaped flexible base material of the old roll on a cutting and joining drum and holding a portion in the vicinity of a tail end portion of the band-shaped flexible base material of the old roll by an old web holding device of the cutting and joining drum; holding a bonding tape at a joining drum; while rotating the cutting and joining drum at the same speed as conveyance speed of the band-shaped flexible base material, and rotating the cutting drum at the same speed as conveyance speed of the band-shaped flexible base material, cutting the band-shaped flexible base material of the old roll and the band-shaped flexible base material of the new roll in an overlapped state by a cutting member which is provided at a cylindrical portion of a peripheral surface of the cutting drum or the cutting and joining drum with its tip end protruded and which forms an inclined angle of 0.5 degrees to 5 degrees with respect to an axial direction of the cylindrical portion; casting away a portion in the vicinity of the tail end portion of the band-shaped flexible base material of the old roll and the tip end portion of the band-shaped flexible base material of the new roll which are cut, and holding the band-shaped flexible base material of the old roll and the band-shaped flexible base material of the new roll on the peripheral surface of the cutting drum or the cutting and joining drum; and bonding the bonding tape held at the joining drum to the band-shaped flexible base material of the old roll and the band-shaped flexible base material of the new roll held at the peripheral surface of the cutting drum or the cutting and joining drum.
[0015] According to the present invention, the cutting member is provided to form an inclined angle of 0.5 degrees to 5 degrees with respect to the axial direction of the cylindrical portion, and therefore, the web is cut so that the cut line advances from one end side of the cutting member to the other end side thereof. Accordingly, cutting accuracy is enhanced by such cutting, and the cut end is further fed to the joining drum in sequence from the one end side to the other end side, as a result of which, joining accuracy is enhanced.
[0016] In order to attain the above described object, the present invention provides a web butt-joining apparatus characterized by including a turret device that supports an old roll and a new roll on which band-shaped flexible base materials are wound to be capable of being unwound, and is rotatable at every predetermined angle, a cutting drum including a cutting member, which is provided at a cylindrical portion with a radius R of a peripheral surface with its tip end protruded with a protruded amount h, forms an inclined angle θ with respect to a radius direction of the cylindrical portion, and has substantially the same length as a width of the band-shaped flexible base material, a cushioning member composed of foaming rubber provided at both sides of the cutting member, and a holding device that holds a tip end portion of the band-shaped flexible base material of the new roll, with the inclined angle θ in the relationship of 20 degrees≧θ≧cos −1 (R/(R+h)), and capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, a cutting and joining drum which includes a cutting receiving member of substantially the same length as the width of the band-shaped flexible base material, and a holding device which holds a portion in the vicinity of a tail end portion of the band-shaped flexible base material of the old roll, and is capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, and a joining drum which holds a bonding tape to be separable and is capable of rotating at the same speed of the conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, and characterized in that while transferring the band-shaped flexible base material, the web butt-joining apparatus performs cutting and butt-joining of the tail end of the band-shaped flexible base material of the old roll and the tip end of the band-shaped flexible base material of the new roll.
[0017] For this purpose, the present invention provides, in a web butt-joining method for performing cutting and butt-joining of a tail end of a band-shaped flexible base material of an old roll and a tip end of a band-shaped flexible base material wound around a new roll while causing the band-shaped base material wound around the old roll, a web butt-joining method including the steps of: winding the band-shaped flexible base material of the new roll on a cutting drum, and holding a tip end portion of the band-shaped flexible base material of the new roll by a new web holding device of the cutting drum; winding the band-shaped flexible base material of the old roll on a cutting and joining drum and holding a portion in the vicinity of a tail end portion of the band-shaped flexible base material of the old roll by an old web holding device of the cutting and joining drum; holding a bonding tape at a joining drum; while rotating the cutting and joining drum at the same speed as conveyance speed of the band-shaped flexible base material, and rotating the cutting drum at the same speed as conveyance speed of the band-shaped flexible base material, cutting the band-shaped flexible base material of the old roll and the band-shaped flexible base material of the new roll in an overlapped state by a cutting member which is provided at a cylindrical portion with a radius R of a peripheral surface of the cutting drum or the cutting and joining drum with its tip end protruded with a protruded amount h and which forms an inclined angle 0 with respect to a radius direction of the cylindrical portion, which is a cutting member with the inclined angle θ being in relationship of 20 degrees≧θ≧cos −1 (R/(R+h)), and cushioning members composed of foaming rubber provided at both sides of the cutting member; casting away a portion in the vicinity of the tail end portion of the band-shaped flexible base material of the old roll and the tip end portion of the band-shaped flexible base material of the new roll which are cut, and holding the band-shaped flexible base material of the old roll and the band-shaped flexible base material of the new roll on the peripheral surface of the cutting drum or the cutting and joining drum; and bonding the bonding tape held at the joining drum to the band-shaped flexible base material of the old roll and the band-shaped flexible base material of the new roll held at the peripheral surface of the cutting drum or the cutting and joining drum.
[0018] According to the present invention, the old web and the new web are cut in the state in which one is overlaid on the other by the cutting member of which tip end is projectingly provided at the cylindrical portion of the peripheral surface of the cutting drum or the cutting and joining drum, and which forms the inclined angle θ in the relationship of 20 degrees≧θ≧cos −1 (R/(R+h)) with respect to the radius direction of the cylindrical portion, and the cushioning members composed of a foaming rubber which are provided at both sides of the cutting member, and therefore the disadvantage of causing chips at the time of cutting the webs can be significantly eliminated.
[0019] Namely, the cutting member forms the inclined angle θ in the relationship of 20 degrees≧θ≧cos −1 (R/(R+h)), and the cushioning members composed of a foaming rubber which are provided at both sides of the cutting member. Therefore, the cutting member bends to form inclination further, the web held by the cushioning members also deforms in the optimum shape, and it can be made difficult to cause chips at the time of cutting the web. The details will be described later.
[0020] In order to attain the above described object, the present invention provides a web butt-joining apparatus, including a turret device that supports an old roll and a new roll on which a band-shaped flexible base materials are wound to be capable of being unwound, and is rotatable at every predetermined angle, a cutting drum including a cutting member block, which is provided at a front surface of a block with its tip end protruded, with a cutting member of substantially the same length as the width of the band-shaped flexible base material embedded therein, a cylindrical portion having a peripheral surface capable of fitting the cutting member block in a recessed portion formed on a front surface to be flush with each other, and a holding device holding a tip end portion of the band-shaped flexible base material of the new roll, and capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, a cutting and joining drum which includes a cutting receiving member of substantially the same length as the width of the band-shaped flexible base material, and a holding device which holds a portion in the vicinity of a tail end portion of the band-shaped flexible base material of the old roll, and is capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, and a joining drum which holds a bonding tape to be separable and is capable of rotating at the same speed as the conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, and characterized in that while transferring the band-shaped flexible base material, the web butt-joining apparatus performs cutting and butt-joining of the tail end of the band-shaped flexible base material of the old roll and the tip end of the band-shaped flexible base material of the new roll.
[0021] According to the present invention, the cutting member provided at the cutting drum is embedded in the block, and the cutting member block is capable of being fitted in the recessed portion formed in the cylindrical portion of the cutting drum surface to be flush with the recessed portion. Accordingly, replacement of the cutting member and fine adjustment of the cutting blade position and the like can be performed by only replacing the cutting member block, the mechanism of the apparatus can be simplified, joining accuracy and quality can be enhanced, and downtime can be reduced.
[0022] In the present invention, it is preferable that Vickers hardness of the cutting receiving member is 1000 or more. When the cutting receiving member on which the cutting blade of the cutting member abuts is hard, and the Vickers hardness is 1000 or more in particular, the trouble of the cutting edge biting the cutting receiving member hardly occurs, and the disadvantage of causing chips when cutting the old web and the new web in the state in which one is overlaid on the other can be significantly reduced.
[0023] In the present invention, it is preferable that a metallizing plating layer of a thickness of 10 to 30 μm is formed on a front surface of the cutting receiving member. With the metallizing plating layer of such a thickness, the disadvantage of the metallizing plating layer curling up and being damaged can be reduced, and the useful life of the cutting receiving member can be significantly extended.
[0024] In the present invention, it is preferable that Vickers hardness of the cutting member is 600 to 1000.
[0025] When the hardness of the cutting member is lower than the hardness of the cutting receiving member like this, damage to the cutting receiving member is small, and the useful life of the cutting receiving member can be significantly extended.
[0026] As described thus far, according to the present invention, joining accuracy can be enhanced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 is a schematic view of a web butt-joining apparatus of the present invention;
[0028] FIG. 2 is a schematic view of an essential part of a joining unit;
[0029] FIG. 3 is a structural view of a removing unit which removes a cut remaining portion of an old roll;
[0030] FIG. 4 is a schematic view of an essential part of a cutting drum of the joining unit;
[0031] FIGS. 5A and SB are plane views and the like showing a butting state of webs;
[0032] FIG. 6 is a state view showing a state directly before joining;
[0033] FIG. 7 is an explanatory view explaining drawing-out of a new roll tip end portion;
[0034] FIG. 8 is a graph explaining the drawing-out of the new roll tip end portion;
[0035] FIG. 9 is an enlarged view of an essential part explaining cutting of the web;
[0036] FIG. 10 is an enlarged view of an essential part explaining joining of the web;
[0037] FIG. 11 is a schematic view of an essential part of a cutting drum of a joining unit of a second embodiment;
[0038] FIG. 12 is a table showing a result of example 1; and
[0039] FIG. 13 is a table showing a result of example 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0040] Hereinafter, a preferred embodiment (first embodiment) of a web butt-welding apparatus and method according to the present invention will be described in detail with reference to the attached drawings.
[0041] FIG. 1 is a schematic view of a web butt-joining apparatus 10 according to the present invention. In the web butt-joining device 10 , a support column 14 is vertically provided on a base stand 12 , a trifurcated turret arm 18 is rotatably supported at a turret shaft 16 at a tip end portion of the support column 14 . The turret arm 18 can rotate intermittently at every 120 degrees around the turret shaft 16 .
[0042] Roll shafts 20 , 22 and 24 are rotatably supported at the respective tip end portions of the turret arm 18 , and an old roll 28 on which an old web 26 under conveyance is wound and a new roll 30 on which a new web 80 (see FIGS. 5A and SB, 9 and 10 ) is wound are pivotally supported respectively on the two roll shafts 22 and 24 among these roll shafts 20 , 22 and 24 to be capable of being unwound.
[0043] On the remaining unused roll shaft 20 , a new roll which is used next to the new roll 30 is pivotally supported. Each of the roll shafts 20 , 22 and 24 is connected to a rotary drive source not shown, so that the new roll 30 can be rotated at the same speed as the conveyance speed of the old web 26 at the time of joining the new and old webs that will be described later. A tip end portion of the new roll 30 is temporarily bonded to web source winding so that a tip end portion of a new web 80 is not detached from the web source winding while the new roll 30 is rotating, and a tip end mark 32 is attached to the tip end portion of the new roll 30 .
[0044] A guide rail 34 is laid on the base stand 12 along a conveyance direction of the web, and a joining unit 36 is provided to be travelable on-the guide rail 34 . Thereby, the joining unit 36 is capable of advancing to and retreating from the turret arm 18 in the direction of the arrow 38 in the drawing.
[0045] In a casing 40 of the joining unit 36 , a cutting drum 42 , a cutting and joining drum 44 and a joining drum 46 are rotatably supported at respective rotary shafts 42 A, 44 A and 46 A. The respective rotary shafts 42 A, 44 A and 46 A are connected to the rotary drive source not shown, so that the cutting drum 42 , the cutting and joining drum 44 and the joining drum 46 can be rotated in the directions of the arrows 48 , 50 and 52 in the drawing at the same speed as the conveyance speed of the old web 26 at the time of joining the webs.
[0046] As shown in FIG. 2 , in the cutting drum 42 , its outer peripheral portion is formed of an elastic material such as rubber, a cutter 42 B is included in a substantially center of the outer peripheral portion, a suction pad 42 C is formed at the outer peripheral portion of a front side in a rotating direction and is connected to a suction device not shown via a hollow shaft portion 42 D. The detail of a peripheral portion of the cutter 42 B will be described later.
[0047] The cutting and joining drum 44 has an abutting plate 44 B which is a cutting receiving member at a front side in the rotating direction of its outer peripheral portion, and a shearing force works as a result that the abutting plate 44 B and the cutter 42 B of the cutting drum 42 abut on each other to be able to cut the webs (the old web 26 , the new web 80 ). A suction pad 44 C is formed on the outer peripheral portion of the rear side in the rotating direction of the cutting and joining drum 44 , and is connected to a suction device not shown via a hollow shaft portion 44 D.
[0048] The joining drum 46 has a suction pad 46 B, which separably sucks a back surface of a bonding tape 47 in a substantially center of its outer peripheral portion, and which is connected to a suction device not shown via a hollow shaft portion 46 C. Guide rollers 42 E and 44 E are mounted to the cutting drum 42 and the cutting and joining drum 44 so as to support the web (old web 26 ) between the old roll 28 and a pass roller 60 .
[0049] A guide member 54 with a triangular section which guides the webs (the old web 26 , the new web 80 ) at the time of joining so as not to deviate from a web conveyance route is provided in a substantially triangular space portion surrounded by the rotational outer periphery of each of the drums 42 , 44 and 46 . The guide member 54 is mounted to a casing 40 (see FIG. 1 ).
[0050] As shown in FIG. 3 , a removing unit 56 for removing a remaining portion of the old web 26 which is cut at the time of joining from the web conveyance route is provided in the vicinity of the area above the cutting and joining drum 44 . In the removing unit 56 , a plurality of revolving rollers 56 B, 56 B are rotatably arranged with a slightly larger space than the thickness of the web along an arc-shaped guide plate 56 A to form a removing passage 58 in a space from a guide plate 56 A.
[0051] A plurality of revolving rollers 56 B, 56 B are connected to a rotary driving source not shown, so as to rotate in the direction opposite from the rotating direction of the cutting and joining drum 44 , and at a higher circumferential speed than the rotation (circumferential speed) of the cutting and joining drum 44 . Thereby, the remaining portion of the old web 26 which is cut, and sucked and held by the suction pad 44 C of the cutting and joining drum 44 is pinched by the cutting and joining drum 44 and the plurality of revolving rollers 56 B, 56 B, raised up to the removing passage 58 , and is removed from the conveyance route of the web.
[0052] As shown in FIG. 1 , a roll outside diameter sensor 64 which measures an outside diameter of the new roll 30 is mounted to a wall surface 62 located above the new roll 30 . The outside diameter of the new roll 30 can be measured by measuring the distance up to the outer periphery of the new roll 30 by causing light beam 66 from the roll outside diameter sensor 64 to reflect at the outer peripheral surface of the new roll 30 .
[0053] A tip end mark sensor 68 is provided at a tip end portion of the guide rail 34 at the turret arm 18 side. The tip end mark sensor 68 is adapted to detect the tip end mark 32 of the new roll 30 when the turret arm 18 rotates 120 degrees and the new roll 30 moves to the position in FIG. 6 at the time of joining the webs.
[0054] A tail end mark sensor 74 which detects a tail end mark 72 attached to a tail end portion of the old roll 28 is mounted to a wall surface 70 above the old roll 28 that moves to the position shown in FIG. 6 . The signals of these sensors 64 , 68 and 74 are inputted into a controller not shown so as to control the moving distance of the joining unit 36 and the rotation timing of the respective drums 42 , 44 and 46 .
[0055] Next, the detail of the peripheral portion of the cutter 42 B in the cutting drum 42 will be described. FIG. 4 is a sectional view of an essential part of the cutting drum 42 . In the peripheral portion of the cutter 42 B in the cutting drum 42 , a cutting drum main body 42 F and an insert 42 G, which is fitted into a recessed portion formed on the surface of the cutting drum main body 42 F, form a cylindrical portion of the peripheral surface.
[0056] The cutter 42 B is provided at the cylindrical portion with its tip end protruded, and is fixed to form an inclined angle θ 1 with respect to the direction of a radius CL of the cylindrical portion. The inclined angle θ 1 is in the relationship of 20 degrees≧θ 1 ≧cos −1 (R/(R+H 2 )) when the radius of the peripheral surface is set as R and the protruded amount of the tip end of the cutter 32 B is set as H 1 .
[0057] Fixing of the cutter 42 B is achieved by sandwiching the cutter 42 B by the cutting drum main body 42 F and the insert 42 G. The cutting drum main body 42 F and the insert 42 G at both sides of the cutter 42 B are flush with each other.
[0058] Cushioning members 42 H and 42 I formed of foaming rubber are provided at both sides of the cutter 42 B. The cushioning members 42 H and 42 I preferably have hardness of 50 or less in the hardness defined in JIS K 6301.
[0059] A protruded amount HI of the cutter 42 B from the surfaces of the cutting drum main body 42 F and the insert 42 G is preferably in the range of 3 to 5 mm. A protruded amount H 2 of the cutter 42 B from the circumferential surface of the cutting drum main body 42 F is preferably in the range of the thickness of the webs (the total thickness of the old web 26 and the new web 80 ) plus 0.05 to 0.1 mm.
[0060] Next, the disposition of the cutter 42 B in the width direction of the cutting drum 42 will be described. FIGS. 5A and SB are views explaining the relationship, FIG. 5A is a plane view of the cutting drum 42 , and FIG. 5B is a plane view showing a butting state of the webs. In FIG. SA, the cushioning members 42 H and 42 I, and the like are not shown.
[0061] As shown in FIG. 5A , the cutter 42 B forms an inclined angle α of 0.5 to 5 degrees with respect to the axial direction of the cutting drum 42 . Thereby, as shown in FIG. 5B , butt-joining is performed so that the joining line of the webs (the end portion 26 A of the old web 26 , the end portion 80 A of the new web 80 ) after butt-joining forms an inclined angle α of 0.5 to 5 degrees with respect to a vertical line HL relative to the supplying direction of the web.
[0062] Next, the cutter 42 B will be described. The Vickers hardness Hv of the cutter 42 B is preferably 600 to 1000, and Hv is more preferably 750 to 800. If the hardness Hv of the cutter 42 B is lower than the Vickers hardness Hv (that will be described later) of the abutting plate 44 B (see FIG. 2 already described) like this, the abutting plate 44 B is less damaged, and the useful life of the abutting plate 44 B can be remarkably extended.
[0063] The Vickers hardness Hv of the abutting plate 44 B which is the cutting receiving member is preferably 1000 or higher. If the abutting plate 44 B on which the cutting edge of the cutter 42 B abuts is hard, and especially has the Vickers hardness Hv of 1000 or higher like this, the problem that the cutting edge of the cutter 42 B bites into the abutting plate 44 B hardly occurs, and the disadvantage of causing chips when cutting the old web 26 and the new web 80 in the overlaid state can be solved. As the material of the abutting plate 44 B, the material enhanced in the quenching hardness by quenching of the nitride steel, and carbonizing can be preferably adopted.
[0064] A metallizing plating layer of a thickness of 10 to 30 μm is preferably formed on the surface of the abutting plate 44 B. With the metallizing plating layer of such a thickness, the disadvantage of the metallizing plating layer curling up, and being damaged can be eliminated, and the useful life of the abutting plate 44 B can be remarkably extended. For this metallizing plating layer, hard chromium metallizing plating can be preferably adopted.
[0065] As already described, the cutter 42 B forms an inclined angle 01 with respect to the radius CL direction of the cylindrical portion and is fixed. The cutter 42 B is fixed in an open sided state with the inclined angle 9 1 formed with respect to the radius CL direction like this. Therefore, when cutting is started by causing a crack to the web on the occasion of abutting on the web, the locus of the cutting edge after the tip end of the cutter 42 B abuts on the web until it further abuts on the cutting and joining drum 44 , and the direction of the crack at the time of start of the cutting substantially coincide with each other by having the inclined angle 01 , and beautiful cutting is performed without fluff on the cutting surface.
[0066] Since the cushioning members 42 H and 42 I with proper hardness are provided at both sides of the cutter 42 B, the cutter 42 B is held more firmly by the cushioning members 42 H and 42 I, but it does not cause the compression stress to the inside of the web by compression deformation, and therefore, the web has no cutting strain, thus making it difficult to cause chips at the time of cutting the web.
[0067] On this occasion, it is important that the inclined angle θ 1 of the cutter 42 B inclines to the rotating direction side (forms the inclined angle θ 1 to the right side with respect to the radius CL direction) as shown in FIG. 4 .
[0068] Next, an operation of the web butt-joining apparatus 10 of the present invention constructed as above will be described. As shown in FIG. 1 , the old web 26 which is unwound from the old roll 28 is conveyed in the direction of the arrow 76 in the drawing through the space between the cutting and joining drum 44 and the cutting drum 42 , and the joining drum 46 while being supported by the pass roller 60 , and is fed to a coating process step and a treatment process step not shown. At this time, in order to prevent warp of the old web 26 , the intermediate portion of the old web 26 is supported with the guide rollers 42 E and 44 E of the cutting drum 42 and the cutting and joining drum 44 .
[0069] While the old web 26 is unwound in the state in FIG. 1 , the outside diameter dimension of the new roll 30 is measured by the roll outside diameter sensor 64 , and its signal is inputted into the aforementioned controller not shown. When the outside diameter dimension of the new roll is measured, the turret arm 18 rotates 120 degrees to move the old roll 28 and the new roll 30 to the position shown in FIG. 6 , the joining unit 36 moves on the guide rail 34 in the direction of the arrow 78 in the drawing based on the moving distance determined from the outside diameter dimension of the new roll inputted into the controller, and stops at the position close to the outer peripheral surface of the new roll 30 .
[0070] Next, the tail end mark sensor 74 detects the tail end mark 72 attached to the old roll 28 , and the signal which informs that the web amount of the old roll 28 is the predetermined amount or less is inputted into the controller. The controller gives an instruction to the driving source which drives the rotary shaft 22 of the new roll 30 to rotate the new roll 30 counterclockwise, and accelerates the new roll 30 to the same speed as the conveyance speed of the old web 26 (for example, 100 m/minute or higher).
[0071] Next, when the tip end mark detector 68 detects the tip end mark 32 of the new roll 30 , and the signal is inputted into the controller, the controller gives an instruction to the rotary drive source which rotates the rotary shafts 42 A, 44 A and 46 A of the respective drums- 42 , 44 and 46 to rotate the respective drums 42 , 44 and 46 at the same speed as the conveyance speed of the old web 26 , and the suction pads 42 C, 44 C and 46 B of the respective drums 42 , 44 and 46 in the suction state.
[0072] At this time, the cutting drum 42 starts rotation in a timing at which its speed becomes the same as the conveyance speed of the old web 26 at the drawing-out position for drawing out the tip end portion of the new roll 30 , and draws the tip end portion of the new roll 30 by sucking it with the suction pad 42 C of the cutting drum 42 .
[0073] Namely, as shown in FIG. 7 , when the outer peripheral speed of the new roll 30 is set as V, and the time in which the new roll 30 moves a distance A from the tip end portion detecting position B to the above described drawing-out position C is set as t seconds, the cutting drum 42 is rotationally driven in a timing at which its speed becomes equal to the outer peripheral speed V of the new roll 30 t seconds later from the start of rotation as shown in the graph of FIG. 8 .
[0074] Thereby, the web tip end portion of the new roll 30 can be reliably drawn out with the suction pad 42 C of the cutting drum 42 . Similarly, the cutting and joining drum 44 and the cutting drum 42 are also started to rotate in a timing of cutting and joining of the web that will be described later.
[0075] When the cutting drum 42 and the cutting and joining drum 44 rotate to the angles in the state shown in FIG. 9 , the cutting drum 42 and the cutting and joining drum 44 pinch the old web 26 and the new web 80 with the old web 26 overlaid on the new web 80 , and the cutter 42 B of the cutting drum 42 and the abutting plate 44 B of the cutting and joining drum 44 cut the old and new webs 26 and 80 .
[0076] Since the cutter 42 B is fixed in an open-sided state, forming the inclined angle θ 1 with respect to the radius CL direction, it provides a proper warp amount in the traveling direction in which the web is cut when it abuts on the webs (overlapping body of the old web 26 and the new web 80 ). Since the cushioning members 42 H and 421 with proper hardness are provided at both sides of the cutter 42 B, the cutter 42 B is firmly held by the cushioning members 42 H and 42 I, but they do not apply compression deformation to the web. Therefore, there is no compression strain, and strain is not applied to the web under cutting, thus making it difficult to cause chips at the time of cutting the webs.
[0077] As shown in FIG. 5A which is already described, the cutter 42 B is provided to form an inclined angle α of 0.5 to 5 degrees with respect to the axial direction of the cylindrical portion, and therefore, the web is cut so that the cutting line advances from one end side of the cutter 42 B to the other end side. Therefore, cutting accuracy is enhanced by such cutting, and the web is smoothly fed in sequence to the joining drum 46 from the one end which is cut, as a result of which, the joining accuracy is enhanced.
[0078] In FIG. 9 , on cutting, the web tip end portion after cutting of the new web 80 is quickly taken into a gap between the cutting drum 42 and the cutting and joining drum 44 which rotate in the reverse directions from each other and while being pinched by them, it is guided by the guide member 54 and moves in the transfer direction. Further, the tip end of the new web 80 is fed out to the tip end portion side by the rotation of the new roll 30 , and therefore, it does not deviate from the cut portion.
[0079] Meanwhile, the tail end of the old web 26 after cutting moves in the conveyance direction of the web while being pinched by the cutting and joining drum 44 and the joining drum 46 . Thereby, the tail end of the old web 26 after cutting and the tip end of the new web 80 after cutting are reliably conveyed to the joining position in the butted state.
[0080] Next, when the respective drums 42 , 44 and 46 rotate to the angle shown in FIG. 10 , while the old and new webs 26 and 80 are pinched with the cutting and joining drum 44 and the joining drum 46 , the butting portions of the old and new rolls 26 and 80 are joined by the bonding tape 47 suction-held by the suction pad 46 B of the joining drum 46 .
[0081] Then, the respective drums 42 , 44 and 46 which finish joining rotate to the original position and stop, and the suction state of the suction pads 42 B, 44 B and 46 B of the respective drums 42 , 44 and 46 is released. The joining unit 36 moves on the guide rail 34 to retreat to the original position, and conveyance of the web of the new roll 30 is started in the state in FIG. 1 again.
[0082] While the cut remaining portion of the old web 26 which is cut at the time of cutting is removed from the transfer route by the removing unit 56 shown in FIG. 3 , the cut remaining portion of the new web 80 is suction-held by the suction pad 42 B of the cutting drum 42 to move to the stop position of the cutting drum 42 , and by releasing suction of the suction pad 42 B, it falls from the cutting drum 42 with self-weight. From the above, butt-joining of the old and new webs 26 and 80 is completed.
[0083] Next, in accordance with FIG. 11 , a second embodiment of the web butt-joining apparatus of the present invention will be described. The same members as in the first embodiment already described will be explained by giving the same reference numerals and characters.
[0084] As shown in FIG. 11 (corresponding to FIG. 4 of the first embodiment), in the cutting drum 42 , a cutting member block 42 J is fitted into the recessed portion formed on surface of the cutting drum main body 42 F to form the cylindrical portion of the peripheral surface of the cutting drum 42 so that the surface of the cutting member block 42 J and the surface of the cutting drum main body 42 F are flush with each other.
[0085] A tip end of the cutter 42 B is provided to protrude from the surface of the cutting member block 42 J. A protruded amount H 2 of the cutter 42 B from the surface of the cutting member block 42 J is set substantially similarly to the H 2 of the first embodiment. In this embodiment, cushioning members are not provided at both sides of the tip end portion of the cutter 42 B, but the cushioning members may be provided as in the first embodiment.
[0086] The material of the cutter 42 B (Vickers hardness Hv, and the like), the inclined angle θ 1 with respect to the direction of the radius CL of the cylindrical portion of the cutter 42 B, the inclined angle a of the cutter 42 B with respect to the axial direction of the cutting drum 42 , and the like are set substantially similarly to the first embodiment.
[0087] As for the method for fixing the cutting member block 42 J to the cutting drum main body 42 F, various known methods such as fixing by the screw member not shown and shrinkage fitting utilizing thermal expansion can be adopted.
[0088] Since according to this embodiment, the cutter 42 B provided at the cutting drum 42 is embedded into the cutting member block 42 J, and the cutting member block 42 J is capable of being fitted into the recessed portion formed in the cylindrical portion of the surface of the cutting drum main body 42 F to be flush with each other, replacement of the cutter 42 B and fine adjustment of the cutting blade position or the like can be performed by only replacing the cutting member block 42 J, the mechanism of the device can be simplified, joining accuracy and quality can be enhanced, and downtime can be reduced.
[0089] Namely, by, adopting the mode in which a plurality of cutting member blocks 42 J with the protruded amount H 2 , the inclined angle θ 1 , the inclined angle α that are already described and the like changed are prepared and the cutting member block 42 J is replaced with the optimum cutting member block 42 J in accordance with the thickness and quality of the web, joining accuracy and quality can be enhanced and downtime can be reduced.
[0090] As above, according to the web butt-joining apparatus 10 of the present invention, the first problem of the disadvantage of poor joining accuracy of cutting by the conventional devices, the second problem of the disadvantage of occurrence of chips at a time of cutting webs in cutting by the conventional devices, the third problem of the disadvantage of reduction in productivity, increase in consumables cost and the like in cutting by the conventional devices, and the fourth problem of the disadvantage of reduction in productivity and the like in cutting by the conventional devices are all solved.
[0091] The web butt-joining apparatus 10 of the present invention brings the joining unit 36 close to the outer periphery of the new roll 30 based on the signal of the roll outside diameter sensor 64 which detects the outside diameter of the new roll 30 , rotates the new roll 30 at the same speed as the conveyance speed of the old web 26 , draws out the tip end portion of the new roll 30 with the suction pad 42 C of the cutting drum 42 of the joining unit 36 , and buts and joins the end portions of the old and new webs 26 and 80 in corporation with the cutting drum 42 , the cutting and joining drum 44 and the joining drum.
[0092] Thereby, joining can be performed without decreasing the unwinding speed of the old web 26 at the time of joining, and therefore, an accumulator becomes useless. It is not necessary to stop or slow down the operation of the line at the time of joining, and therefore, production efficiency can be enhanced.
[0093] Since the joining unit 36 is provided to be capable of advancing and retreating, and the tip end portion of the rotating new roll 30 is directly drawn out with the cutting drum 42 , the tip end portion of the new roll does not have to be conveyed to the joining unit. Since thereby, the joining mechanism can be simplified, joining accuracy can be enhanced and the device cost can be reduced.
[0094] The examples of the embodiments of the web butt-welding apparatus and method according to the present invention are described thus far, but the present invention is not limited to the examples of the above described embodiments, and various modes can be adopted.
[0095] For example, in the examples of the embodiments, the three-drum construction with the cutting drum 42 , the cutting and joining drum 44 and the joining drum 46 is adopted, but a four-drum construction with the cutting drum 42 , the cutting and joining drum 44 , the joining drum 46 and a nip drum can be adopted. In this case, the cutting and joining drum 44 is not used for butt-joining of webs, but the joining drum 46 and the nip drum disposed to be opposed to this perform butt-joining.
[0096] The construction of the web butt-joining apparatus is not limited to the examples of these embodiments, and the constructions as in, for example, the apparatus disclosed in Japanese Examined Application Publication No. 6-57579 and the apparatus disclosed in Japanese Patent No. 3584456 can be adopted.
EXAMPLES
Example 1
[0097] Butt-joining of the webs was performed by using the web butt-joining apparatus 10 shown in FIG. 1 . The diameter of the cutting drum 42 was 300 mm (the radius R was 150 mm). The protruded amount of the tip end of the cutter 42 B shown in FIG. 4 was 0.25 mm, and the inclined angle θ 1 was 5 degrees.
[0098] For the web, TAC (Triacetyl Cellulose) of a width of 1400 mm and a thickness of 100 μm was used. The conveyance speed of the web was 100 m/minute.
[0099] The inclined angle α shown in FIGS. 5A and 5B was changed from 0 to 10 degrees under the 5 conditions, the cut edge state of the web and the joined portion deviation was visually evaluated. The butt-joining test of the webs was repeated ten times under the same conditions. The result is shown in the table in FIG. 12 .
[0100] According to the table in FIG. 12 , when the inclined angle α is in the range of 0.5 to 5 degrees, each of the cut edge states of the webs is favorable, the joined portion deviations are favorable, and the judgment is OK for all. On the other hand, in the test of 0 degrees in which the inclined angle a was less than 0.5 degrees, fine splits occurred to the two cases in the cut edge state of the web, and judgment was NG. Namely, it has been confirmed that the cutter without the inclined angle α, performs poor cutting.
[0101] In the test of 10 degrees in which the inclined angle α exceeds 5 degrees, deviation occurred to one case in the joined portion deviation, and the judgment was NG. Namely, it has been confirmed that when the inclined angle a is too large, the joining accuracy becomes worse.
Example 2
[0102] Butt-joining of the webs was performed by using the web butt-joining apparatus 10 shown in FIG. 1 . The diameter of the cutting drum 42 is under the two conditions of 250 mm and 300 mm (the radius R is under the two conditions of 125 mm and 150 mm). The inclined angle a shown in FIGS. 5A and 5B was 1 degree.
[0103] For the web, TAC (Triacetyl Cellulose) of a width of 1400 mm and a thickness of 100 μm was used. The conveyance speed of the web was 100 m/minute.
[0104] The protruded amount of the tip end of the cutter 42 B shown in FIG. 4 was changed in the four steps from 0.20 to 0.5 mm, the inclined angle θ 1 was changed in the six steps from 2.0 to 25 degrees, and the cut edge state of the web and the blade breakage were visually evaluated. The web butt-joining test was repeated 10 times under the same condition. The result is shown in the table in FIG. 13 . In the table, β is the value of cos −1 (R/(R+H 1 )).
[0105] According to the table in FIG. 13 , in the condition of the inclined angle θ 1 in the range of 20 degrees≧θ≧1≧β, the cut edge states of the webs were all favorable, blade breakage was favorable (no breakage), and the judgment was OK for all. On the other hand, with the inclined angle θ 1 of less than the above described range, the cut edge state of the web was unfavorable, and with the inclined angle θ 1 exceeding the above range, blade breakage occurred, and judgment was NG for both of them.
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The present invention provides a web butt-joining apparatus, comprising: a turret device that supports an old roll and a new roll on which band-shaped flexible base materials are wound to be capable of being unwound, and is rotatable at every predetermined angle; a cutting drum including a cutting member and a holding device; a cutting and joining drum which includes a cutting receiving member, and a holding device which is capable of rotating at the same speed as conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base material; and a joining drum which is capable of rotating at the same speed as the conveyance speed of the band-shaped flexible base material at a time of joining the band-shaped flexible base materials, wherein while conveying the band-shaped flexible base material, the web butt-joining apparatus performs cutting and butt-joining of the tail end of the band-shaped flexible base material of the old roll and the tip end of the band-shaped flexible base material of the new roll.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application corresponds to French applications 96 14606 of Nov. 28, 1996 and 97 06257 of May 22, 1997.
FIELD OF THE INVENTION
The present invention relates to a device for material and heat exchange and, in particular, a device for material and heat exchange adapted to serve as packing in distillation columns with a high number of theoretical plates, typically in columns for the distillation of air or mixtures of carbon monoxide, nitrogen, hydrogen or hydrocarbons, or in isotopic separation columns. It can also serve for isotopic distillation. Typically, it will be installed in distillation columns with a high number of theoretical plates.
BACKGROUND OF THE INVENTION
The packing ordinarily used comprises corrugated strips comprising alternate parallel corrugations each disposed in a general vertical plane and against each other, the undulations being oblique and descending in opposite directions from one strip to the next. The degree of perforation is about 10% for this so-called cross corrugated packing.
GB 1 004 046 discloses packings of the cross corrugation type.
CA-1 095 827 provides an improvement of this type of packing by adding dense perforations of small diameter to permit the liquid to move from one side to the other of the cross corrugated strips.
WO 94/12258 provides an improvement of this type of packing based on exact positioning of the strips relative to each other in a vertical plane, by a system of interlocking. This device has for its object to provide more packing surface in a same volume, because the interlocking permits an interpenetration of the strips.
WO 86/06296 and WO 90/10497 disclose a packing comprising horizontal superposed layers, each layer comprising rows of pyramids.
In WO 86/06296, the structure comprises pyramids with open bases, and lateral surfaces alternately open and closed, connected at their points so as to constitute a multitude of ventilator blades placing the gas in rotation to intensify the contact between the gas and the liquid. A fundamental characteristic of this structure is that it can be made by assembly of perforated and bent metal sheets. This time, the perforation is not only adapted to optimize the circulation of the liquid but also to permit the gas to pass through the bent crossing strips, the rate of perforation being of the order of 50%.
Paradoxically, it is just at this moment at the beginning of serious contestation of the cross corrugated packing that the latter began to be used in the separation of air gases. This relatively late use is explained in part by the high performances of cryogenic plates relative to other plates on the market (HETP, height equivalent to a theoretical plate, of the order of 10 cm, and low pressure drop).
In WO 90/10497, the structure obtained above is improved by causing the surfaces of the pyramids of two successive layers to coincide, which creates transverse channels relative to the strips, and promotes the transverse movement of the mixture. It mentions clearly the interest of a double perforation: one with a checkerboard pattern (hence with 50% of the surface perforated) for the gas, and a secondary perforation in the "closed surfaces" to promote the streaming of the liquid.
This latter patent application gave rise to the Sulzer product "Optiflow"™ which represents the first embodiment of a new generation, making possible substantially improved performance relative to the now-conventional cross corrugation structures (HETP reduced by an order of 25 to 30% with constant vapor flow rate, or flooding flow rate increased by the order of 25 to 30% with HETP constant).
This patent and these patent applications permit isolating two important directions of research. The first has for its object to improve the flow of the liquid so that the wetted surface will be as large as possible and so that the liquid will distribute itself in all directions whilst remixing in the course of trickling through the packing. The second has for its object to optimize the gas flow, which is to say to obtain a vertical flow as turbulent as possible, without favored flow paths nor regions of low circulation.
Until now, the flow of the liquid phase has been studied in structures of the cross corrugated type. It has been discovered that small diameter perforations (about 10%) promote the passage of the liquid on each side of the strips. Several improvements have been proposed: CA-A-1095827 claims a precise positioning of the holes relative to the bends and WO 94/12258 claims the relative positioning of the strips, by interpenetration of the strips. Thus it appears that the positioning of the holes does not substantially increase the efficiency of the packing because the principal function of the holes is to cause the liquid to pass from one side to the other of the strip. Only the amount of perforation and the diameter of the holes therefore influence efficiency.
The idea of pyramids introduced by WO 86/06296 and WO 90/10497 introduces a new type of perforations: perforations for the passage of gas (representing about 50% of the surface). These perforations permit reducing the pressure drop and creating ventilators favoring the mixing of the gas. These documents are silent as to liquid circulation.
Connecting the pyramids by their points ("summits" and "corners", there is designated by "corners" the points located on the base) has an important drawback: because of there being little material at these points, the mechanical strength of the assembly requires physically connecting these "points" by a mechanical process of the type of clipping, tying, welding or cutting which requires complicated and costly tools, and hence results in a fairly high price. It can also be noted that the number of these connections varies as the number of the pyramids, which is to say as the cube of the inverse of their size, which limits the specific surface economically accessible in this type of packing. On the other hand, the principle of perforating in a checkerboard pattern gives rise to a loss of material of the order of 50%; this is particularly undesirable when the material of the packing is of high cost, a woven material for example.
It also appears that this structure is very aerated and that the HETP could be further reduced if a portion of the waste material was integrated back into the structure without impairing the turbulence of the gas or the rate of wetting of the surface.
SUMMARY OF THE INVENTION
The object of the present invention is to create a device for heat and material exchange having good properties as to gas flow, including a series of improvements relating to the spreading, distribution and mixing of the liquid and of simplified manufacture relative to those of the prior art and hence permitting the practical realization of very thin packing, hence with an even smaller HETP.
According to an object of the invention, there is provided a heat and/or material exchange device constituted by a stack of fixed ventilators, so as to promote gaseous mixture, each ventilator being constituted by four deflectors whose mean normals are inclined and substantially generated one from the others by rotation about vertical axes, the sum of the four angles of rotation being 360° and the ventilators being stacked in successive horizontal layers within which each deflector forms a portion of two adjacent ventilators turning in opposite directions and such that there is sufficient space between two adjacent deflectors for the passage of gas.
The deflectors of the ventilators can be flat or not, symmetrical or not, generated by rotation about a vertical axis or not.
The structure thus described permits creating turbulent flow of the gas which improves exchange between the liquid film streaming over the deflectors and the gas. It has the advantage of giving great freedom of design to define the shape and connections of the deflectors. This freedom can be used to improve the other functions of the product and to reduce its cost.
It should be noted that the open pyramidal structure of the patent applications WO 86/06296 and WO 90/10497 is a very particular case of the general structure which has been described when the following conditions are simultaneously satisfied:
1. the deflectors of the ventilators are rhombi whose one diagonal is horizontal or triangles whose base is horizontal.
2. the angles of rotation of the deflectors are 90°.
3. the axes of rotation pass through the ends of the horizontal diagonals of the deflectors of rhombus shape or through the ends of the horizontal bases of the deflectors of triangular shape.
4. the upper summits of the rhombi or of the triangles of one layer coincide with a summit of a rhombus or a triangle of the immediately superjacent layer.
According to another aspect of the invention
the deflectors of the ventilators are neither rhombi of which one diagonal is horizontal, nor triangles of which the base is horizontal or
the angles of rotation of the deflectors are not 90° or
the axes of rotation do not pass through the ends of the horizontal diagonals of the deflectors of rhombus shape or
the axes of rotation do not pass through the ends of the horizontal bases of the deflectors of triangular shape or
the upper summits of the rhombi or of the triangles of one layer do not correspond with a summit of a rhombus or of a triangle of the immediately superjacent layer.
According to another aspect of the invention, there is provided a device in which:
the lower portion of certain ones or all of the deflectors is bisymmetric.
the upper portion of certain ones or all of the deflectors is symmetrical relative to the line of greatest slope, and substantially of inverted V shape, so as to promote spreading of the liquid.
certain ones or all of the deflectors are pierced by one or several holes, with or without symmetry about the vertical axis, so as to promote the passage of liquid below the deflectors.
certain ones or all of the deflectors are connected to several of their neighbors in a same horizontal plane by a common edge segment, rounded, flattened or stamped, so as to permit lateral distribution of the liquid between deflectors.
certain ones or all of the deflectors penetrate the space located in vertical alignment with an adjacent deflector.
certain ones or all of the deflectors are designed to supply liquid to another deflector, generally with the aid of a point, or to collect the liquid from another deflector.
the lower portion of certain ones or all of the deflectors is at least partly enlarged, so as to preserve for the liquid a streaming surface as large as possible.
at least one end of the two deflectors forms a projection.
one or each projection nests with another projection or a notch so as to secure together the layers of ventilators.
It should also be noted that the application WO 94/12258 describes a structure in which each point of interpenetration is the center of four deflectors which are not generated by rotation. However, the deflectors are secured together such that there is no longer a passage for gas between two deflectors of vertically superposed ventilators. The concept of ventilators as such disappears because of the absence of perforations for gas.
In the device proposed here, the positioning of the strips relative to each other is motivated by the gas perforations which must be positioned precisely relative to each other.
According to another object of the invention, there is provided a process for the production of a device, in which flat sheets of metal or of another material are cut out and folded and/or bent, twisted or stamped to form accordion sheets, with or without projections, the plain surfaces forming flat, bent, curved or twisted deflectors.
The flat product used could be laminated, woven or knitted.
According to other aspects of the invention, there is provided a process for production in which:
the accordion sheets are placed side by side, parallel to a vertical plane.
the accordion sheets are pierced at least 45% before folding.
the structure is constituted by substantially identical accordion sheets in which the accordion sheets of uneven rows are reversed relative to the sheets of even rows about a vertical or horizontal axis included in the mean plane of the accordion sheet.
the positioning of the accordion sheets is ensured by a contact region permitting nesting the sheets and also permitting ensuring the stability of the accordion sheets, once locked against each other. The nesting can be designed so as to block the two degrees of freedom of translation at certain or all of the contact points. Moreover, it can be designed so as to block one degree of freedom in translation at certain contact points and the other degree of freedom at other contact points.
the accordion sheets are pierced and folded so as to connect the plain surfaces by two bend lines, curved or not, permitting liquid exchange between adjacent deflectors.
the bend lines are not continuous so as to create projections beyond the region comprised between two planes containing the bends.
the contact region is formed by a local stamping.
the contact region is formed by cutting out and folding and/or bending or twisting.
the projections permit positioning accordion sheets by nesting projections and/or notches.
the projections permit creating distributors or collectors for the deflectors of an adjacent layer.
the piercing proportion of the accordion sheets permits creating wide streaming surfaces.
According to an object of the invention, there is provided a process for the separation of air gases or hydrocarbons, or carbon dioxide, or isotopes, in a distillation column comprising at least one device as described.
According to another object of the invention, there is provided an installation for the separation of air gases or hydrocarbons, or carbon dioxide, or isotopes, in a distillation column comprising at least one device as described.
BRIEF DESCRIPTION OF THE DRAWINGS
Other aspects of the invention will now be described, with reference to the following drawings, in which:
FIG. 1 is a perspective view of two ventilators of alternate directions of a device according to the invention.
FIG. 2 shows the flow of liquid over the deflectors of a device according to the invention.
FIG. 3 is a schematic view of the cutting out of a metallic sheet according to the invention.
FIG. 4 shows two schematic representations of the metallic sheet of FIG. 3 accordion folded including a perspective view and a view along the axis of the folds.
FIGS. 5A and 5B show two schematic representations of two metallic sheets of FIG. 4 assembled: FIG. 5A shows a perspective view and FIG. 5B a view along the axis of the folds of one of the sheets.
FIG. 6 shows the industrial cutting out of a metallic sheet according to the invention.
FIG. 7 shows the structure obtained by assembling two cutout and folded sheets according to FIG. 6.
FIGS. 8A, 8B, and 8C show several details of the structure of FIG. 7: FIG. 8A shows four blades which take part in a contact zone, FIG. 8C shows a plan view of FIG. 8A and FIG. 8B shows two superposed ventilators created by the structure.
FIG. 9 shows an enlargement of the region 7B of FIG. 7 in which is shown the flow of the liquid.
FIGS. 10A, 10B, and 10C show the production of a contact point by cutting out, folding and interfitting two layers.
FIGS. 11A, 11B, 11C, and 11D show several folding programs permitting interfitting the layers with each other.
FIG. 12 shows a column casing with structured packings constituted by the device of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows two fixed adjacent ventilators (1A and 1B) in a horizontal layer. The deflectors are not necessarily generated by rotation. These two ventilators direct the gas flow in opposite directions (vortex 1D and 1E), thereby creating a maximum of turbulence. It should be noted that the deflector 1C is common to the two ventilators. The complete structure is obtained by repeating this motif in three directions, with or without modifications of the geometry of the deflectors. The above cited documents are silent as to the circulation of the liquid in the structure.
FIG. 2 shows the spreading of the liquid on the deflectors. It will be seen later the manner of interconnecting the deflectors between two horizontal layers. Let it be supposed only that each deflector is supplied at its summit (2C) by the streaming liquid. It is of course necessary that the maximum surface of the deflectors be wetted. This concern suffices to indicate the best form to be given to the deflectors.
The upper portion (2A) must be "pointed" so as to follow the spreading of the liquid from its supply point. On the other hand, once this spreading is obtained, the deflector can keep its maximum width for a certain distance to increase the streaming surface (2B). Thus, the collection is easier and can take place on edges of low slope with a slightly inclined contour. This leads to a "potbellied" shape.
The optimum distribution of liquid from the two sides of the deflectors leads to piercing a hole (2D) near the summit (2C) permitting a portion of the liquid to pass to the other side.
So that there is no preferred route for the liquid, a same stream of liquid should be distributed in several directions and continuously remixed. Thus, an edge segment (2E) common to two deflectors divides the liquid flowing over the deflector in two and creates a mixing region (2F).
For cost reasons, it is necessary that the deflectors be made from sheet material. Unfortunately, the perforation-folding and/or perforation-bending technique used until now to produce structured packings does not permit obtaining suitable shapes for the needs of the structure described above.
There exists however a method which permits obtaining very varied shapes from a flat product: cutting out folding. It suffices, to establish this point, to consider certain "pop-ups" or certain cardboard packages. The folding is well known to produce polyhedra. This process has never, to our knowledge, been used to produce structured packings. There could also be used a stamping technique, so as to obtain non-developable surfaces. Although very rich in possibilities, this process could be particularly economical because the successive operations of cutting out, folding and even stamping can be integrated in a same press tool.
FIG. 3 shows the schematic cutting out of a sheet before folding, in which the deflectors are "plain" quadrilaterals (3E). The sheet thus cut out is then accordion folded according to the dotted lines. The thick dotted lines (3A) are "valley" folds, whilst the slender pointed lines (3B) show the "crest" folds. It should be noted that these fold lines are discontinuous because the gray portions (3C) are not folded with the rest and therefore form, after folding, projections beyond the two planes containing the crest and valley folds. Thus, the folding takes place only in regions symbolized by black dots (3D), which form both a connection between the deflectors and a contact point and/or interlocking points serving for the stacking and positioning during stacking of the accordion sheets. It will be seen later by what devices these regions can be made.
FIG. 4 shows two schematic representations of a sheet of FIG. 3 accordion folded including a perspective view of the folded sheet and a view from above the sheet along the axis of the folds, on which can be clearly seen the accordion formed by the sheet (4G) . The fold creates two planar orientations, characterized by two different grays of the deflectors (4A and 4B). Notice the projections (4C and 4D) which extend beyond the region comprised between the two planes containing the fold lines. It will therefore be seen that the deflectors, once folded, offer to the liquid a spreading surface (4E) which is "pointed" and symmetrical relative to the line of greatest slope, then an enlarged streaming surface (4F).
FIGS. 5A and 5B show two schematic representations of the structure obtained by assembly of the two folded strips according to FIG. 4. FIG. 5A is a perspective view of the structure. FIG. 5B is a plan view, along the axis of the folds of the sheet of the front plane, on which are seen the two stacked strips 5F and 5G. There will be seen in the foreground of FIG. 5A and at 5F the accordion sheet of FIG. 4. In the background of FIG. 5A and at 5G there is an identical sheet turned 180° relative to a vertical axis. Two superposed ventilators are created by this structure (5A and 5B) . It will be noted that these ventilators are of two different types: 5A is a "closed" ventilator relative to the center of rotation; which is to say that the enlargement of the streaming surface is disposed to the side of the center of rotation, thereby offering a narrower passage to the gas. Conversely, 5B is an "open" ventilator. On a same vertical, there are alternately two types of ventilator. To obtain ventilators turned in the opposite direction, it would be necessary to add a supplemental accordion sheet. The structure obtained at 5C indicates why the bottom of the deflectors has no symmetrical streaming surface. Thus, if the base of the deflectors were symmetrical rectangular, it would have, of course, a larger streaming surface but there would be obtained at 5C a junction of the edges of the two deflectors forming a sort of horizontal gutter. Such a structure would be very undesirable, both for gas flow and for liquid flow. Finally, it should be noted that the projections of the accordion sheet of the first plane (5D), are insertable exactly between two successive folds of the sheet of the second plane. Similarly, the projections of the sheet in the background (5E) interfit between the folds of the sheet of the first plane. The relative position of the sheets to each other is thus ensured in all directions and a simple locking ensures the stability of the structure.
All the preceding figures, which are deliberately schematic, have for their object to demonstrate the characteristic principles of the structure. It is quite evident that the structure of FIG. 5A has no mechanical strength because it does not provide material at the points of connection between the deflectors. The cutout-folding principle, associated if desired with a stamping, permits obtaining a very great variety of shapes from which it is necessary to select to improve the structure, both as to its performance and as to simplicity of manufacture. The figures which follow describe an appropriate industrial structure, having high mechanical strength and including several improvements, relative to liquid flow and to manufacture.
FIG. 6 shows the cutting out of an unfolded sheet. The fold lines (6A) are shown in phantom line; it will be seen that they are discontinuous. So as to obtain good mechanical strength, there remains at the connection points 1/3 of the material which would be folded if there were no cutting out. So as to preserve a structure as close as possible to ideal, this material has been distributed unequally over the different connection points. At 6B, to add a vertical edge is a good solution to obtain great length of fold while losing a minimum of open surface. On the other hand, it is necessary to avoid introducing a horizontal edge on which the liquid can accumulate, there is accordingly provided a fold line which constitutes an edge segment (6C) permitting the lateral distribution of the liquid. The projection at 6D serves both for the distribution of the liquid and to secure the strips to each other. Finally, there can be pierced in each deflector a hole (6E) which permits the passage of the liquid from one side to the other of the sheet.
FIG. 7 shows two sheets of FIG. 6 folded and assembled. Notice the series of stacked ventilators (7A). It was seen in FIG. 5 that the strips were positioned perfectly by the projections. The fold lines introduce relative to this position an imprecision equal to the length of the fold line. To compensate that, one can at the time of folding carry out a local stamping along the fold line such that the deepest point will be centered on the contact point. Thus, at the time of assembly, the structure is maintained in position by simple gripping of the strips against each other. In 7B, there is seen a contact point in which the projection of the strip in the background is provided with a point constituting both a sort of attachment securing together the strips and a liquid distributor for remixing.
FIGS. 8A, 8B, and 8C show several enlargements of FIG. 7. FIG. 8A shows an enlargement of the contact region 7B. FIG. 8C shows a view from above of FIG. 8A without hidden surfaces on which it will be seen that the deflectors penetrate the space located in vertical alignment with the adjacent deflectors so as to create a wide streaming surface (8.2A) and a liquid supply for another deflector (8.2B) FIG. 8B shows two types of superposed ventilators, created by the structure: an "open" ventilator (8.3A) and a "closed" ventilator (8.3B).
FIG. 9 shows a detail of FIG. 7, located about 7B. The deflectors 9D and 9F belong to the accordion sheet of the second plane whilst 9C and 9E belong to the sheet of the first plane. The black arrows indicate the liquid flow over the deflectors. The structure is symmetrical relative to the contact point (9A). There is seen the manner in which the point (9B) and its symmetrical point form attachments which stabilize the structure. When the two accordion sheets are arranged face to face, the structure deforms a bit and returns to place when the point has taken its final position. In 9C, there is a lateral parting region of the liquid and then remixing. The liquid which flows over the deflector in the rear separates into two portions (9D). One portion, after passage through free fall (9G), will wet the deflector of the first plane (9E) by means of the distributor formed by the pointed projection (9B) and therefore mixes with the liquid flowing over the adjacent accordion sheet. The other portion of the liquid remains on the same accordion sheet and will wet the underside of the deflector 9F.
FIGS. 10A, 10B, and 10C show the possibility of interlocking the sheets at a contact point which can replace the local stamping at a point such as 6C, which is to say the center of a ventilator. For easier readability, the figures are projected such that the top to bottom direction extends toward the rear of the sheet. FIG. 10A shows only the detail of the cutout at the contact point. The cutout line is 10.1A. Then, the sheets are folded at 10.1C and at 10.1B. FIG. 10B shows the two folded sheets face to face before interlocking and FIG. 10C shows the interlocking. The interlocking forms the center of a ventilator and the four orientations of the deflectors can be seen in FIG. 10C upon holding upright the figure.
The interconnection can be designed so as to block the two degrees of freedom of translation at certain contact points or at all contact points. Or it can be designed to block one degree of freedom of translation at certain contact points and the other degree of freedom at other contact points.
FIGS. 11A, 11B, 11C, and 11D show the sheets 11 according to the invention in which a contact surface is flat and delimited by two folds (FIG. 11B) or is curved (FIG. 11C) or uses more than two folds (FIG. 11D). In these three cases, the cutout permits the edges of the deflectors to form the projections (11A) . FIG. 11A shows a single accordion fold. FIG. 11B shows the case in which the facet (11B) comprising the interior of one pair of folds is flat, as is the case for FIGS. 10A, 10B, and 10C. In FIG. 11C, in place of folds, there is a curved surface (11C). Finally, in FIG. 11D, there is an extra fold (11D).
FIG. 12 shows a casing 100 of a distillation column containing two blocks 200 of structured packing constituted by a heat and/or material exchange device according to the present invention.
The folded sheets 300 are assembled obliquely to the axis of the casing 100.
The heat and material exchange device of the present invention can be installed in any kind of column of an air separation apparatus, for example the medium pressure column, the low pressure column, the argon column, or the nitrogen removal column.
Each column can contain heat and material exchange devices according to the present invention as well as conventional structured packings (of the cross corrugation type for example) and/or bulk packing and/or plates.
The specific surface of the heat and material exchange device of the present invention can vary from one section of a column to another.
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Heat and material exchange device including a stack of fixed ventilators to promote gas mixing, each ventilator being constituted by four deflectors whose mean normals are inclined and generated one after another by rotation about vertical axes, the sum of the four angles of rotation being 360°. The ventilators are stacked in successive horizontal layers amidst which each deflector forms a part of two adjacent ventilators turned in opposite directions and such that there is sufficient space between two adjacent deflectors for the passage of gas. The deflectors are pierced by at least one hole so as to promote passage of the liquid to the underside of the deflectors. At least some of the deflectors are connected to at least one of their neighbors in a same horizontal plane by a common edge segment so as to permit lateral division of the liquid between deflectors. The device is useful in columns for separating the components of air, or mixtures of carbon monoxide, nitrogen, hydrogen or hydrocarbons, or for the separation of isotopes.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This non-provisional application claims priority from provisional application U.S. Ser. No. 60/202,931 filed May 9, 2000.
FIELD OF THE INVENTION
[0002] The present invention relates to diamino derivatives of pyrimidines and triazines having pharmacological activity at the 5-HT 7 receptor. As such, the compounds are useful for treating various central nervous system and peripheral disorders; as well as disorders of the eye.
BACKGROUND OF THE INVENTION
[0003] The 5-HT 7 receptor is a recent member of the growing serotonin receptor family. Both human and animal 5-HT 7 receptors have recently been cloned, expressed and shown to be present in various brain areas and peripheral tissues (Eglen et al., Trend Pharmacol. Sci., 1997, 18, 104-107). The 5-HT 7 receptor has been implicated in the pathophysiology of CNS disorders, such as, sleep disorders, depression, (Schwartz, et al., Adv. Int. Med. 1993, 38, 81-106), schizophrenia (Roth, et al., J. Pharmacol. Exp. Ther., 1994, 268, 1403-1410), anxiety, obsessive compulsive disorder, migraine (Terron, Idrugs, 1998, 1, 302-310), pain and centrally and peripherally mediated hypertension (Eglen et al., supra).
[0004] Although it is not clear which serotonergic receptor(s) activity is responsible for lowering intraocular pressure (IOP), increasing blood flow and providing neuroprotection in the eye, the 5-HT 7 receptor has been found in the retina, choroid and possibly the optic nerve head (May, et al., WO9959499, 4). The stimulation of the 5-HT 7 receptor has caused relaxation of blood vessels in mammals such as the monkey (Leung, et al., Br. J. Pharmacol., 1996, 117, 926-930), dog (Cushing, et al., J. Pharmacol. Exp. Ther., 1996, 277,1560-1566) and rabbit (Martin, et al., Br. J. Pharmacol., 1995,114, 383). Stimulation of the 5-HT 7 receptor may therefore improve blood flow to the optic nerve head, macula and the retina, which is believed to be beneficial in the treatment of retinal diseases such as, glaucoma, age related macular degeneration (ARMD), and diabetic retinopathy (Chiou, et al., J. Ocular Pharmacol., 1993, 9,13-24).
[0005] The therapeutic utility of 5-HT 7 receptor ligands for the treatment of CNS and ocular disorders therefore requires the discovery of therapeutic agents with a high affinity for the 5-HT 7 receptor.
SUMMARY OF THE INVENTION
[0006] The present invention comprises 5-HT 7 receptor antagonists and partial agonists, useful for the treatment of CNS and ocular disorders. The present invention also comprises methods of treating CNS and ocular disorders in a subject in need thereof comprising the administration of 5-HT 7 antagonists and partial agonists which include compounds described in DE 2163873, DE 3717480, U.S. Pat. No. 5,491,234, WO 92/18498, U.S. Pat. No. 3,816,629, GB 1288903, WO 98/15538, DE 19704922, Mohr et al. Arch. Pharm. (Weinheim, Ger.) 1986, 319(10), 878-885, and Hadjuk et al. in J. Med. Chem. 1999, 42, 3852-3859, incorporated by reference herein.
[0007] A first embodiment of a first aspect of the present invention is a method of treating CNS and ocular disorders comprising administration to a subject in need thereof an effective amount of a compound of Formula (I)
[0008] or a pharmaceutically acceptable salt or hydrate thereof, wherein
[0009] V, W and X are CH or N, provided that no more than one of V, W or X can be CH;
[0010] Y is O, S(O) m , CH 2 , NR 9 or a covalent bond;
[0011] Z is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl, pyridinyl and phenyl;
[0012] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NHSO 2 C 1-6 alkyl, NR 7 R 8 , C(O)NH 2 and C 1-3 alkylene;
[0013] m and n are each independently 0, 1 or 2;
[0014] R 1 is hydrogen, halogen, C 1-6 alkyl, C 3-7 cycloalkyl, or NR 7 R 8 ;
[0015] provided that
[0016] if V, W or X is CH, then R 1 is not halogen or NR 7 R 8 ;
[0017] if V, W and X are each N, then R 1 is not hydrogen;
[0018] R 2 is C 1-4 alkyl substituted with Z′, wherein
[0019] Z′ is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl, pyridinyl and phenyl;
[0020] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NHSO 2 C 1-6 alkyl, NR 7 R 8 and C(O)NH 2 ;
[0021] R 3 is hydrogen, C 1-6 alkyl or C 3-7 cycloalkyl;
[0022] R 4 and R 5 are independently hydrogen or C 1-6 alkyl or together are C 2-3 alkylene;
[0023] R 6 is hydrogen or C 1-3 alk(en)ylene
[0024] provided that
[0025] if R 6 is C 1-3 alk(en)ylene, it is attached to Z;
[0026] R 7 and R 8 are independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3-7 cycloalkyl, SO 2 C 1-6 alkyl;
[0027] or R 7 and R 8 together with the nitrogen to which they are attached can form a 5 to 8 membered heterocycle;
[0028] said heterocycle optionally containing a second heteroatom selected from the group consisting of N, O and S;
[0029] said heterocycle being optionally substituted with up to three of the same or different substituents independently selected from C 1-6 alkyl or O—C 1-6 alkyl; and
[0030] R 9 is hydrogen or (C 1-6 )alkyl.
[0031] A second embodiment of the first aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first embodiment of the first aspect.
[0032] A first embodiment of a second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according the first aspect wherein
[0033] V and W are each N;
[0034] X is CH; and
[0035] R 1 is H.
[0036] A second embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according the first aspect wherein
[0037] V and W are each N;
[0038] X is CH;
[0039] Z is substituted or unsubstituted phenyl; and
[0040] R 1 is H.
[0041] A third embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first aspect wherein
[0042] V and W are each N;
[0043] X is CH;
[0044] Y is O or a covalent bond; and
[0045] R 1 is H.
[0046] A fourth embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first aspect wherein
[0047] V and W are each N;
[0048] X is CH;
[0049] Y is O or a covalent bond;
[0050] Z is substituted or unsubstituted phenyl; and
[0051] R 1 is H.
[0052] A fifth embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first aspect wherein
[0053] V and W are each N;
[0054] X is CH;
[0055] Y is O, S or a covalent bond;
[0056] Z is substituted or unsubstituted phenyl, indolyl, pyridinyl, thienyl or benzodioxolyl;
[0057] Z′ is substituted or unsubstituted phenyl, pyridinyl, indolyl, benzodioxolyl, thienyl. napthenyl or furanyl;
[0058] R 1 is H;
[0059] R 2 is C 1-3 alkyl substituted with Z′;
[0060] R 3-6 are each H;
[0061] m is O; and
[0062] n is O or 1.
[0063] A sixth embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0064] N 4 -(3,4-Dichlorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0065] N 2 -(2-Phenoxyethyl)-N 4 -[(1R)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0066] N 2 -(2-Phenoxyethyl)-N 4 -[4-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0067] N 4 -(3,5-Difluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0068] N 2 -(2-Phenoxyethyl)-N 4 -[(1R)-1-phenylethyl]pyrimidine-2,4-diamine,
[0069] N 4 -[3-Fluoro-5-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0070] N 4 -(3,5-Dimethoxyphenylmethyl)- N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0071] N 4 -(1-Phenylethyl)-N 2 -[2-(3-pyridinyl)ethyl]pyrimidine-2,4-diamine, Compound 1,
[0072] N 4 -(3,4-Dichlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0073] N 4 -(2-Furanylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 2
[0074] N 4 -(3-Chloro-4-methylphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0075] N 2 -[2-(4-Methoxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0076] N 4 -(3-Chlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0077] N 2 -(2-Phenylethyl)-N 4 -[(1R)-1-phenylethyl]pyrimidine-2,4-diamine,
[0078] N 2 -(2-Phenylethyl)-N 4 -[4-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0079] N 4 -[4-Fluoro-3-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0080] N 2 -[2-(4-Benzodioxolyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine and
[0081] N 2 -[2-(5-Fluoro-1H-indol-3-yl)]ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 3,
[0082] N 4 -(2-Furanylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 4, and
[0083] N 2 -(2-Phenylethyl)-N 4 -(4-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 5.
[0084] A seventh embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0085] N 4 -(3-Fluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0086] N 4 -[4-Fluoro-3-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0087] N 4 -[3-(Aminocarbonyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 6,
[0088] N 4 -[(1R)-1-(4-Methylphenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0089] N 4 -(1-Phenylethyl)-N 2 -(2-phenylpropyl)pyrimidine-2,4-diamine,
[0090] N 4 -(1-Phenylethyl)- N 2 -(3-phenylpropyl)pyrimidine-2,4-diamine,
[0091] N 2 -(2-Phenthioethyl)-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0092] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0093] N 4 -[2-(1H-Indol-3-yl)ethyl]-N 2 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 7,
[0094] N 2 -(2-Phenylethyl)-N 4 -[(1R)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0095] N 2 -[2-(3-Bromophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 8,
[0096] N 2 -[2-(4-Bromophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 9,
[0097] N 4 -(2,4-Dichlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0098] N 2 -[2-(3,4-Dichlorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0099] N 2 -(lndan-2-yl)-N4-(1-phenylethyl)pyrimidine-2,4-diamine, Compound 10,
[0100] N 2 -(2-Phenylethyl)-N 4 -(3-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 11,
[0101] N 4 -(1-Phenylethyl)-N 2 -{2-[3-(trifluoromethyl)phenyl]ethyl}pyrimidine-2,4-diamine,
[0102] N 2 -[2-(2-Methoxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, and
[0103] N 4 -(1-Phenylethyl)-N 2 -[2-(2-pyridinyl)ethyl]pyrimidine-2,4-diamine, Compound 12.
[0104] An eighth embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0105] N 4 -[(1S)-1-(4-Bromophenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 13,
[0106] N 4 -(3-Methylphenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0107] N 2 -(2-Phenoxyethyl)-N 4 -[(1S)-1-phenylethyllpyrimidine-2,4-diamine,
[0108] N 4 -{3-[(Methylsulfonyl)amino]phenylmethyl}-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 14,
[0109] N 2 -(2-Phenoxyethyl)-N 4 -[3-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0110] N 4 -(3-Chlorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0111] N 2 -(2-Phenoxyethyl)-N 4 -[(1S)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0112] N 4 -(4-Chlorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0113] N 4 -(3-lodophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 15,
[0114] N 4 -(3,4-Difluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0115] N 4 -(4-Benzodioxolylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0116] N 2 -(2-Phenoxyethyl)-N 4 -(phenylmethyl)pyrimidine-2,4-diamine,
[0117] N 4 -(3-Methylphenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0118] N 4 -(3-Chloro-4-methylphenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0119] N 4 -[1-(4-Chlorophenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0120] N 4 -(1-Napthalenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 16,
[0121] N 4 -[(1S)-1-(1-Napthalenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 17,
[0122] N 2 -(2-Phenoxyethyl)-N 4 -(2-thienylmethyl)pyrimidine-2,4-diamine, Compound 18,
[0123] N 4 -[(1S)-1-(4-Methylphenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0124] N 4 -[4-(1-Methylethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0125] N 4 -[2-Fluoro-5-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0126] N 2 -(2-Phenoxyethyl)-N 4 -(4-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 19,
[0127] N 4 -(3-Chloro-4-fluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0128] N 2 -(2-Phenoxyethyl)-N 4 -(3-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 20,
[0129] N 2 -[2-(3-Hydroxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 21,
[0130] N 4 -[(1S)-1-Phenylethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0131] N 2 -(2-Phenylethyl)-N 4 -[(1S)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0132] N 2 -[2-(4-Hydroxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0133] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0134] N 4 -[1-(4-Fluorophenyl)ethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0135] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0136] N 4 -(2-Methoxyphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0137] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0138] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0139] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0140] N 2 -[2-(3-Cyanophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 22,
[0141] N 2 -[2-(1-Cyclohexenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 23,
[0142] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0143] N 4 -[(1S)-1-(1-Napthalenyl)ethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 24,
[0144] N 4 -(1-Methyl-1-phenyl)ethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0145] N 4 -(3-Iodophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 25,
[0146] N 2 -(2-Phenylethyl)-N 4 -(phenylmethyl)pyrimidine-2,4-diamine,
[0147] N 4 -(3-Methylphenylmethyl)-N 2 -(2-phenylethyl)pyrim idine-2,4-diamine,
[0148] N 4 -(4-Chlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0149] N 4 -(3-Bromophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 26,
[0150] N 4 -(3-Fluorophenylmethyi)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0151] N 2 -(2-Phenylethyl)-N 4 -(2-thienylmethyl)pyrimidine-2,4-diamine, Compound 27,
[0152] N 4 -[1-(4-Chlorophenyl)ethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0153] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0154] N 2 -(Methyl)-N 2 -(2-phenylethyl)-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0155] N 4 -(3,4-Difluorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0156] N 4 -(4-Benzodioxolylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0157] N 4 -(2-Chlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0158] N 4 -(3-Chloro-4-fluorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0159] N 4 -(3-Methoxyphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0160] N 4 -(4-Methoxyphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0161] N 2 -(2-Phenylethyl)-N 4 -[3-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0162] N 2 -[2-(1H-Indol-1-yl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 28,
[0163] N 4 -(1-Phenylethyl)-N 2 -[2-(2-thienyl)ethyl]pyrimidine-2,4-diamine, Compound 29,
[0164] N 2 -[2(1H-Indol-3-yl)ethyl]-N 2 -(methyl)-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 30 and
[0165] N 2 -[2-(6-Fluoro-1H-indol-3-yl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 31.
[0166] A ninth embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according the first aspect wherein
[0167] V and W are each N;
[0168] X is CH; and
[0169] R 1 is C 1-6 alkyl or C 3-7 cycloalkyl.
[0170] An tenth embodiment of the second aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0171] N 2 -[2-(3-Fluorophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0172] N 2 -[2-(3-Methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0173] N 2 -[2-(3-Bromophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0174] N 2 -[2-(3-Cyanophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0175] N 2 -[2-(4-Chlorophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0176] N 2 -[2-(4-Methylphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0177] N 2 -[2-(2-Methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0178] N 2 -[2-(3,5-Dimethoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0179] N 2 -[2-(3-Bromo-4-methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0180] N 2 -[2-(4-Methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine, and
[0181] N 2 -[2-(3-Acetamidophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine.
[0182] A first embodiment of a third aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first aspect wherein
[0183] X and W are each N;
[0184] V is CH; and
[0185] R 1 is H.
[0186] An second embodiment of the third aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention said compound being N 4 -[2-(4-Fluorophenoxy)ethyl]-N 2 -(1-phenylethyl)pyrimidine-2,4-diamine.
[0187] A first embodiment of a fourth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first aspect wherein
[0188] X and V are each N;
[0189] W is CH; and
[0190] R 1 is H.
[0191] A second embodiment of the fourth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0192] N 4 -[2-(4-Aminophenyl)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine, and
[0193] N 4 -[2-(4-Bromoophenyl)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine.
[0194] A third embodiment of the fourth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0195] N 4 -[2-(4-Hydroxyphenyl)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine, and
[0196] N 4 -[2-(4-Fluorophenoxy)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine, Example 16.
[0197] A first embodiment of a fifth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first embodiment of the first aspect wherein
[0198] V, W and X are each N; and
[0199] R 1 is NH 2 .
[0200] A second embodiment of a fifth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) according to the first embodiment of the first aspect wherein
[0201] V, W and X are each N;
[0202] R 1 is NH 2 ; and
[0203] Y is O.
[0204] A second embodiment of the fifth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0205] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 32,
[0206] N 2 -[2-(3,4-Dichlorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 33,
[0207] N 2 -[(1S)-1-(4-Bromophenyl)ethyl]-N 4 -[2-(4-methylphenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 34,
[0208] N 2 -[(1S)-1-Phenylpropyl]-N 4 -(2-phenylpropyl)-1,3,5-triazine-2,4,6-triamine, Compound 35,
[0209] N 2 -[(1S)-1-Phenylpropyl]-N 4 -[2-(3-(trifluoromethyl)phenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 36,
[0210] N 2 -[(1S)-1-Phenylethyl]-N 4 -(2-phenylpropyl)-1,3,5-triazine-2,4,6-triamine, Compound 37,
[0211] N 2 -[(1S)-1-(1-Napthalenyl)ethyl]-N 4 -[2-(phenylamino)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 38, and
[0212] N 2 -[2-(4-Bromophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 39.
[0213] A third embodiment of the fifth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0214] N 2 -[2-(Phenoxy)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 40,
[0215] N 2 -[2-(Phenoxy)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 41, Example 19-20,
[0216] N 2 -[(1S)-1-(1-Napthyl)ethyl]-N 4 -[2-(phenoxy)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 42,
[0217] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 43,
[0218] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[(1S)-1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 44,
[0219] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 45,
[0220] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[(1R)-1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 46,
[0221] N 2 -[2-(3,4-Difluorophenoxy)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 47,
[0222] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 48,
[0223] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 49,
[0224] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 50,
[0225] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 51,
[0226] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 52,
[0227] N 2 -[(1S)-1-Phenylethyl]-N 4 -{2-[3-(trifluoromethyl)phenyl]ethyl}-1,3,5-triazine-2,4,6-triamine, Compound 53,
[0228] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 54,
[0229] N 2 -[2-(3-Cyanophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 55,
[0230] N 2 -[(1S)-1-(1-Napthalenyl)ethyl]-N 4 -(2-phenylethyl)-1,3,5-triazine-2,4,6-triamine, Compound 56,
[0231] N 2 -[2-(1-Cyclohexenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 57
[0232] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 58 and
[0233] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 59.
[0234] A fourth embodiment of the fifth aspect of the present invention is a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (I) as described in the first aspect of the invention selected from the group consisting of
[0235] N 2 -[(1S)-1-Phenylethyl]-N 4 -(2-phenylethyl)-1,3,5-triazine-2,4,6-triamine, Compound 60,
[0236] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 61,
[0237] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 62,
[0238] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 63,
[0239] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 64,
[0240] N 2 -2-Phenylethyl-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 65,
[0241] N 2 -[2-(3-Bromophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 66,
[0242] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 67,
[0243] N 2 -[(1S)-1-(4-Bromophenyl)ethyl]-N 4 -[2-(3-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 68,
[0244] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 69,
[0245] N 2 -[(1S)-1-(4-Bromophenyl)ethyl]-N 4 -[2-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 70,
[0246] N 2 -[2-(3,4-Dichlorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 71,
[0247] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 72,
[0248] N 2 -[2-(3-Hydroxyphenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 73,
[0249] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]--1,3,5-triazine-2,4,6-triamine, Compound 74,
[0250] N 2 -[2-(4-Hydroxyphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 75,
[0251] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 76,
[0252] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 77,
[0253] N 2 -[2-(4-Aminophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 78,
[0254] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 79,
[0255] N 2 -[2-(4-Hydroxy-3-methoxyphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 80,
[0256] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Example 17,
[0257] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Example 18, 21, and
[0258] N 2 -(2-Chlorophenylmethyl)-N 4 -(2-phenylethyl)-1,3,5-triazine-2,4,6-triamine.
[0259] A first embodiment of a sixth aspect of the present invention are compounds of Formula (I)
[0260] or a pharmaceutically acceptable salts or hydrates thereof, wherein
[0261] V, W and X are each N, or V and X are each N and W is CH;
[0262] Y is O, S(O) m , CH 2 , NR 9 or a covalent bond;
[0263] Z is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl, pyridinyl and phenyl;
[0264] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NH SO 2 C 1-6 alkyl, NR 7 R 8 , C(O)NH 2 and C 1-3 alkylene;
[0265] m and n are each independently 0, 1 or 2;
[0266] R 1 is hydrogen, halogen or NR 7 R 8 ;
[0267] provided that
[0268] if W is CH, then R 1 is not halogen or NR 7 R 8 ;
[0269] if V, W and X are each N, then R 1 is not hydrogen;
[0270] R 2 is C 1-4 alkyl substituted with Z′, wherein
[0271] Z′ is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl, pyridinyl and phenyl;
[0272] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NH SO 2 C 1-6 alkyl, NR 7 R 8 and C(O)NH 2 ;
[0273] R 3 is hydrogen, C 1-6 alkyl or C 3-7 cycloalkyl;
[0274] R 4 and R 5 are independently hydrogen or C 1-6 alkyl or together are C 2-3 alkylene;
[0275] R 6 is hydrogen or C 1-3 alk(en)ylene
[0276] provided that
[0277] if R 6 is C 1-3 alk(en)ylene, it is attached to Z;
[0278] R 7 and R 8 are independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3-7 cycloalkyl, SO 2 C 1-6 alkyl;
[0279] or R 7 and R 8 together with the nitrogen to which they are attached form a 5 to 8 membered heterocycle;
[0280] said heterocycle optionally containing a second heteroatom selected from the group consisting of N, O and S;
[0281] said heterocycle being optionally substituted with up to three of the same or different substituents independently selected from C 1-6 alkyl or O—C 1-6 alkyl; and
[0282] R 9 is hydrogen or (C 1-6 )alkyl.
[0283] A second embodiment of the sixth aspect of the present invention are compounds of formula (I) according to the first embodiment of the sixth aspect, wherein
[0284] V, W and X are each N.
[0285] A third embodiment of the sixth aspect of the present invention are compounds of formula (I) according to the first embodiment of the sixth aspect, wherein
[0286] V and X are each N and W is CH.
[0287] A fourth embodiment of the sixth aspect of the present invention are compounds of formula (I) according to the first embodiment of the sixth aspect, wherein
[0288] Y is NR 9 .
[0289] A fifth embodiment of the sixth aspect of the present invention are compounds of formula (I) according to the first embodiment of the sixth aspect, wherein
[0290] Z is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl and pyridinyl;
[0291] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NH SO 2 C 1-6 alkyl, NR 7 R 8 , C(O)NH 2 and C 1-3 alkylene; and
[0292] Z′ is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl and pyridinyl;
[0293] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NH SO 2 C 1-6 alkyl, NR 7 R 8 and C(O)NH 2 .
[0294] A sixth embodiment of the sixth aspect of the present invention are compounds of formula (1) according to the first embodiment of the sixth aspect, wherein
[0295] Z′ is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl and pyridinyl;
[0296] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NH SO 2 C 1-6 alkyl, NR 7 R 8 and C(O)NH 2 .
[0297] A seventh embodiment of the sixth aspect of the present invention are compounds of formula (I) according to the first embodiment of the sixth aspect, wherein
[0298] Z is selected from the group consisting of benzodioxolyl, cyclohexenyl, furanyl, indolyl, napthalenyl, thienyl and pyridinyl;
[0299] optionally substituted with one to five groups, the same or different independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, O—C 1-4 alkyl, cyano, hydroxy, nitro, NH SO 2 C 1-6 alkyl, NR 7 R 8 , C(O)NH 2 and C 1-3 alkylene.
[0300] A first embodiment of a seventh aspect of the present invention are compounds of formula (Ia)
[0301] and pharmaceutically acceptable salts and solvates thereof, wherein
[0302] R 1 is phenyl optionally substituted with one or more of the same or different halogens; and
[0303] R 2 is phenyl or pyridyl optionally substituted with one or more of the same or different halogens.
[0304] A second embodiment of the seventh aspect of the present invention are compounds according to the first embodiment of the seventh aspect of the present invention wherein
[0305] R 1 is phenyl optionally substituted with one or more of the same halogens; and
[0306] R 2 is phenyl or pyridyl optionally substituted with one or more of the same halogens.
[0307] A third embodiment of the seventh aspect of the present invention are compounds according to the first embodiment of the seventh aspect of the present invention wherein
[0308] R 1 is phenyl optionally substituted with one halogen; and
[0309] R 2 is phenyl or pyridyl optionally substituted with one halogen.
[0310] A fourth embodiment of the seventh aspect of the present invention are compounds according to the first embodiment of the seventh aspect of the present invention wherein
[0311] R 1 is phenyl optionally substituted with fluoro; and
[0312] R 2 is phenyl or pyridyl optionally substituted with fluoro.
[0313] A fifth embodiment of the seventh aspect of the present invention are compounds according to the first embodiment of the seventh aspect of the present invention wherein
[0314] R 1 is unsubstituted phenyl; and
[0315] R 2 is monofluoro-phenyl or unsubstituted pyridyl.
[0316] A sixth embodiment of the seventh aspect of the present invention are compounds according to the first embodiment of the seventh aspect of the present invention wherein R 2 is unsubstituted 4-pyridyl.
[0317] A seventh embodiment of the seventh aspect of the present invention are compounds according to the first embodiment of the seventh aspect of the present invention selected from the group consisting of (S,S)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, (S,S)-trans-N-[2-(2-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, (±)-trans-N-(1-Phenyl-ethyl)-N′-(2-pyridin-4-yl-cyclopropylmethyl)-[1,3,5]triazine-2,4,6-triamine, (±)-trans-N-[2-(2-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, (S,S)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-[1-(4-fluoro)phenyl-ethyl]-[1,3,5]triazine-2,4,6-triamine and (±)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine.
[0318] Embodiments of an eighth aspect of the present invention comprise a method of treating CNS and ocular disorders comprising administration to a subject in need thereof an effective amount of a compound of Formula (Ia) as described in the seventh aspect of the present invention.
[0319] Embodiments of a ninth aspect of the present invention comprise a method of treating sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension comprising administration to a subject in need thereof an effective amount of a compound of Formula (Ia) as described in the seventh aspect of the present invention.
[0320] Embodiments of a tenth aspect of the present invention comprise a method of inhibiting methyltransferase proteins comprising administration of an effective amount of a compound of Formula (Ia) as described in the seventh aspect of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0321] The description of the invention herein should be construed in congruity with the laws and principals of chemical bonding. An embodiment or aspect which depends from another embodiment or aspect, will describe only the variables having values and provisos that differ from the embodiment or aspect from which it depends. Thus, for example, an embodiment which reads “the compound of formula (I) according to the n th aspect of the invention, wherein W is CH” should be read to include all remaining variables with values defined in the n th aspect and should be read to further include all the provisos, unless otherwise indicated, pertaining to each and every variable in the n th aspect.
[0322] As used herein the term “C 1-4 alkyl” may be a straight or branched chain having from 1 to 4 carbon atoms and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. As used herein the term “C 1-6 alkyl” may be a straight or branched chain having from 1 to 6 carbon atoms and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, n-hexyl, etc. The term “C 3-7 cycloalkyl” are cyclic alkanes with or without branching having from 3 to 7 carbon atoms and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 2-methylcyclopropyl etc. The term “C 2-3 alkylene” can be a straight or branched chain having from 2 to 3 carbon atoms and includes —(CH 2 ) 2 —, —(CH 2 ) 3 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, and —CH(CH 3 )CH 2 —. The term “alk(en)ylene” can mean alkenylene or alkylene. The term “halogen” or “halo” includes fluoro, chloro, bromo and iodo.
[0323] It is to be understood that the present invention includes stereoisomers, e.g. optical isomers including individual enantiomers and mixtures of enantiomers which can arise as a consequence of structural asymmetry due to the presence of an asymmetric carbon atom which may be incorporated in some examples of the Formula I compounds. The compounds of the present invention may be prepared enantioselectively, or alternatively, the separation of the individual stereoisomers can be accomplished by application of various methods which are well known to practitioners in the art.
[0324] For medicinal use, the pharmaceutically acceptable acid addition salts of Formula (I) compounds are included in the invention. Such salts are those in which the anion does not contribute significantly to toxicity or pharmacologic activity of the organic cation. These salts may be preferred in some cases. The acid addition salts may be prepared from inorganic or organic acids, e.g. salts with acids such as hydrochloric, hydrobromic, hydroiodic, phosphoric, sulfuric, maleic, acetic, citric, succinic, tartaric, benzoic, fumaric, mandelic, p-toluenesulfonic, methanesulfonic, ascorbic, lactic, gluconic, trifluoroacetic and the like. The compounds of the present invention may be hydrated or non-hydrated.
[0325] The compounds of this invention can be administered in such oral dosage forms as tablets, capsules (each of which includes sustained release or timed release formulations), pills, powders, granules, elixirs, tinctures, suspensions, syrups and emulsions. The compounds of this invention may also be administered intravenously, intraperitoneally, subcutaneously, or intramuscularly, all using using dosage forms well known to those of ordinary skill in the pharmaceutical arts. The compounds can be administered alone but generally will be administered with a pharmaceutical carrier selected upon the basis of the chosen route of administration and standard pharmaceutical practice.
[0326] Compounds of this invention can also be administered in intranasal form by topical use of suitable intranasal vehicles, or by transdermal routes, using transdermal skin patches. When compounds of this invention are administered transdermally the dosage will be continuous throughout the dosage regimen.
[0327] The compounds of this invention can also be administered to the eye, preferrably as a topical opthalmic formulation. The opthalmic formulation may be a sterile opthalmic suspension or solution, formed by combining a compound of this invention with opthalmologically acceptable preservatives, surfactants, viscosity enhancers, penetration enhancers, buffers, sodium chloride, and water. Opthalmic solution formulations may be prepared by dissolving a compound of this invention in a physiologically acceptable isotonic buffer which may include an opthalmologically acceptable surfactant to assist in dissolving the compound. The opthalmic solution may also contain an agent to increase viscosity such as hydroxymethylcellulose or a gelling agent such as gellan or xanthan gum. The compounds of this invention can also be combined with a preservative and an appropriate vehicle such as mineral oil or liquid lanolin to provide an opthalmic ointment. Opthalmic gels can be prepared by suspending a compound of this invention in a hydrophilic base such as carbopol-940. The preferred opthalmic formulation is the opthalmic suspension or solution. The opthalmic suspension or solution will contain approximately 0.01% to 5% by weight of a compound of this invention and will have a pH of about 5 to 8. The opthalmic suspension or solution can be topically administered by delivering 1 to 2 drops of the formulation to the surface of the eye. This dosage can be administered between 1 to 4 times daily at the discretion of the clinician.
[0328] The dosage can vary within wide limits and will have to be adjusted to the individual requirements in each particular case. By way of general guidance, the daily oral dosage can vary from about 0.01 mg to 1000 mg, 0.1 mg to 100 mg, or 10 mg to 500 mg per day of a compound of Formula (I) or of the corresponding amount of a pharmaceutically acceptable salt thereof. The daily dose may be administered as single dose or in divided doses and, in addition, the upper limit can also be exceeded when this is found to be indicated.
Synthesis
[0329] The compounds of Formula I can be synthesized as shown in Schemes 1-3. Specific reactions employed for the preparation of compounds of Formula I are described below. Many of the reactions are conventional and their modification for adaptation for specific compounds of Formula I would be known to one skilled in the art of organic synthesis. It will be understood by one skilled in the art that the functionality present on the molecule should be consistent with the desired transformation and that modification of the order of the synthetic steps may be necessary to prepare a compound of the invention. Preferred methods for the synthesis of Formula I compounds include, but are not limited to, the methods described below. The abbreviations used in the description and examples are conventional abbreviations well-known to those skilled in the art. Some of the abbreviations used are as follows:
CH 2 Cl 2 = Dichloromethane CH 3 CN = Acetonitrile DMF = N,N-Dimethylformamide DMSO = Dimethylsulfoxide EtOAc = Ethyl acetate EtOH = Ethanol Et 2 O = Diethyl ether Fmoc = (9-Fluorenylmethoxycarbonyl) THF = Tetrahydrofuran MeOH = Methanol NMP = 1-Methyl-2-pyrrolidinone TFA = Trifluoroacetic acid
[0330] [0330]
[0331] Compounds of Formula I may be prepared, as shown in Scheme 1, by sequential displacement of leaving groups on a heterocycle, V, with appropriate amines, IV and II, in the presence of a base in an appropriate solvent. Examples of useful leaving groups, LG, on heterocycle V include, but are not limited to, Cl, Br, I, alkylsulfonate, arylsulfonate or perhaloalkylsulfonate. Useful bases include, but are not limited to, an excess of the amine itself (IV or 11), metal carbonates such as K 2 CO 3 or CsCO 3 , hindered alkoxides such as potassium t-butoxide, or non-nucleophilic tertiary organic amines such as triethylamine, N,N-diisopropylethylamine or 4-methylmorpholine. Typical solvents include, but are not limited to, aprotic solvents such as NMP, DMF, dimethylacetamide, CH 3 CN, dioxane, CH 2 Cl 2 , THF or protic solvents such as MeOH, EtOH, isopropanol, butanol, amyl alcohol, cyclohexanol and ethoxyethoxyethanol. The temperature range used for both steps in Scheme 1 is between −10° C. and 200° C. It is understood by one skilled in the art that mixtures of regioisomers of intermediate III may be obtained from the initial displacement reaction in Scheme 1. It is also understood by one skilled in the art that the regioisomers thus obtained can be separated and purified by recrystallization or column chromatography and then further reacted to give compounds of Formula I.
[0332] In a more detailed description of the procedure, one molar equivalent of an optionally substituted pyrimidine, such as 4,6-dichloropyrimidine or 2,4-dichloropyrimidine, and one molar equivalent of a tertiary amine such as triethylamine, diisopropylethylamine or 4-methylmorpholine and one molar equivalent of an amine, ZY(CH 2 ) n CH(R 5 )CH(R 6 )NH(R 4 ), are combined in a solvent such as EtOH and maintained between −10° C. to 200° C. for a period of 1 to 48 hours. A preferred temperature range for this step is between 0° C. and 80° C.
[0333] The reaction mixture can be filtered and the filtrate concentrated under reduced pressure to provide the intermediate product, III. Alternatively, the reaction mixture can be diluted with an organic solvent such as CH 2 Cl 2 or EtOAc. The organic layer can then be washed with water and brine, dried over magnesium sulfate or sodium sulfate, filtered, and concentrated under reduced pressure to provide the intermediate product. The intermediate product may be purified by recrystallization or by chromatography on silica gel using an eluant such as EtOAc, hexanes, CH 2 Cl 2 , chloroform, Et 2 O, MeOH, EtOH or mixtures thereof.
[0334] The second step of the synthesis consists of combining one molar equivalent of the intermediate product, III, such as a 2-chloro-4-aminopyrimidine, 4-chloro-2-aminopyrimidine or 4-chloro-6-aminopyrimidine derivative, with either two or more molar equivalents of amine, R 3 R 2 NH, or one molar equivalent of amine, R 3 R 2 NH, and one molar equivalent of a tertiary amine such as triethylamine, diisopropylethylamine, or 4-methylmorpholine, in a solvent such as NMP or ethoxyethoxyethanol for a period of 1 to 48 hours at reaction temperatures between −10° C. and 200° C.
[0335] The reaction mixture is then allowed to cool to room temperature. In cases where more than two equivalents of amine, R 3 R 2 NH, were used, the mixture can be stirred with polystyrene-bound aldehyde resin in order to scavenge the excess amine. (The aldehyde resin was prepared by treating chloromethyl polystyrene resin (Merrifield resin) with 1.4 molar equivalents of sodium bicarbonate in anhydrous DMSO at 160° C. for 24 hours. The resin was then collected by filtration, washed with DMSO, H 2 O, 1:1 DMSO/H 2 O, DMF, acetone, EtOH, CH 2 Cl 2 , Et 2 O and MeOH, then was dried under vacuum). The reaction mixture is filtered and the filtrate is concentrated under reduced pressure. The crude material can be purified by either chromatography on silica gel using an eluant such as CH 2 Cl 2 , hexane, EtOAc, chloroform, Et 2 O, MeOH, EtOH or mixtures thereof. Alternatively, the crude material can be purified by reverse phase HPLC on C-18 using eluent such as MeOH, CH 3 CN, H 2 O, TFA or mixtures thereof. If necessary, further purification of the compound can be accomplished by recrystallization.
[0336] Other compounds of Formula I may be prepared, as shown by Scheme 2, by sequential displacement of leaving groups on a substituted heterocycle, XIV, which has been attached to an insoluble polymer support, XV, with appropriate amines, IV and II, in the presence of a base in an appropriate solvent. Examples of useful leaving groups, LG, on heterocycle XIV include, but are not limited to, Cl, Br, I, alkylsulfonate, arylsulfonate or perhaloalkylsulfonate. Useful bases include, but are not limited to, an excess of the amine itself (IV or II), metal carbonates such as K 2 CO 3 or CsCO 3 , or non-nucleophilic tertiary organic amines such as triethylamine, N,N-diisopropylethylamine or 4-methylmorpholine. Typical solvents include, but are not limited to dichloroethane, DMF and NMP and the reactions are typically carried out between 0° C. and 100° C. The resulting resin bound compound, XI, is treated with acid, such as TFA, in an appropriate solvent such as CH 2 Cl 2 , then the resin is filtered and rinsed with solvent. The filtrate and combined rinsing solution is then combined and concentrated under reduced pressure to afford compounds of Formula I wherein R 1 =NH 2 .
[0337] Some compounds of Formula I may be prepared, as shown in Scheme 3, by sequential displacement of leaving groups on a heterocycle, XIV, with appropriate amines, in the presence of base in an appropriate solvent. The leaving groups, solvents, bases, and techniques used for isolating the intermediate products as well as the compounds of Formula I are the same as previously described for Scheme 1.
[0338] In a more detailed description of the procedure, one molar equivalent of a heterocycle, XIV, such as cyanuric chloride, and one molar equivalent of a tertiary amine such as triethylamine, diisopropylethylamine, or 4-methylmorpholine, and one molar equivalent of an amine, R 3 R 2 NH, are combined in a solvent such as THF and maintained between −10° C. to 30° C. for a period of 1 to 48 hours. The reaction mixture is concentrated under reduced pressure, the residue is dissolved in a solvent, such as EtOAc or CH 2 Cl 2 , and then extracted with 1 N HCl, H 2 O, and brine. The organic layer is dried, filtered, and concentrated to afford intermediate, XXIII. Intermediate XXIII can be combined with an amine, R 1 H, such as ammonium hydroxide, dimethylamine or morpholine in a solvent such as THF in the presence of base at ambient temperature for a period of 1 to 48 hours. The reaction mixture is concentrated under reduced pressure and the residue is dissolved in a solvent such as CH 2 Cl 2 or EtOAc then extracted with H 2 O. The organic layer is dried, filtered and concentrated in vacuo to afford intermediate, XXII. Intermediate XXII can be combined with either two or more molar equivalents of amine, ZY(CH 2 ) n CH(R 5 )CH(R 6 )NH(R 4 ), or one molar equivalent of amine, ZY(CH 2 ) n CH(R 5 )CH(R 6 )NH(R 4 ), and one molar equivalent of a tertiary amine such as triethylamine, diisopropylethylamine, or 4-methylmorpholine, in a solvent such as THF or NMP at reaction temperatures between approximately 30° C. and 80° C. for 1 to 48 hours. The reaction may then be concentrated under reduced pressure and the residue dissolved in a solvent such as CH 2 Cl 2 or EtOAc. The organic layer can be extracted with H 2 O, dried, and concentrated to afford compound of Formula I as the free base. Alternatively, the organic layer can be washed with 1 N HCl and solids which precipitate from the organic layer can be collected by filtration. The solids can be washed with H 2 O and CH 3 CN, triturated with hot CH 3 CN, collected by filtration, and dried to afford compounds of Formula I as the hydrochloride salt.
[0339] The amines, ZY(CH 2 ) n CH(R 5 )CH(R 6 )NH(R 4 ) and R 3 R 2 NH, employed in the synthesis of Formula I compounds, are either commercially available or can be readily synthesized by the methods shown in Schemes 4-6.
[0340] Racemic mixtures of an amine may be resolved by methods known to those skilled in the art and the chiral amine may then be used in the synthesis. A typical preparation of an amine, as shown in Scheme 4, may be accomplished by refluxing an acetonitrile solution of an aniline, phenol, thiophenol or amino, thio or hydroxyl bearing heterocycle with chloroacetonitrile in the presence of a base, such as potassium carbonate. The resulting acetonitrile derivative may then be reduced, with a reducing agent such as alane, to provide an amine of Formula IV wherein n=0, R 4 , R 5 , and R 6 are H. Alternatively, the amines can be prepared as shown in Scheme 5, by alkylating a substituted aniline, phenol, thiophenol or amino, thio or hydroxyl bearing heterocycle with a protected aminoalkylhalide to provide protected alkylamine derivatives. A preferred protecting group (PG) is the tert-Butoxycarbonyl (Boc) group. These derivatives can then be deprotected to provide amine intermediates of Formula IV. For example, when PG is Boc, treatment of the protected intermediate with an acid such as trifluoroacetic acid or hydrochloric acid provides amines of Formula IV.
[0341] A third method used to synthesize amine intermediates is shown in Scheme 6 and consists of the preparation of an oxime which is then reduced to provide the amine intermediate, II.
[0342] All of the compounds were synthesized by using the preceding general methodologies and were characterized by LC/MS. The following tables provide retention times and the mass observed for selected compounds of the invention. For LC/MS analysis all Liquid Chromatography (LC) data were recorded on a Shimadzu LC-10AS liquid chromatograph using a SPD-10AV UV-Vis detector and Mass Spectrometry (MS) data were determined with a Micromass Platform for LC in electrospray mode. The various LC/MS methods used for the analysis of the compounds are given below. Purification of compounds by preparative HPLC was accomplished using either a Shimadzu LC-8A liquid chromatograph using a SPD-10AV UV-Vis detector and equipped with FRC-10A fraction collectors or a Varian Prostar Model 215 liquid chromatograph using a Rainin Dynamax UV-Vis detector. A typical preparative HPLC method is given below. In the LC/MS methods and the preparative HPLC method Solvent A is 10% MeOH/90% H 2 O/0.1% TFA and Solvent B is 90% MeOH/10% H 2 O/0.1% TFA.
[0343] Preparative HPLC Method
[0344] Column: YMC ODS S5 30×100 mm
[0345] Gradient: Linear gradient from 100% Solvent A 0% Solvent B to 0% Solvent A/100% Solvent B
[0346] Gradienttime: 11 minutes
[0347] Hold time: 5 minutes
[0348] Flow rate: 49 mL/min
[0349] Detector Wavelength: 254 nm
[0350] LC/MS Method A
[0351] Column: YMC ODS S5 4.6×50 mm Ballistic
[0352] Gradient: Linear gradient from 100% Solvent A/0% Solvent B to 0% Solvent A/100% Solvent B
[0353] Gradient time: 3 minutes
[0354] Hold time: 1 minute
[0355] Flow rate: 4 mL/min
[0356] Detector Wavelength: 220 nm
[0357] LC/MS Method B
[0358] Column: YMC ODS-A S7 3.0×50 mm
[0359] Gradient: Linear gradient from 100% Solvent A/0% Solvent B to 0% Solvent A/100% Solvent B
[0360] Gradient time: 2 minutes
[0361] Hold time: 1 minute
[0362] Flow rate: 5 mL/min
[0363] Detector Wavelength: 220 nm
TABLE 1 All of the compounds in Table 1 were analyzed using LC/MS Method A. HPLC RetentionTime MS Data Compound # (min) (M + H) + 1 1.71 320 2 2.84 295 3 3.09 376 4 1.53 311 5 1.49 306 6 2.29 364 7 3.06 356 8 3.17 399 9 3.26 399 10 3.37 331 11 1.61 306 12 1.79 320 13 3.03 413 14 2.44 414 15 2.99 447 16 3.00 371 17 3.03 385 18 2.69 327 19 1.11 322 20 1.29 322 21 2.77 335 22 2.80 342 23 3.49 324 24 3.25 369 25 3.21 431 26 3.15 383 27 2.94 311 28 2.96 358 29 3.19 325 30 3.30 372 31 3.24 374
[0364] [0364] TABLE 2 HPLC Retention Time MS Data LC/MS Compound (min) (M + H) + Method 32 3.24 383 A 33 3.48 417 A 34 3.44 427 A 35 3.17 363 A 36 3.36 417 A 37 3.09 349 A 38 2.94 400 A 39 1.63 460 B 40 3.07 365 A 41 2.96 351 A 42 3.16 401 A 43 — 385 — 44 1.57 387 B 45 1.49 414 B 46 1.57 387 B 47 1.52 432 B 48 3.01 353 A 49 3.37 363 A 50 3.16 369 A 51 3.13 367 A 52 3.11 379 A 53 3.29 403 A 54 3.00 365 A 55 2.80 360 A 56 3.20 385 A 57 3.22 339 A 58 1.61 414 B 59 1.61 414 B 60 3.02 335 A 61 3.15 353 A 62 3.14 369 A 63 3.25 367 A 64 3.16 353 A 65 3.11 349 A 66 3.16 413 A 67 3.26 367 A 68 3.31 431 A 69 3.23 383 A 70 3.31 431 A 71 3.40 403 A 72 3.29 349 A 73 2.72 351 A 74 1.51 398 B 75 1.28 396 B 76 1.53 398 B 77 1.50 410 B 78 1.00 395 B 79 1.61 394 B 80 1.29 426 B
[0365] [0365] TABLE 3 The Formula IV intermediates in Table 3 were analyzed using LC/MS method B. HPLC Re- tention Time MS Data Formula IV Intermediate (min) observed m/z 3-(2-Fluorophenoxy)propylamine hydrochloride 0.54 170 3-(3-Fluorophenoxy)propylamine hydrochloride 0.64 170 3-(4-Fluorophenoxy)propylamine hydrochloride 0.60 170 3-(2-Methoxyphenoxy)propylamine hydrochloride 0.63 182 3-(3-Methoxyphenoxy)propylamine hydrochloride 0.66 182 3-(4-Methoxyphenoxy)propylamine hydrochloride 0.59 182 3-(2-Cyanophenoxy)propylamine hydrochloride 0.59 177 3-(3-Cyanophenoxy)propylamine hydrochloride 0.54 177 3-(4-Cyanophenoxy)propylamine hydrochloride 0.48 177 2-(2-Cyanophenoxy)ethylamine hydrochloride 0.45 163 2-(3-Cyanophenoxy)ethylamine hydrochloride 0.38 163 2-(4-Cyanophenoxy)ethylamine hydrochloride 0.31 163 2-(2-Pyridinyl)ethylamine dihydrochloride 0.11 139 2-(3-Pyridinyl)ethylamine dihydrochloride 0.09 139 2-(4-Pyridinyl)ethylaminedi hydrochloride 0.08 139
EXAMPLES
[0366] The following examples illustrate the invention, but are not intended as a limitation thereof. In the following examples, all temperatures are given in degrees Centigrade. Melting points were determined on an electrothermal apparatus and are not corrected. Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded on a Bruker AM-300 or a Varian Gemini 300 spectrometer. All spectra were determined in CDCl 3 , DMSO-d 6 , CD 3 OD or D 2 O unless otherwise indicated. Chemical shifts are reported in • units relative to tetramethylsilane (TMS) or a reference solvent peak and interproton coupling constants are reported in Hertz (Hz). Splitting patterns are designated as follows: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad peak; dd, doublet of doublets; dt, doublet of triplets; and app d, apparent doublet, b broad, etc. Mass spectra were recorded on a Kratos MS-50 or a Finnegan 4500 instrument utilizing direct chemical ionization (DCI, isobutene), fast atom bombardment (FAB), or electron ion spray (ESI).
[0367] Analytical thin-layer chromatography (TLC) was carried out on precoated silica gel plates (60F-254) and visualized using UV light, iodine vapors, and/or staining by heating with methanolic phosphomolybdic acid. Column chromatography, also referred to as flash chromatography, was performed in a glass column using finely divided silica gel at pressures somewhat above atmospheric pressure.
[0368] A. Synthesis of Intermediates
Example 1
Example of Scheme 6
[0369] Preparation of 1-(4-Chlorophenyl)ethylamine (Intermediate of Formula II)
[0370] To a mixture of 4′-chloroacetophenone (15.5 g, 100 mmol) and hydroxylamine sulfate (24.6 g, 300 mmol) in EtOH (150 mL) was added 50% (w/w) aqueous NaOH (24 g, 300 mmol) and H 2 O (50 mL). The mixture was refluxed for 4 h then was diluted with H 2 O (400 mL) and allowed to cool. The mixture was extracted with CH 2 Cl 2 . The organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to provide the oxime intermediate as a white solid (16.5 g, 98%). The oxime intermediate was reduced with alane [generated from lithium aluminum hydride (31.0 g, 817 mmol) and sulfuric acid (40.1 g, 409 mmol) by the method of Brown in Fieser and Fieser, Vol 1, 35] in THF at reflux for 6 h, and after the standard workup according to Fieser and Fieser, Vol 1, 584; provided the titled compound (12 g).
Example 2
[0371] 2-(4-Fluorophenoxy)ethylamine (Intermediate of Formula IV)
[0372] The 2-(4-Fluorophenoxy)ethylamine was prepared by both the method of Scheme 4 and Scheme 5.
Example of Scheme 4
[0373] A mixture of 4-fluorophenol (22.4 g, 200 mmol), chloroacetonitrile (17.1 g, 220 mmol) and excess powdered potassium carbonate was refluxed for 7 h then the mixture was concentrated under reduced pressure. The residue was mixed with H 2 O and was extracted with Et 2 O. The combined organic layers were dried, filtered and concentrated under reduced pressure. The residue was Kugelrohr distilled to provide 2-(4-Fluorophenoxy)acetonitrile (25 g, 84%). The 2-(4-Fluorophenoxy)acetonitrile (25 g, 185 mmol) was reduced with alane [generated from lithium aluminum hydride (19.6 g, 516 mmol) and sulfuric acid (25.3 g, 258 mmol) according to the procedure in Example 1]. The crude product was purified by Kugelrohr distillation to provide the titled compound (12 g).
Example of Scheme 5
[0374] A mixture of 4-fluorophenol (2.2 g, 20 mmol), 2-Bromo-N-(t-butoxycarbonyl)ethylamine (4.5 g, 20 mmol) and excess powdered potassium carbonate in CH 3 CN was refluxed for 48 h then was allowed to cool. The mixture was filtered and the filtrate was concentrated under reduced pressure. The residue was dissolved in Et 2 O and was washed with 1 N NaOH. The organic layer was then concentrated under reduced pressure. The residue was stirred in 2N HCl for 16 h at ambient temperature then the mixture was made basic. The mixture was then extracted with Et 2 O. The organic layer was dried, filtered and concentrated under reduced pressure to provide the titled compound (1.5 g)
[0375] 2-(4-Fluorophenoxy)ethylamine, hydrochloride: was prepared by treating a CH 3 CN solution of 2-(4-Fluorophenoxy)ethylamine hydrochloric acid then concentrating under reduced pressure. 1 H NMR (dmso-d 6 ) δ 8.46 (b s, 3H), 7.11(dd, J=9, 9, 2H), 7.00 (dd, J=9, 4, 2H), 4.18 (t, J=5, 2H), 3.16 (t, J=5, 2H).
Example 3
[0376] The following intermediates of Formula IV were prepared according to the method of Scheme 4 as in Example 2.
[0377] 2-(2-Fluorophenoxy)ethylamine, hydrochloride: 1 H NMR (dmso-d 6 ) δ 8.35 (b s, 3H), 7.12-7.28 (m, 3H), 6.96-7.03 (m, 1H), 4.28 (t, J=5, 2H), 3.21 (t, J=5, 2H).
[0378] 2-(3-Fluorophenoxy)ethylamine, hydrochloride: 1 H NMR (dmso-d 6 ) δ 8.25 (b s, 3H), 7.35 (q, J=8, 1H), 6.78-6.89 (m, 3H), 4.20(t, J=5, 2H), 3.19 (t, J=5, 2H).
[0379] 2-(3-Methoxyphenoxy)ethylamine, hydrochloride: 1 H NMR (dmso-d 6 ) δ 8.36 (b s, 3H), 7.21 (dd, J=8, 8,1H), 6.56 (d, J=8, 1H), 6.55 (d, J=8, 1H), 6.53 (s, 1H), 4.18 (t, J=5, 2H), 3.73 (s, 3H), 3.16 (t, J=5, 2H).
[0380] 2-(4-Methoxyphenoxy)ethylamine, hydrochloride: 1 H NMR (dmso-d 6 ) δ 8.27 (b s, 3H), 6.94 (d, J=9, 2H), 6.87 (d, J=9, 2H), 4.11 (t, J=5, 2H), 3.70 (s, 3H), 3.15 (b s, 2H).
Example 4
Example of Scheme 1
[0381] 4-Chloro-r2-(2-phenylethyl)amino]pyrimidine and 2-Chloro-[4-(2-phenylethyl)amino]pyrimidine (Intermediates of Formula III)
[0382] To a solution of 2,4-dichloropyrimidine (750 mg, 5.0 mmol) and triethylamine (0.7 mL, 5.0 mmol) in EtOH (5 mL) was added a solution of 2-phenylethylamine (606 mg, 5.0 mmol) in EtOH (10 mL). The reaction mixture was stirred at rt for 24 h then was diluted with CH 2 Cl 2 . The organic layer was washed with H 2 O and brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford an oil. The crude oil was purified by column chromatography on silica gel (eluted with EtOAc/Hexane, 30/70) to afford 4-chloro-[2-(2-phenylethyl)amino]pyrimidine [200 mg, 17%, (Rf=0.55, SiO 2 eluted with EtOAc/Hexane, 30/70); 1 H NMR (CDCl 3 ) δ 8.14 (d, J=5, 1H), 7.21-7.35 (m, 5H), 6.57 (d, J=5, 1H), 5.31 (bs, 1H), 3.71 (q, J=7, 2H), 2.92 (t, J=7, 2H); LC/MS (ESI + ) 233.8 obs] and 2-chloro-[4-(2-phenylethyl)amino]pyrimidine [685 mg, 59%, (R f =0.33, SiO 2 eluted with EtOAc/Hexane, 30/70); 1 H NMR (CDCl 3 ) δ 8.01 (bs, 1H), 7.20-7.36 (m, 5H), 6.24 (dd, J=2,4, 1H), 5.34 (bs, 1H), 3.64 (bs, 2H), 2.94 (t, J=7, 2H); LC/MS (ESI + ) 233.8 obs]. A small portion of 4-chloro-[2-(2-phenylethyl)amino]pyrimidine was recrystallized from diisopropyl ether to obtain crystalline material as colorless plates. A single 0.05×0.30×0.30 mm crystal was subjected to X-ray crystallography on a Bruker AXS and the structure was found to be 4-chloro-[2-(2-phenylethyl)amino]pyrimidine.
Example 5
Example of Scheme 1
[0383] 4-Chloro-2-[(2-(4-fluorophenoxy)ethyl)amino]pyrimidine and 2-Chloro-4-[(2-(4-fluorophenoxy)ethyl]aminolpyrimidine (Intermediates of Formula III)
[0384] The titled compounds were prepared according to the method of Example 4 starting from 2,4-dichloropyrimidine and 2-(4-fluorophenoxy)ethylamine to afford the titled compounds as white solids. 4-Chloro-2-[(2-(4-fluorophenoxy)ethyl)amino]pyrimidine 1 H NMR (CDCl 3 ) δ 8.16 (d, J=5, 1H), 6.96 (m, 2H), 6.86 (m, 2H), 6.61 (d, J=5, 1H), 5.82 (bs, 1H), 4.10 (t, J=5, 2H), 3.85 (q, J=5, 2H); MP 85-86° C. 2-Chloro-4-[(2-(4-fluorophenoxy)ethyl)amino]pyrimidine: 1 H NMR (CDCl 3 ) δ 8.03 (d, J=5, 1H), 6.97 (m, 2H), 6.86 (m, 2H), 6.33 (d, J=6, 1H), 5.60 (bs, 1H), 4.11 (t, J=5, 2H), 3.82 (bs, 2H); MP 143-144° C.
Example 6
Example of Scheme 1
[0385] 6-Chloro-4-[(1S)-(1-phenylethyl)amino]pyrimidine (Intermediate of Formula III)
[0386] A solution of 4,6-dichloropyrimidine (14.9 g, 100 mmole) and (1S)-1-phenylethylamine (13.3 g, 110 mmole) in CH 3 CN (100 mL) was refluxed for 4 hours. The reaction was partitioned between Et 2 O (500 mL) and H 2 O (250 mL). The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel 60 with Hexane/EtOAc 3:1. Pure fractions were combined, concentrated under reduced pressure, and dried under high vacuum to afford the titled compound (18.6 g, 80%) as a yellow oil. 1 H NMR (CDCl 3 ): δ 1.57 (d, J=7.0 Hz, 3H), 4.6 (b s,1H), 5.6 (b s,1H), 6.19 (s,1H), 7.34 (m, 5H), 8.30 (s,1H); LC/MS (MH+) 233.62.
Example 7
Example of Scheme 2
[0387] Intermediate XV
[0388] Knorr resin, XVI, (25 g, 20 mmol) was shaken in DMF (150 mL) for 5 minutes and drained. The swollen resin was treated with 30% piperidine in DMF (150 mL) and shaken at ambient temperature for 25 minutes. The resin was then drained and washed sequentially with DMF and CH 2 Cl 2 (4×200 mL each) and dried under vacuum at ambient temperature to yield resin XV.
Example 8
Example of Scheme 2
[0389] Intermediate XIII of structure:
[0390] To resin XV was added diisopropylethylamine (17.4 mL, 100 mmol) and a solution of cyanuric chloride [XIV, wherein V, W, X are N and LG is Cl (36.9 g, 200 mmol)] in dichloroethane (250 mL). The mixture was shaken for 1 h, drained, and washed sequentially with DMF and CH 2 Cl 2 (4×200 mL each). The resin was then dried under vacuum at ambient temperature to yield resin XIII.
Example 9
Example of Scheme 2
[0391] Intermediate XII of structure:
[0392] To Intermediate XIII, Compound of Example 8, (20 mmol) in NMP (300 mL) was added 1-[(1S)-(4-fluorophenyl)ethyl]amine, 11 (3.06 g, 22 mmol) and diisopropylethylamine (2.59 g, 20 mmol). The mixture was shaken at 40° C. for 18 h, drained, and washed sequentially with DMF, THF, CH 2 Cl 2 , and MeOH (4×200 mL each). Drying under vacuum at ambient temperature afforded a pale tan free flowing resin of formula XII, above.
Example 10
Example of Scheme 2
[0393] Intermediate XII of Structure:
[0394] To Intermediate XIII, Compound of Example 8, (8.0 g, 6.4 mmol) in NMP (60 mL) was added [(1S)-1-(phenylethyl)]amine (1.0 mL, 7.6 mmol) and diisopropylethylamine (1.12 mL, 6.4 mmol). The mixture was vortexed (100 rpm) at 40° C. for 16 hours. The solution was drained, then the resin was washed sequentially with DMF (3×50 mL), THF (3×50 mL), CH 2 Cl 2 (3×50 mL) and MeOH (3×50 mL) and dried to provide XII, above.
Example 11
Example of Scheme 2
[0395] Intermediate XI of structure:
[0396] Intermediate XI was synthesized in a 48 tube reactor shaker. To a reaction tube containing Intermediate XII, Compound of Example 9, (0.100 g, 90 μmoles), was added 2-(4-fluorophenyl)ethylamine, IV (0.9 mL, 450 μmoles as a 0.5 M solution in NMP). The reactor was shaken at 80° C. for 4 days, drained, and the resin washed sequentially with DMF, THF, CH 2 Cl 2 , and MeOH (4×2 mL each) to provide the Intermediate XI above.
Example 12
Example of Scheme 2
[0397] Intermediate XI of structure:
[0398] Intermediate XI (above) was prepared from Intermediate XII, Compound of Example 9, (0.100 g, 90 μmoles) and 2-(2-aminoethyl) pyridine (0.9 mL, 450 μmoles as a 0.5 M solution in NMP) as described previously for Example 11.
Example 13
Example of Scheme 2
[0399] Intermediate XI of structure:
[0400] To Intermediate XII, Compound of Example 10, (5.5 g, 4.4 mmol) in NMP (40 mL) was added 2-phenoxyethylamine (4.83 g, 35.2 mmol). The mixture was vortexed (100 rpm) at 85° C. for 72 h then the solution was drained. The resin was washed sequentially with DMF (3×50 mL), THF (3×50 mL), CH 2 Cl 2 (3×50 mL) and MeOH (3×50 mL) then dried to provide Intermediate XI, above.
Example 14
Example of Scheme 3
[0401] 4,6-Dichloro-N 2 -[(1S)-1-phenylethyl]-1,3,5-triazine-2-amine (Intermediate of Formula XXIII)
[0402] To a solution of cyanuric chloride (25.0 g, 0.135 mol), diisopropylethylamine (17.5 g, 0.135 mol) in THF (500 mL) at 0° C. was added dropwise a solution of (1S)-1-phenylethylamine (16.4 g, 0.135 mol) in THF (100 mL) while maintaining the reaction temperature at or near 0° C. The reaction mixture was allowed to warm to ambient temperature then was concentrated under reduced pressure. The residue was dissolved in EtOAc (500 mL) and extracted with 1 N HCl (250 mL), H 2 O (250 mL) and brine (250 mL). The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to afford the titled compound as a white solid (35 g, 96%) MP 146-147° 1 H NMR (CDCl 3 ) δ 7.39 (m, 5H), 6.40 (b d, 1H), 5.25 (m, 1H), 1.59 (d, 3H); MS (ESI + ) (M + ) 269.1 obs.
Example 15
Example of Scheme 3
[0403] 4-Chloro-N 2 -r(1S)-1-henylethyll-1,3,5-triazine-2,4-diamine (Intermediate of Formula XXII)
[0404] To a solution of 4,6-Dichloro-N 2 -[(1S)-1-phenylethyl]-1,3,5-triazine-2-amine, (Compound of Example 14), in THF (500 mL) was added conc. NH 4 OH (50 mL). The reaction mixture was stirred at ambient temperature for 48 h then was concentrated under reduced pressure. The residue was dissolved in CH 2 Cl 2 (500 mL) and was washed with H 2 O (2×250 mL). The organic layer was filtered through a cotton plug then dried over sodium sulfate, filtered and concentrated under reduced pressure to afford 4-Chloro-N 2 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4-diamine as a white solid (29.7 g, 90%) MP 163-164° C., 1 H (CDCl 3 ) δ 7.78 (m, 5H), 6.1-6.2 (m, 4H), 1.52 (d, 3H), MS (ESI + ) (M + ) 249.7 obs.
[0405] B. Synthesis of Formula I Products
Example 16
Example of Scheme 1
[0406] N 4 -[2-(4-Fluorophenoxy)ethyl]-N 6 -[(1S)-(1-phenylethyl)]pyrimidine-4,6-diamine
[0407] 4-[(1S)-(1-phenylethyl)amino]-6-chloropyrimidine, (Intermediate III, Compound of Example 6), (234 mg, 1.0 mmole) and [2-(4-fluorophenoxy)ethyl]amine (357 mg, 2.3 mmole) were combined in a 2 mL pressure vial which was then securely capped. The vial was heated at 150° C. for 20 hours. After cooling, the solid mass was dissolved in CH 2 Cl 2 (25 mL) and extracted with saturated sodium carbonate (25 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was recrystallized from CH 2 Cl 2 (5 mL) to afford the titled compound as a white solid (191 mg, 54%). 1 H NMR (CDCl 3 ) δ 1.54 (d, J=6.6 Hz, 3H), 3.54 (q, J=5.5 Hz, 2H), 3.94 (t, J=5.5 Hz, 2H), 4.59 (p, J=6.6 Hz, 1H), 5.05 (broad m, 1H), 5.08 (s, 1H), 5.34 (broad d,1H), 6.77 (m, 2H), 6.95 (t, J=9.1 Hz, 2H), 7.23 (m,1H), 7.32 (d, J=4.4 Hz, 4H), 8.09 (s, 1H), LC/MS (MH + ) m/e 353.79 obs.
Example 17
Example of Scheme 2
[0408] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl1-N 4 -[2-(4-fluorophenyl)ethyll-1,3,5-triazine-2,4,6-triamine, TFA Salt
[0409] To the Intermediate XI, Compound of Example 11 was added 50% TFA in dichloroethane (1 mL). The mixture was shaken at ambient temperature for 0.5 h, drained into a custom microtube, rinsed with dichloroethane (0.5 mL), and concentrated by centrifugal evaporation to afford the titled compound (74 mg) as a thick amber oil. HPLC-MS (C-18, MeOH/H 2 O/TFA linear gradient elution, 5 ml/min, 220 nm): product peak (70%) at 1.61 minutes; MS (ESI + ) obsd m/z=371.21.
Example 18
Example of Scheme 2
[0410] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine, TFA Salt
[0411] The titled compound was prepared from Intermediate XI, Compound of Example 12 and 50% TFA in dichloroethane (1 ml) as described in Example 17 to afford the titled product (128 mg) as a thick amber oil. HPLC-MS (C-18, MeOH/H 2 O/TFA linear gradient elution, 5 ml/min, 220 nm): product peak (80%) at 0.93 minutes; MS (ES + ) obsd m/z=354.24.
Example 19
Example of Scheme 2, Compound 41
[0412] N 2 -(2-Phenoxyethyl)-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, TFA salt
[0413] The Intermediate XI, Compound of Example 13, was treated with 50% TFA in CH 2 Cl 2 (50 mL) and the mixture was vortexed for 1 hour. The resin was filtered and was rinsed with CH 2 Cl 2 (2×50 mL). The filtrate and CH 2 Cl 2 rinses were combined and concentrated under reduced pressure to afford the titled compound as a reddish oil (1.1 g).
Example 20
Example of Scheme 3, Compound 41
[0414] N 2 -[2-(2-Phenoxyethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, hydrochloride
[0415] A solution of 4-Chloro-N 2 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4-diamine, Compound of Example 15, (15.0 g, 0.056 mol), 2-phenoxyethylamine (8.6 g, 0.062 mol), diisopropylethylamine (25 mL, 0.178 mol) in THF (500 mL) was refluxed for 24 h, then allowed to cool to ambient temperature and concentrated under reduced pressure. The amber residue was dissolved in CH 2 Cl 2 and was washed with 1 N HCl (300 mL). Product precipitated from the organic layer was collected by filtration, washed with H 2 O and CH 3 CN, and dried. The product was then triturated in hot CH 3 CN, collected by filtration and dried to afford the titled compound (18.2 g, 88%) as a white solid. MP 207-208° C., 1 H NMR (CDCl 3 ) δ 7.19-7.3 (m, 7H), 6.91-6.96 (m, 3H), 5.16-6.08 (b m, 3H), 4.90 (b s, 2H), 3.32-4.04 (m, 4H), 1.49 (d, 3H); MS (ESI + ) (M+H) + 351.2 obs; C, H, N Calc'd. for C 19 H 22 N 6 O 1 .HCl C, 58.98:H, 5.99: N, 21.72; Found C, 59.02:H, 5.87: N, 21.67.
Example 21
Example of Scheme 3
[0416] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine, dihydrochloride salt
[0417] The 4-Chloro-N 2 -[(1S)-1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,6-diamine used was prepared from (1S)-1-(4-Fluorophenyl)ethylamine (resolved by the procedure of Takenaka, S. et al. J. Chem. Soc., Perkins Trans. 2 1978, 95-99), cyanuric chloride and ammonium hydroxide according to the procedure outlined in the first two steps of Scheme 3 and by the procedure as described in Examples 14 and 15. A stirred solution of 4-Chloro-N 2 -[(1S)-1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,6-diamine (1.15 g, 4.30 mmol), 2-(2-aminoethyl)pyridine (0.58 g, 4.73 mmol), diisopropylamine (20 ml), and THF (10 ml) was heated at reflux for 18 hours and then concentrated under reduced pressure. The yellow residue was taken up in CH 2 Cl 2 and washed with H 2 O and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was chromatographed on silica, eluting with 3% MeOH/CH 2 Cl 2 to afford N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine (free base) as a pale tan foam (1.10 g, 72%). 1 H NMR (CDCl 3 ) δ 8.51 (s, 1H), 7.56 (t, 1H), 7.31 (s, 2H), 7.08 (m, 1H), 6.97 (m, 3H), 5.88-5.44 (b m, 1H), 5.42-5.19 (b m, 1H), 5.15 (m, 1H), 4.95 (b s, 2H), 3.72 (d, 2H), 3.20-2.81 (b m, 2H), 1.47 (d, 3H). HPLC-MS (C-18, MeOH/H 2 O/TFA linear gradient elution, 5 ml/min, 220 nm): 1 peak at 0.84 minutes; MS (ES+) obs. m/z 353.83. A stirred solution of N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine was treated with 10 mL of 1 N HCl in Et 2 O and allowed to stand at ambient temperature for 30 minutes. The mixture was concentrated by rotary evaporation to afford the titled compound as a pale white fine powder. LC/MS (C-18, MeOH/H 2 OTFA linear gradient elution, 5 ml/min, 220 nm): 1 peak at 0.86 minutes; MS (ES+) obsd m/z=354.26. MP=161° C.
[0418] Compounds of Formula (Ia) may be prepared as follows:
[0419] Compound 2
[0420] A mixture of compound 1 (10 g, 68 mmol) and SOCl 2 (100 mL) in CH 2 Cl 2 (68 mL) was refluxed for 3 h. After concentration, the residue was dissolved in CH 2 Cl 2 (100 mL) followed by addition of a suspension of MeONHMe.HCl (10 g, 102 mmol) in Et 3 N (20 g) at 0° C. The resulting mixture was allowed to warm to room temperature and stirred for 1 h. The reaction was quenched with water. The organic layer was washed with brine and dried over MgSO 4 , concentrated to give 2 (11 g, 84%) as a solid which was used in the next step without purification. 1 H NMR (300 MHz, CDCl 3 ) δ 3.31 (s, 3H), 3.77 (s, 3H), 7.21 (d, 1H, J=15.9 Hz), 7.41 (d, 2H, J=6.0 Hz), 7.66 (d, 1H, J=15.9 Hz), 8.64 (d, 2H, J=6.0 Hz).
[0421] Compound 2a
[0422] The title compound was prepared by the general procedure described in 2 using 1a (10 g, 66 mmol). Concentration gave 2a (12.51 g, 99%) as an oil. 1 H NMR (300 MHz, CDCl 3 ): δ 3.41 (s, 3H), 3.86 (s, 3H), 7.27-7.15 (m, 3H), 7.70-7.64 (m,1H), 7.93 (d, 1 h, J=16.0 Hz). MS (ESI) (M+H) + 209.61.
[0423] Compound 2b
[0424] The title compound was prepared by the general procedure described in 2 using 1b (10 g, 66 mmol). Concentration gave 2b (12.50 g, 99%) as an oil. 1 H NMR (300 MHz, CDCl3): δ 3.27 (s, 3H), 3.73 (s, 3H), 6.93 (d, 1H, J=15 Hz), 7.00-7.07 (m, 2H), 7.49-7.55 (m, 2H), 7.66 (d, 1H, J=15 Hz). MS (ESI) (M+H) + 209.61.
[0425] Compound 3
[0426] NaH (2.4 g, 100 mmol) was added to a suspension of trimethylsulfoxonium iodide (22 g, 100 mmol) in DMF (100 mL) at 0° C. The resulting mixture was allowed to warm to room temperature and stirred for 0.5 h. A solution of compound 2 (9 g, 50 mmol) was added to the above reaction mixture at 0° C. The resulting reaction was allowed to warm to room temperature and stirred for 1 h. The reaction was quenched with water and extracted with CH 2 Cl 2 . The organic layer was washed with brine, dried over MgSO 4 , and concentrated to give a reside. The residue was purified by flash chromatography over silica gel (elution with 2% methanol in ethyl acetate) to give compound 3 (2.1 g, 20%) as an oil.
[0427] Compound 3a
[0428] The title compound was prepared by the general procedure described in 3 using 2a (12.5 g, 60 mmol). Purification on silica gel gave 3a (2.8 g, 21%) as an oil. 1 H NMR (300 MHz, CDCl 3 ): δ 1.35-1.29 (m, 1H), 1.63-1.57 (m, 1H), 2.46-2.36 (m, 1H), 3.22 (s, 3H), 3.69 (s, 3H), 7.06-6.95 (m, 3H), 7.19-7.10 (m, 1H). MS (ESI)(M+H) + 224.25.
[0429] Compound 3b
[0430] The title compound was prepared by the general procedure described in 3 using 2b (12.5 g, 60 mmol). Purification on silica gel gave 3b (12.7 g, 95%) as an oil. 1 H NMR (300 MHz, CDCl3): δ 1.19-1.25 (m, 1H), 1.54-1.60 (m, 1H), 2.25-2.37 (m, 1H), 2.41-2.49 (m, 1H), 3.20 (s, 3H), 3.66 (s, 3H), 6.89-6.97 (m, 2H), 7.02-7.08 (m, 2H). MS (ESI) (M+H) + 224.20
[0431] Compound 4
[0432] A mixture of compound 3 (2.06 g, 10 mmol) and LiAlH 4 (418 mg, 11 mmol) in THF (60 mL) was stirred for 0.5 h at 0° C. After cooling to −30 C, the resulting mixture was quenched sequentially with water (0.4 mL, 10 N NaOH (0.4 mL), and water (0.8 mL). After filtration and concentration, the residue was extracted with CH 2 Cl 2 . The organic layer was washed with brine, dried over MgSO 4 , and concentrated to give concentrated to give 4 (1.46 g, 99%) as an oil which was used in the next step without purification. 1 H NMR (300 MHz, CDCl 3 ) δ 1.46-1.58 (m, 1H), 1.76-1.86 (m, 1H), 2.23-2.30 (m, 1H), 2.54-2.63 (m, 1H), 7.00 (d, 2H, J=6 Hz), 8.50 (d, 2H, J=6.0 Hz), 9.41 (d, 1H, J=4.5 Hz).
[0433] Compound 4a
[0434] The title compound was prepared by the general procedure described in 4 using 3a (2.8 g, 12.5 mmol). Concentration gave 4a (2.06 g, 100%) as an oil. 1 H NMR (300 MHz, CDCl3): δ 1.41-1.48 (m, 1H), 1.53-1.59 (m, 1H), 1.96-2.02 (m,1H), 2.72-2.82 (m,1H), 6.92-7.24 (m, 4H), 9.34 (d, 1H, J=4.7 Hz).
[0435] Compound 4b
[0436] The title compound was prepared by the general procedure described in 4 using 3b (5.5 g, 24.6 mmol). Concentration gave 4b (4.05 g, 100%) as an oil. 1 H NMR (300 MHz, CDCl 3 ): δ 1.43-1.50 (m, 1H), 1.67-1.73 (m, 1H), 2.07-2.14 (m, 1H), 2.56-2.63 (m, 1H), 6.93-6.99 (m, 2H), 7.03-7.09 (m, 2H), 9.31 (d,1H, J=4.6 Hz).
[0437] Compound 5
[0438] A mixture of compound 4 (1.46 g, 10 mmol), NH 2 O H.HCl (1.4 g, 20 mmol), and 5 N NaOH (4 mL) in THF (50 mL) was refluxed for 0.5 h. After cooling to −30° C., the resulting mixture was quenched sequentially with water (0.4 mL, 10 N NaOH (0.4 mL), and water (0.8 mL). After concentration, the residue was extracted with CH 2 Cl 2 . The organic layer was washed with brine, dried over MgSO 4 , and concentrated to give concentrated to give 5 (1.6 g, 99%) as an oil which was used in the next step without purification. 1 H NMR (300 MHz, CDCl 3 ) δ 1.34-1.46 (m, 1H), 1.82-1.99 (m, 1.7H), 2.10-2.16 (m, 1H), 2.65-2.72 (m, 0.3H), 6.23 (d, 0.3 H, J=8.4 Hz), 7.00 (m, 2H), 7.21 (d, 0.7H, J=7.3 Hz), 8.4(m, 2H).
[0439] Compound 5a
[0440] The title compound was prepared by the general procedure described in 5 using 4a (2.06 g, 12.5 mmol). Concentration gave 5a (2.03 g,90%) as an oil.
[0441] Compound 5b
[0442] The title compound was prepared by the general procedure described in 5 using 4b (4.05 g, 24.6 mmol). Concentration gave 5b (4.35 g, 98%) as an oil.
[0443] Compound 6
[0444] A mixture of compound 5 (1.58 g, 9.7 mmol) and LiAlH 4 (0.57 g, 15 mmol) in THF (60 mL) was refluxed for 1. After cooling to −30° C., the resulting mixture was quenched sequentially with water (0.6 mL), 10 N NaOH (0.6 mL), and water (1.2 mL). After concentration, the residue was extracted with CH 2 Cl 2 . The organic layer was washed with brine, dried over MgSO 4 , and concentrated to give concentrated to give 6 (1.3 g, 91%) as an oil which was used in the next step without purification. LCMS (99%); LCMS (M+1) + 149.10.
[0445] Compound 6a
[0446] The title compound was prepared by the general procedure described in 6 using 5a (2.03 g, 11.3 mmol). Concentration gave 6a (1.75 g, 94%) as an oil. 1 H NMR (300 MHz, CDCl 3 ): δ 0.80-1.00 (m, 2H), 1.87-2.00 (m, 2H), 2.22-2.82 (m, 2H), 6.86-7.24 (m, 4H).
[0447] Compound 6b
[0448] The title compound was prepared by the general procedure described in 6 using 5b (4.35 g, 24.3 mmol). Concentration gave 6b (3.39 g, 85%) as an oil. 1 H NMR (300 MHz, CDCl 3 ): δ 0.78-0.89 (m, 2H), 1.15-1.22 (m, 1H), 168-1.88 (m, 1H), 2.69-2.87 (m, 1H), 6.80-7.1 0 (m, 4H).
[0449] Compound 7
[0450] (±)-trans-N-(1-Phenyl-ethyl)-N′-(2-pyridin-4-yl-cyclopropylmethyl)-[1,3,5]triazine-2,4,6-triamine
[0451] A mixture of compound 6 (400 mg, 3 mmol), triazine (249 mg, 1 mmol), and N,N-diisopropyl ethylamine (2 mL) in THF (10 mL) was refluxed for 3 days. After concentration, purification on silica gel gave 7 (320 mg, 80%) as an oil. LCMS (100%); LCMS (M+1) + 362.88.
[0452] Compound 7a
[0453] (±)-trans-N-[2-(2-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazi ne-2,4,6-triamine
[0454] The title compound was prepared by the general procedure described in 7 using 6a (165 mg, 1 mmol). After concentration, purification on silica gel gave 7a (130 mg, 34%) as an oil. LCMS (99%); LCMS (M+1) + 379.22.
[0455] Compound 7b
[0456] (±)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine
[0457] The title compound was prepared by the general procedure described in 7 using 6b (165 mg, 1 mmol). After concentration, purification on silica gel gave 7b (245 mg, 64%) as an oil. LCMS (98%); LCMS (M+1) + 379.22.
[0458] Compound 8a
[0459] (S,S)-trans-N-[2-(2-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine
[0460] Diastereomers 7a (12 mg) was subjected to Chiralpak AD column separation with an eluant of 15% isopropanol/85% hexane to give 8a (6 mg, 50%) as an oil. LCMS (99%); LCMS (M+1) + 379.22.
[0461] Compound 8b
[0462] (S,S)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropyl methyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine
[0463] Diastereomers 7b (20 mg) was subjected to Chiralpak AD column separation with an eluent of 15%isopropanol/85%hexane to give 8b (9.7 mg, 50%) as an oil. LCMS (99%); LCMS (M+1) + 379.22.
[0464] 5-HT 7 Receptor Binding Assay
[0465] Membranes are prepared for binding using the human 5-HT 7 receptor expressed in CHO cells. Cells are collected and ruptured using a dounce homogenizer. The cells are spun at 18000× g for 10 minutes and the pellet is resuspended in assay buffer, frozen in liquid nitrogen and kept at −80° C. until the day of the assay.
[0466] A total of 30 ug protein is used per well. The assay is carried out in 96-deep-well plates. The assay buffer is 50 mM HEPES. The membrane preparation is incubated at 25° C. for 60 minutes with 0.1 nM to 1000 nM test compound and 1 nM 3 H-5-carboxamidotryptamine. 10 uM serotonin is used as blocking agent to determine non-specific binding. The reaction is terminated by the addition of 1 ml of ice cold 5OmM HEPES buffer and rapid filtration through a Brandel Cell Harvester using Whatman GF/B filters. The filter pads are counted in an LKB Trilux liquid scintillation counter. IC 50 values are determined using non-linear regression by Exel-fit.
Biological Activity
[0467] The compounds of this invention are useful as antagonists or partial agonists for the treatment of CNS and ocular disorders. The compounds of the present invention have been evaluated for 5-HT 7 receptor activity and have IC 50 s of approximately 200 nM or less in the 5-HT 7 receptor binding assay. A compound of this invention has also been assessed in an in vivo model, the rat pup isolation-induced ultrasonic vocalization test. This animal model has proven to be a sensitive and reliable method for detecting anxiolytics and antidepressants across a broad spectrum of pharmacological classes such as benzodiazepines, serotonin reuptake inhibitors, serotonin agonists and NMDA antagonists (Gardner, C.; Drug Devel. Res. 1985, 5,185-193 and Winslow, J.; Insel, T.; Psychopharmacology 1991,105, 513-520). Administration of N 2 -[(1S)-1-(4-Methylphenyl)ethyl]-N 4 -(2-phenoxyethyl)-1,3,5-triazine-2,4,6-triamine, produced a dose dependent and significant supression of rat pup ultrasonic vocalization at doses which did not suppress locomotor activity. The amount of compound dosed which reduced the rat pup ultrasonic vocalization by 50% (ID 50 ) was 23.8 mg/kg.
[0468] The following compounds were found to have an IC 50's less than or equal to 50 nM in the 5-HT7 receptor assay:
[0469] N 4 -[(1S)-1-(4-Bromophenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 13,
[0470] N 4 -(3-Methylphenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0471] N 2 -(2-Phenoxyethyl)-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0472] N 4 -{3-[(Methylsulfonyl)amino]phenylmethyl}-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 14,
[0473] N 2 -(2-Phenoxyethyl)-N 4 -[3-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0474] N 4 -(3-Chlorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0475] N 2 -(2-Phenoxyethyl)-N 4 -[(1S)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0476] N 4 -(4-Chlorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0477] N 4 -(3-lodophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 15,
[0478] N 4 -(3,4-Difluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0479] N 4 -(4-Benzodioxolylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0480] N 2 -(2-Phenoxyethyl)-N 4 -(phenylmethyl)pyrimidine-2,4-diamine,
[0481] N 4 -(3-Methylphenyl methyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0482] N 4 -(3-Chloro-4-methylphenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0483] N 4 -[1-(4-Chlorophenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0484] N 4 -(1-Napthalenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 16,
[0485] N 4 -[(1S)-1-(1-NapthalenyI)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 17,
[0486] N 2 -(2-Phenoxyethyl)-N 4 -(2-thienylmethyl)pyrimidine-2,4-diamine, Compound 18,
[0487] N 4 -[(1S)-1-(4-Methylphenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0488] N 4 -[4-(1-Methylethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0489] N 4 -[2-Fluoro-5-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0490] N 2 -(2-Phenoxyethyl)-N4-(4-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 19,
[0491] N 4 -(3-Chloro-4-fluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0492] N 2 -(2-Phenoxyethyl)-N 4 -(3-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 20,
[0493] N 2 -[2-(3-Hydroxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 21,
[0494] N 4 -[(1S)-1-Phenylethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0495] N 2 -(2-Phenylethyl)-N 4 -[(1S)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0496] N 2 -[2-(4-Hydroxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0497] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0498] N 4 -[1-(4-Fluorophenyl)ethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0499] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0500] N 4 -(2-Methoxyphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0501] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0502] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0503] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0504] N 2 -[2-(3-Cyanophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 22,
[0505] N 2 -[2-(1-Cyclohexenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 23,
[0506] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0507] N 4 -[(1S)-1-(1-Napthalenyl)ethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 24,
[0508] N 4 -(1-Methyl-1-phenyl)ethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0509] N 4 -(3-lodophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 25,
[0510] N 2 -(2-Phenylethyl)-N 4 -(phenylmethyl)pyrimidine-2,4-diamine,
[0511] N 4 -(3-Methylphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0512] N 4 -(4-Chlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0513] N 4 -(3-Bromophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 26,
[0514] N 4 -(3-Fluorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0515] N 2 -(2-Phenylethyl)-N 4 -(2-thienylmethyl)pyrimidine-2,4-diamine, Compound 27,
[0516] N 4 -[1-(4-Chlorophenyl)ethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0517] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0518] N 2 -(Methyl)-N 2 -(2-phenylethyl)-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0519] N 4 -(3,4-Difluorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0520] N 4 -(4-Benzodioxolylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0521] N 4 -(2-Chlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0522] N 4 -(3-Chloro-4-fluorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0523] N 4 -(3-Methoxyphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0524] N 4 -(4-Methoxyphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0525] N 2 -(2-Phenylethyl)-N 4 -[3-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0526] N 2 -[2-(1H-Indol-1-yl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 28,
[0527] N 4 -(1-Phenylethyl)-N 2 -[2-(2-thienyl)ethyl]pyrimidine-2,4-diamine, Compound 29,
[0528] N 2 -[2(1H-Indol-3-yl)ethyl]-N 2 -(methyl)-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 30,
[0529] N 2 -[2-(6-Fluoro-1H-indol-3-yl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 31,
[0530] N 4 -[2-(4-Fluorophenoxy)ethyl]-N 2 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0531] N 4 -[2-(4-Hydroxyphenyl)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine,
[0532] N 4 -[2-(4-Fluorophenoxy)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine, Example 16,
[0533] N 2 -[(1S)-1-Phenylethyl]-N 4 -(2-phenylethyl)-1,3,5-triazine-2,4,6-triamine, Compound 60,
[0534] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 61,
[0535] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 62,
[0536] N 2 -[2-(3-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 63,
[0537] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 64,
[0538] N 2 -2-Phenylethyl-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 65,
[0539] N 2 -[2-(3-Bromophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 66,
[0540] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 67,
[0541] N 2 -[(1S)-1-(4-Bromophenyl)ethyl]-N 4 -[2-(3-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 68,
[0542] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 69,
[0543] N 2 -[(1S)-1-(4-Bromophenyl)ethyl]-N 4 -[2-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 70,
[0544] N 2 -[2-(3,4-Dichlorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 71,
[0545] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 72,
[0546] N 2 -[2-(3-Hydroxyphenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 73,
[0547] N 2 -[2-(4-Fluorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 74,
[0548] N 2 -[2-(4-Hydroxyphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 75,
[0549] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 76,
[0550] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 77,
[0551] N 2 -[2-(4-Aminophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 78,
[0552] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 79,
[0553] N 2 -[2-(4-Hydroxy-3-methoxyphenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]--1,3,5-triazine-2,4,6-triamine, Compound 80,
[0554] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Example 17,
[0555] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Example 18, 21,
[0556] N 2 -[(1S)-1-(4-Fluorophenyl)ethyl]-N 4 -[2-(2-pyridinyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Examples 18, 21, and
[0557] N 2 -(2-Chlorophenylmethyl)-N 4 -(2-phenylethyl)-1,3,5-triazine-2,4,6-triamine,
[0558] N 2 -[2-(3-Fluorophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0559] N 2 -[2-(3-Methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0560] N 2 -[2-(3-Bromophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0561] N 2 -[2-(3-Cyanophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0562] N 2 -[2-(4-Chlorophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine, and
[0563] N 2 -[2-(4-Methylphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine.
[0564] N 2 -[2-(2-Methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine,
[0565] (S,S)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine,
[0566] (S,S)-trans-N-[2-(2-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, and
[0567] (±)-trans-N-(1-Phenyi-ethyl)-N′-(2-pyridin-4-yl-cyclopropylmethyl)-[1,3,5]triazine-2,4,6-triamine. The following compounds were found to have an IC 50 within the range of 51-100 nM in the 5-HT7 receptor assay:
[0568] N 4 -(3-Fluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0569] N 4 -[4-Fluoro-3-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0570] N 4 -[3-(Aminocarbonyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 6,
[0571] N 4 -[(1R)-1-(4-Methylphenyl)ethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0572] N 4 -(1-Phenylethyl)-N 2 -(2-phenylpropyl)pyrimidine-2,4-diamine,
[0573] N 4 -(1-Phenylethyl)- N 2 -(3-phenylpropyl)pyrimidine-2,4-diamine,
[0574] N 2 -(2-Phenthioethyl)-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0575] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0576] N 4 -[2-(1H-Indol-3-yl)ethyl]-N 2 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 7,
[0577] N 2 -(2-Phenylethyl)-N 4 -[(1R)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0578] N 2 -[2-(3-Bromophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 8,
[0579] N 2 -[2-(4-Bromophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine, Compound 9,
[0580] N 4 -(2,4-Dichlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0581] N 2 -[2-(3,4-Dichlorophenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0582] N 2 -(Indan-2-yl)-N4-(1-phenylethyl)pyrimidine-2,4-diamine, Compound 10,
[0583] N 2 -(2-Phenylethyl)-N 4 -(3-pyridinylmethyl)pyrimidine-2,4-diamine, Compound 11,
[0584] N 4 -(1-Phenylethyl)-N 2 -{2-[3-(trifluoromethyl)phenyl]ethyl}pyrimidine-2,4-diamine,
[0585] N 2 -[2-(2-Methoxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0586] N 4 -(1-Phenylethyl)-N 2 -[2-(2-pyridinyl)ethyl]pyrimidine-2,4-diamine, Compound 12,
[0587] N 2 -[2-(Phenoxy)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 40,
[0588] N 2 -[2-(Phenoxy)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 41, Examples 19, 20,
[0589] N 2 -[(1S)-1-(1-Napthyl)ethyl]-N 4 -[2-(phenoxy)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 42,
[0590] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 43,
[0591] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[(1S)-1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 44,
[0592] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 45,
[0593] N 2 -[2-(4-Fluorophenoxy)ethyl]-N 4 -[(1R)-1-(4-fluorophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 46,
[0594] N 2 -[2-(3,4-Difluorophenoxy)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 47,
[0595] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 48,
[0596] N 2 -[2-(4-Methylphenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 49,
[0597] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 50,
[0598] N 2 -[2-(2-Fluorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 51,
[0599] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 52,
[0600] N 2 -[(1S)-1-Phenylethyl]-N 4 -{2-[3-(trifluoromethyl)phenyl]ethyl}-1,3,5-triazine-2,4,6-triamine, Compound 53,
[0601] N 2 -[2-(3-Methoxyphenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 54,
[0602] N 2 -[2-(3-Cyanophenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 55,
[0603] N 2 -[(1S)-1-(1-Napthalenyl)ethyl]-N 4 -(2-phenylethyl)-1,3,5-triazine-2,4,6-triamine, Compound 56,
[0604] N 2 -[2-(1-Cyclohexenyl)ethyl]-N 4 -[(1S)-1-phenylethyl]-1,3,5-triazine-2,4,6-triamine, Compound 57
[0605] N 2 -[2-(3-Chlorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 58 and
[0606] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 59.
[0607] N 2 -[2-(3,5-Dimethoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine, and
[0608] N 2 -[2-(3-Bromo-4-methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine.
[0609] The following compounds were found to have an IC 50 within the range of 101-200 nM in the 5-HT7 receptor assay:
[0610] N 4 -(3,4-Dichlorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0611] N 2 -(2-Phenoxyethyl)-N 4 -[(1R)-1-phenylpropyl]pyrimidine-2,4-diamine,
[0612] N 2 -(2-Phenoxyethyl)-N 4 -[4-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0613] N 4 -(3,5-Difluorophenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0614] N 2 -(2-Phenoxyethyl)-N 4 -[(1R)-1-phenylethyl]pyrimidine-2,4-diamine,
[0615] N 4 -[3-Fluoro-5-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0616] N 4 -(3,5-Dimethoxyphenylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine,
[0617] N 4 -(1-Phenylethyl)-N 2 -[2-(3-pyridinyl)ethyl]pyrimidine-2,4-diamine, Compound 1,
[0618] N 4 -(3,4-Dichlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0619] N 4 -(2-Furanylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine, Compound 2
[0620] N 4 -(3-Chloro-4-methylphenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0621] N 2 -[2-(4-Methoxyphenyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine,
[0622] N 4 -(3-Chlorophenylmethyl)-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0623] N 2 -(2-Phenylethyl)-N 4 -[(1R)-1-phenylethyl]pyrimidine-2,4-diamine,
[0624] N 2 -(2-Phenylethyl)-N 4 -[4-(trifluoromethyl)phenylmethyl]pyrimidine-2,4-diamine,
[0625] N 4 -[4-Fluoro-3-(trifluoromethyl)phenylmethyl]-N 2 -(2-phenylethyl)pyrimidine-2,4-diamine,
[0626] N 2 -[2-(4-Benzodioxolyl)ethyl]-N 4 -(1-phenylethyl)pyrimidine-2,4-diamine and
[0627] N 2 -[2-(5-Fluoro-1H-indol-3-yl)]ethyl]-N 4 -(l -phenylethyl)pyrimidine-2,4-diamine, Compound 3,
[0628] N 4 -(2-Furanylmethyl)-N 2 -(2-phenoxyethyl)pyrimidine-2,4-diamine, Compound 4, and
[0629] N 2 -(2-Phenylethyl)-N 4 -(4-pyridinylmethyl)pyrimidine-2,4-diamine,
[0630] N 4 -[2-(4-Aminophenyl)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine,
[0631] N 4 -[2-(4-Bromoophenyl)ethyl]-N 6 -[(1S)-1-phenylethyl]pyrimidine-4,6-diamine,
[0632] N 2 -[2-(4-Chlorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]-1,3,5-triazine-2,4,6-triamine, Compound 32,
[0633] N 2 -[2-(3,4-Dichlorophenyl)ethyl]-N 4 -[(1S)-1-phenylpropyl]--1,3,5-triazine-2,4,6-triamine, Compound 33,
[0634] N 2 -[(1S)-1-(4-Bromophenyl)ethyl]-N 4 -[2-(4-methylphenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 34,
[0635] N 2 -[(1S)-1-Phenylpropyl]-N 4 -(2-phenylpropyl)-1,3,5-triazine-2,4,6-triamine, Compound 35,
[0636] N 2 -[(1S)-1-Phenylpropyl]-N 4 -[2-(3-(trifluoromethyl)phenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 36,
[0637] N 2 -[(1S)-1-Phenylethyl]-N 4 -(2-phenylpropyl)-1,3,5-triazine-2,4,6-triamine, Compound 37,
[0638] N 2 -[(1S)-1-(1-Napthalenyl)ethyl]-N 4 -[2-(phenylamino)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 38,
[0639] N 2 -[2-(4-Bromophenyl)ethyl]-N 4 -[(1S)-1-(4-nitrophenyl)ethyl]-1,3,5-triazine-2,4,6-triamine, Compound 39,
[0640] N 2 -[2-(4-Methoxyphenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine, and
[0641] N 2 -[2-(3-Acetamidophenyl)ethyl]-6-methyl-N 4 -[(1S)-1-phenylethyl]pyrimidine-2,4-diamine.
[0642] The following compounds were found to have an IC50's less than or equal to 100 nM but greater than 50 nM in the 5-HT7 receptor assay:
[0643] (±)-trans-N-[2-(2-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine,
[0644] (S,S)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-[1-(4-fluoro)phenyl-ethyl]-[1,3,5]triazine-2,4,6-triamine, and
[0645] (±)-trans-N-[2-(4-Fluoro-phenyl)-cyclopropylmethyl]-N′-(1-phenyl-ethyl)-[1,3,5]triazine-2,4,6-triamine.
[0646] Compounds of Formula (Ia) may be useful as inhibitors of methyltransferase proteins. See Stephen W. Fesik et. al. “Novel Inhibitors of Erm Methyltransferases from NMR and Parallel Synthesis” J. Med. Chem. 1999, 42, 3852-3859.
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Amino-pyrimidine and amino-triazine derivatives having 5-HT 7 antagonist activity for the treatment of sleeping disorders, depression, schizophrenia, anxiety, obsessive compulsive disorders, circadian rhythm disorders, ocular disorders and/or centrally and peripherally mediated hypertension are provided.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to disc brakes and clutches for vehicles generally, and more particularly to wheel brakes having wear indicating devices. The disc brake of this invention may operate in an oil bath for cooling purposes.
2. Description of the Prior Art
Wheel brakes carried on axles residing in a fluid bath are in contemporary use on vehicles such as farm machinery, as well as others. Typically, agricultural and industrial tractors are equipped with inboard brakes for the rear axle. These inboard brakes may be disc brakes which operate in an oil bath which also serves as a source of fluid for hydraulic components of the tractor as well as a lubricant for the differential. These brake systems utilize an annular piston to apply pressure to a disc which is splined to a planetary drive shaft. The opposite side of the disc adjoins a stationary outer disc ring and is in contact with it during braking. The brake operates in a fluid environment that ensures adequate cooling of the brake disc. The frictional surface on either side of the disc may have a lining of microscopically porous paper-like material bonded to either side thereof.
Through normal braking the lining is gradually worn away. When the lining is completely worn away the disc will, upon braking, be clamped between the surfaces of a brake center disc being biased by the annular piston and the pressure plate or outer disc ring. As metal-to-metal contact is now possible (as the lining material has been worn away), galling of the contacting surfaces will occur.
In brake systems without wear indicating devices the vehicle operator may not be aware that the lining has worn away. Generally when the brake lining on brakes of this type do eventually fail there will still be adequate stopping force available to control the vehicle. As a matter of fact, the vehicle operator may not be aware of brake failure until deterioration of the metal components has taken place. One of the first signs of defective brake components shows up in the hydraulic system of the vehicle as the brakes generally operate in a bath of hydraulic fluid which is also used in the vehicle hydraulic system. Hydraulic system component failures are quite possible as metal particles from the brake disc or plates may produce significant damage to filters, pumps, and piston seals.
There are brake pad wear warning systems available for use with conventional dry type disc brakes. A typical embodiment shows a metallic reed bonded to the pad backing plate perpendicular to the surface of the brake rotor. The reed contacts the rotor after the pad has partially worn away and produces an audible signal. This type of warning device could not be used for a hydraulic fluid cooled brake as it would produce metallic particles which may damage the hydraulic systems of the host vehicle.
The device disclosed herein is, to our knowledge, the only audible wear indicating device that can be effectively used with disc brakes which operate in a hydraulic fluid bath.
It is therefore, an object of this invention to present a disc brake system that has a built in warning indicator that indicates worn brakes before such wear becomes detrimental to the brake components or the various hydraulic components of the vehicle.
Another object of this invention is to present a warning device for use with liquid cooled brakes that will not detrimentally contaminate the cooling fluid.
Also an object of the invention is to present a warning system having an audible warning signal which can be heard by the vehicle operator over the noise of the vehicle.
Furthermore, it is an object of this invention to provide an audible warning device that can provide a high level of braking effectiveness.
It is also an object of the present invention to provide a warning device for use on a disc brake which is easily manufactured and relatively inexpensive.
Inasmuch as this invention could find application in other areas, such as wet or dry clutches, it is an object of this invention to provide an assembly using two frictional medias of different properties such that upon contact with a moving reactive member and a primary frictional material a first set of desirable characteristics is evident and upon contact with a secondary frictional material a second set of desirable characteristics is evident.
These and other objects and many of the attendant advantages of the present invention will become more readily apparent upon a perusal of the following description and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view in elevation, with portions broken away or omitted, of a disc brake system incorporating a preferred embodiment of the present invention;
FIG. 2 is a side elevation view of the friction plate disc shown in FIG. 1;
FIG. 3 is an elevation view of a partially complete friction plate disc showing an alternative embodiment;
FIG. 4 is another alternative embodiment showing an elevation view of a partially complete friction plate disc;
FIG. 5 is an enlarged cross-sectional view of the frictional lining material as taken through the plane shown as 5--5 of FIG. 2;
FIG. 6 is an enlarged cross-sectional view of the frictional lining material through plane 6--6 of the alternative friction plate disc shown in FIG. 4;
FIG. 7 is a broken away quandrant from a friction plate showing an alternative arrangement of frictional materials;
FIG. 8 is a cross sectional view through plane 8--8 of FIG. 8;
FIG. 9 is a broken away quandrant from a friction plate showing another alternative arrangement of frictional materials;
FIG. 10 is a cross sectional view through plane 10--10 of FIG. 9; and
FIG. 11 is a cross sectional view of a friction plate.
In the following description like numerals are associated with like components wherever possible.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1 and 2 a disc brake mechanism, indicated generally at 10, is utilized to constrain or stop a planetary drive shaft 12 rotatably mounted by a bearing 14 within a housing 16. The housing 16 may consist of several parts which are secured together and function as a unitary structure.
The brake mechanism 10 includes a brake disc 20 having a lining bonded to the opposite faces thereof. The disc 20 is splined or otherwise secured to, while being axially slidable on, the shaft 12 and consequently rotates therewith.
The brake disc 20 is a circular flat plate having a splined centrally located aperture which allows mounting of the brake disc to the splines of the drive shaft 12. The brake disc has an inner surface and an outer surface, each surface having two-part lining material 22 and 24 respectively, bonded thereto (FIG. 5). The two part lining material is composed of a primary frictional material 22 having a microscopically porous paper-like construction and a secondary frictional material 24 which may be a noise producing frictional material. The brake disc 20 has a diameter approximately the diameter of the brake center disc 26 which also approximates the outer diameter of the reaction ring or outer disc ring 30.
A plurality of axially disposed apertures 32 are provided in the brake disc 20 in the area between the splined central aperture 34 of the brake disc and the outer diameter area of the brake disc which hosts the lining material. These apertures allow fluid flow past the brake disc while at the same time reducing the weight of the brake disc.
The inboard reaction ring or brake center disc 26 is retained within, and is movable with respect to the housing 16 axially of the shaft 12. The brake center disc 26 has a flat surface formed on one side for engagement with the lining 22 on the inner surface of the brake disc while the opposite face is also of a flat surface for even contact with the annular piston 36. The brake center disc 26 is equipped with three internal lugs (not shown) which align with three channels in the housing 16. The internal lugs in the channels permit axial movement of the brake center disc 26 parallel to the planetary drive shaft 12 upon displacement by the annular piston 36 while prohibiting rotational movement of the brake center disc 26 around the shaft 12.
The annular piston 36 is suitably sealed for movement within an annular chamber 44 formed in the housing 16. Conventional means are provided for admitting fluid under pressure to a chamber 44 to apply or engage the brake mechanism 10 and for venting or draining the fluid.
The lining material used on the brake disc 20 is the focus of the invention. Looking at FIGS. 2 and 5 it can be seen that the brake disc or friction disc is made up of several laminations.
A core plate 18 is a flat annular disc having obverse and reverse surfaces, further having a plurality of apertures including a splined central aperture 34 compatible with the splines of the planetary drive shaft 12 and a plurality of ventilation apertures 32 to allow the passage of fluid past the brake disc is provided. To the core plate 18 several laminations of material are bonded.
First the secondary frictional material is bonded to both sides of the plate using an appropriate bonding agent. In this preferred embodiment the material will be a flat continuous annular ring around the periphery of the core plate. The secondary frictional material is relatively thin, for instance, on the order of, but not limited to, 0.002 to 0.010 inches in thickness. This material is engineered to produce a resonance resulting in audible sound when it is under pressure in motion such as may be envisioned in a braking situation. Generally, the secondary frictional material is a microporous paper-like material.
Noise producing brake frictional material is not normally desirable for use in braking systems as brake system engineers have always tried to engineer frictional materials for noise-free quiet operation. Noise is generated under normal braking forces in frictional material if the static and dynamic coefficients of friction of the material are far apart. As the static and dynamic coefficients come closer together the frictional material becomes less noisey as there is less resonance generated. The secondary frictional material used in this preferred embodiment is relatively noisy due to the high static coefficient and a low dynamic coefficient. For example, the secondary frictional material may have a static coefficient in the range of 0.20 to 0.30 and a dynamic coefficient in the range of 0.04 to 0.15.
After the secondary frictional material is bonded to the core plate the primary frictional material 22 in the figures may be bonded to the core plate over the secondary frictional material. The primary frictional material may also be a flat continuous annular ring consumable in use through wear disposed around the periphery of the core plate similar in width to the width of the secondary frictional material. The primary material 22 is several times thicker than the secondary material. It is made of a microscopically porous (micro-porous) paper-like material having good heat resistance and wearability. This primary frictional material has relatively close static and dynamic coefficient of friction values thus is generally quiet in operation.
Grooves 46 may be machined into the primary frictional material 22 to allow fluid to circulate and cool the braking surfaces. The horizontal and vertical grooves shown in the drawings are typical although various groove patterns or even non-grooved surfaces may be used.
The audible brake lining wear indicator will perform in the following manner. As the primary frictional material 22 is worn away or consumed through contact with the brake center disc 26 and the outer disc ring 30 the secondary frictional material 24 will be exposed to contact with either the brake center disc 26 or the outer disc ring 30. Upon contact a resonant noise will be emitted due to the characteristics of the secondary frictional material. Of course, the noise emitted by the secondary frictional material will be increased as more and more of the primary frictional material is worn away. The audible signal should be heard by the operator who can then schedule the vehicle for the appropriate brake repair.
It should be noted that the secondary frictional material may be as effective in braking a vehicle as the primary frictional material. Also, even though the secondary material may be relatively thin it may be designed to have a service life great enough to allow the vehicle to be operated until it can be gotten into a repair shop.
Neither the primary nor secondary frictional materials is as detrimental to the hydraulic fluid performance as would be the case if metal particles were generated through the wear of the brake system. This may be attributed to the fiberous structure of the frictional materials as contrasted to the non-fiberous structure of metalic particles.
ALTERNATIVE EMBODIMENTS
Numerous alternative embodiments regarding the secondary frictional material are available. Several of these are shown by FIGS. 3, 4, 6 and 7-11.
It has been found that only a small amount of the secondary frictional material need be exposed in order to generate an audible signal. Thus in FIG. 3 a plurality of alternative segments of secondary frictional material 64 and primary frictional material 62 have been provided to make up the alternative brake disc 60. In FIG. 4 another alternative brake disc 70 is equipped with circular discs of secondary braking material 74 adjacent to and surrounded by filler material 50 below the surface of the primary braking material 22. In either case a continuous flat ring of primary frictional material 22 covers the secondary frictional material as in the preferred embodiment shown in FIG. 2.
In FIG. 6 a cross section of secondary frictional material discs of FIG. 4 shows the core plate 18, a circular disc of secondary material 74 on each side of the core plate and then the primary frictional material 22 outermost on each side. Note that a filler 50 may surround the discs of secondary material. This filler may be either the primary frictional material or an unspecified third type of consumable microporous frictional material.
Also a similar filler may be used in the embodiment of FIG. 3 in place of the segments 62 which are not of secondary frictional material.
In FIG. 7 a portion of a fourth brake disc embodiment 80 is shown. The core plate 18 is similar to those in FIGS. 2 through 4 previously described. However, in FIG. 7 the application of the primary frictional material 82 is directly to the core plate 18 while the secondary frictional material 84 is also affixed to the core plate 18 in a band or annular ring between the inner diameter of the band or annular ring of primary frictional material 82 and the center of the friction plate or brake disc embodiment 80. The cross sectional view of FIG. 8 clearly shows this arrangement. Note that the primary frictional material 82 is thicker than the secondary frictional material 84 and further the primary material does not cover the secondary frictional material. In this embodiment the primary material would wear away in use thus allowing the secondary frictional material to come into contact with a reactive member (not shown).
FIG. 9 also shows a portion of a friction plate or fith embodiment of a brake disc 90 with a core portion 18. A band of primary frictional material 92 is bonded directly to the core plate 18. The secondary frictional material 94 is carried in apertures spaced around the band of the primary material. At least two configurations may be used as shown by FIGS. 10 and 11. First looking at FIG. 10, which is a cross section through the core plate 18 along plane 10-10 of FIG. 9, the primary frictional material 92 can be seen bonded to the core plate 18. A "button" or circlar disc of secondary frictional material 94 is bonded to the core plate in the apertures in the primary frictional material. As in the embodiment of FIG. 7 above note that the primary material does not cover the secondary material. When the primary frictional material 92 wears down to the level of the secondary material 94 the secondary material will be in contact with the reactive members of the system thus emitting a type of audible noise.
FIG. 11 is a further development. A cross section as shown by FIG. 11 shows that the core plate 118 is equipped with another set of apertures, one shown as 56, all the way through it. Into these apertures a slug or puck 52 of secondary frictional material is carried. This slug 52 of material is free to move between each side of the core plate and thus assures that the warning system will be available even when run out in the core plate may hamper the effectiveness of the described device.
Other alternative shapes for the secondary frictional material are possible (diamond, squares, bands, triangles, etc.) and are contemplated to be within the scope of this invention although they are not shown in the figures.
The preferred embodiment, i.e., the full ring laminate, may be more desirable than these alternative embodiments as it could point up localized failures such as a chip out of the primary frictional material. Also it may be less expensive to produce.
Another alternative use for this invention is in the field of clutches. In operation and principle the clutch of a vehicle works similarly to the friction plate brake disc as described above. The clutch is necessary to lock the flywheel to the output shafts thus allowing the engine to drive the drive wheels. The frictional materials used in wet cluches, however, are similar to those used in braking devices. FIG. 2 could alternatively be a wet clutch rather than a disc brake.
In the field of clutches it is also difficult to know when the clutch has worn out. Consequently, there is a possibility of damage as unprotected surfaces of the worn out clutch plate can come in contact with the flywheel and do considerable damage thereto. However, if the vehicle operator is forewarned by means of the warning system described above then the vehicle can be repaired at the first opportunity and thus preclude extensive damage to the vehicle flywheel.
Thus it is apparent that there has been provided in accordance with the invention, an audible brake lining wear indicator that fully satisfies the objects, aims, and advantages set forth above. While 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 of the foregoing description. For instance, this laminated type of brake mounting wear indicator may be used in disc brake pucks for contact with the rotor in a dry brake system. Accordingly, it is intended to embrace all such altenatives, modifications and variations as fall within the spirit and broad scope of the appended claims.
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Providing a secondary frictional material between a primary frictional material and a backing plate for use in a clutch or brake system having a reaction member which operates in an oil bath, whereupon the consumption of the primary frictional material through contact with the reaction member allows contact between the secondary frictional material and the reaction member. The secondary frictional material is of a composition such that upon motion contact with a reaction member an audible sound is produced.
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FIELD OF THE INVENTION
This invention relates to surfboard fins. Specifically, this invention relates to improvements in surfboard fin design and construction.
BACKGROUND AND DISCUSSION OF THE PRIOR ART
Heretofore conventional surfboards and the surfboard fins were constructed of laminated fiberglass which provided the desired strength under the stress and exposure of surfing environments. Such fiberglass fins were of a sharp profile which caused considerable drag effect in surfing. In addition, the weight of such fins was more than was desired by most surfers.
In an attempt to overcome these drawbacks, the prior art sought to hand-shape balsa wood so as to be contoured to reduce drag, and be within the weight control limits desired by surfers. Principal drawbacks of the balsa wood fins were the cost of hand-shaping to the desired contour, as well as its lack of structural integrity, particularly so with long term use. As a consequence, such fins were used by only a small minority of the surfing population.
Now there is provided by the present invention a surfboard fin which is shape-contoured to reduce drag, while being of light-weight and buoyant construction, and yet is readily manufactured.
It is therefore a principal object of the present invention to provide a surfboard fin which alleviates one or more of the problems attendant to the aforesaid prior art fins.
It is another object of the present invention to provide a surfboard fin as aforesaid which combines the desired attributes of low drag, light-weight, high strength and buoyancy, and yet is readily manufactured.
It is a further object of this invention to provide a surfboard fin which may readily be permanently decorated and has an aesthetically desirable appearance.
It is a still further object of this invention to provide a surfboard fin which is of practical design and readily mounted to conventional surfboards.
The aforesaid as well as other objects and advantages as will become apparent from a reading of the following description, the adjoined claims and the drawings.
IN THE DRAWINGS
FIG. 1 is a side elevational view of the fin of the present invention;
FIG. 2 is a sectional view taken along line 2--2 of FIG. 1; and
FIGS. 3A and 3B show a comparison of the profiles of the prior art fin with that of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1 and 2 there is shown the surfboard fin of the present invention generally referred to by numeral 10. Fin 10 comprises two opposed shaped, thermoplastic members 11 and 12. The members are preferably formed of clear translucent polycarbonate, such as Lexan. ("Lexan" is a registered trademark of the General Electric Co., Schnectady, N.Y.). Members 11 and 12 are molded in a pair of shaped contours so when joined to provide a low drag profile as shown in FIG. 3B.
Member 12 is formed with two counter-bores 13a and 13b while member 11 is formed with a threaded female members 14a and 14b, and where female members 14a and 14b and counterbores 13a and 13b are respectively coaxial when members 11 and 12 are in mating contact relationship as shown. Screws 15a and 15b pass through respective counterbores 13a and 13b and engage recess threads 16a and 16b of female members 14a and 14b. With the tightening of screws 15a and 15b, the respective edges 11a and 12a of members 11 and 12 are brought into abutting pressing contact. A silicone sealant 17 is applied to edges 11a, 12a, as well as at 18 within the counterbores and on screw heads 19a and 19b. Sealant 17 is also applied to all mating edges so that the fin is fluid tight. In this manner of construction the joined and sealed members form a hollow cavity 19 so as to render the fin buoyant.
The connecting or mounting member 20 comprises a pair of cut stock members 21 and 22 which are glued together as at 25 so as to form an integral piece. The top rectilinear portion 23 of member 20 is sized to be slidably mounted in a surfboard undergroove (not shown) in the conventional manner. A metal stud 24 is fixedly glued in to transverse hole 26, whereby the stud releasably interconnects to the surfboard in the conventional manner. A second hole 27 is formed at the tail 29 of member 20 and serves as a tie hole for the connecting strap (not shown) which is worn by many surfers to prevent loss of the surfboard.
Member 20 is formed with a depending portion 30 extending downwardly from portion 23 and is formed with two transverse holes 31 and 32 for slidably accommodating screws 15a and 15b, respectively. Portion 30 passes through slot 33 formed at the top 34 of the abutting members, and depends down into the cavity 19 and is spaced from the inside walls 11b and 12b.
FIG. 3B discloses the transverse profile of the fin of the present invention, which profile provides a low drag, whereas FIG. 3A shows the transverse profile of the prior art solid fiberglass fin with the high drag effect. The fin of FIG. 3B is also buoyant as compared with the fin of FIG. 3A which tends to overly weigh-down the tail end of the surfboard.
The fin of the present invention is preferably constructed of thermoformed or molded plastic materials and most preferably the polycarbonates such as Lexan and the like. Other plastics particularly those with high impact strength, and good dimensional stability are most preferred.
The contoured fin may be formed from 1/8 inch Lexan sheet stock which is thermoformed over a mold surface at the working temperature of about 375 degrees F. After thermally working the sheet, the fin members are cooled and trimmed for proper mating and receiving of the surfboard mounting member. The flat head brass screws are inserted, and before final tightening the sealant is applied. With full tightening any excess sealant is trimmed away.
The fin of the present invention is at least about 15% lighter than conventional solid fiberglass fins; and is buoyant as well, whereas the conventional fiberglass fin is not buoyant.
It is to borne in mind that another aspect of the present invention is that the inner surfaces of the translucent members 11 and 12 may be painted or decorated before assembly and provide a decorative fin whereby the decorative material is not subject to wear or damage and remains essentially permanent.
Sealants which may be employed to seal the opposing shaped contoured members of the fin include those well known in the art which provide a fluid-tight seal between abutting plastic surfaces. The preferred sealants include the silicones, and most preferably "Universal Adhesive" manufactured by Universal Sign Corp., West New York, New Jersey 07093, which was found to be effective at temperatures of from -30 degrees F. to 180 degrees F.
Adhesives or glues which may be employed to mount the attachment clip as well as to bond the two pieces of the attaching member are those well known in the adhesives field for bonding plastic surfaces, and a preferred adhesive is "Lexgrip" manufactured by General Electric, Schnectady, New York, which is particularly suited to bonding Lexan surfaces.
While specific embodiments have been described it will be appreciated by one skilled in the art that many modifications may be made therein without departing from the true spirit and scope of the invention.
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A surfboard fin is disclosed which is formed of shaped plastic opposed members which are joined and sealed to form a hollow light-weight buoyant construction, which provides an external contour to reduce drag in surfboarding. The novel profiled plastic surfboard fin is readily mounted to conventional boards and replaces the present conventional fiberglass fins.
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BACKGROUND OF THE INVENTION
The invention relates to a method for the preparation of relief structures by phototechniques from mixtures containing olefinically unsaturated polymers and azides as photo initiators.
One of the most accurate structuring methods for insulating materials, semiconductor and conductor materials in electrical engineering is the phototechnique. Here, resist relief structures generated by phototechniques are copied on substrates by suitable processes such as etching, vapor deposition and electroless or electroplating metallization. Resist relief structures can furthermore take over permanent protection functions, for instance, as insulation.
In a method know from U.S. Pat. No. 3,957,512 and U.S. Pat. No. Re. 30,186, both incorporated herein by reference, relief structures are made from highly heat-resistant polymers. To this end, radiation-sensitive soluble preliminary polymers in the form of a layer or foil are applied to a substrate; the radiation-sensitive layer or foil is then irradiated through negative patterns; and subsequently, the non-irradiated layer or foil portions are removed from the substrate. If necessary, this can be followed by tempering or annealing of the relief structure obtained. In this method, polyaddition or polycondensation products of polyfunctional carbocyclic or heterocyclic compounds carrying radiation-sensitive radicals with diamines, diisocyanates, bis-acid chlorides or dicarboxylic acids are used as soluble preliminary polymers. The compounds carrying the radiation-sensitive radicals contain two carboxyl, carboxylic-acid chloride, amino, isocyanate or hydroxyl groups suitable for addition or condensation reactions, and, partially in ortho- or peri-position thereto, radiation-reactive groups bound to carboxyl groups as esters. According to U.S. Pat. No. Re. 30,186, these radiation-reactive groups are oxyalkylene-acrylate or oxyalkylene-methacrylate groups.
The light sensitivity of resist materials such as photoreactive polymers can be increased further by the addition of photo-initiators and photo-sensitizers. This is important because the economics of structuring of surfaces by phototechniques dictate that the time for which the expensive exposure devices are used be as brief as possible, i.e., the sensitivity of the photoresists used is as high as possible. In the known method, compounds such as Michler's ketone, i.e., 4,4'-bis(dimethylamino)-benzophenone, benzoine ether, 2-tert-butyl-9,10-anthraquinone; 1,2-benz-9,10-anthraquinone and bis(diethylamino)benzophenone are added to the preliminary polymer stages for this purpose.
It is known to use azides as photo-initiators for resists, especially negative resists, with diallylphthalate prepolymers, polyisoprene resins and polyvinylcinnamates as polymers or preliminary polymers (see: W. S. DeForest, "Photoresist", McGraw-Hill Book Company, 1975, pages 35 to 41). As photo-initiators, generally diazides with the following structure have been used: ##STR1##
SUMMARY OF THE INVENTION
It is an object of the present invention to further increase the photo-reactivity of mixtures which contain olefinically unsaturated polymers and, as photo-initiators, azides, in order to render the preparation of relief structures by phototechniques still more efficient.
According to the invention this is achieved through the use of aromatic azidomaleinimides as photo-initiators. Within the scope of the present invention, the term "aromatic" is intended to include benzene derivatives including anellated, i.e., condensed ring systems.
The method according to the present invention permits efficient production of organic relief structures by brief selective irradiation of film layers and subsequent separation of the unexposed film portions. This is possible because the olefinically unsaturated polymers become more photo-reactive through the addition of azidomaleinimides.
The following compounds may be used, for example, as photo-initiators: 3- or 4-azidophenyl maleinimide; 3-azido-3'-maleinimido-diphenyl methane or the corresponding 4,4'-compound; and 4-azido-4'-maleinimido diphenyl ether.
Preferred compounds for use in the method according to the present invention are the aromatic azidosulfonyl maleinimides, for example, azidosulfonyl phenylmaleinimide, 2-(N-maleinimido)-naphthyl-5-sulfonylazide and 2-(N-maleinimido)-naphthyl-6,8-bissulfonylazide. Such compounds, which are described in our concurrently-filed, commonly assigned U.S. Patent Application Ser. No. 148,142 . . . entitled "N-Azidosulfonylaryl-Maleinimide And The Use Thereof" filed May 9, 1980, are thermally stable and, thus, allow a wide processing latitude.
Sensitizers, such as Michler's ketone, can also be added advantageously to the photo-reactive mixture. In this manner, the light sensitivity of the mixture is increased still further. Olefinically unsaturated polymers which can be used in the method of the present invention include diallylphthalate prepolymers, polycinnamates and polyisoprene resins. In particular, however, acrylate- and/or methacrylate-group-containing polymers are used.
DETAILED DESCRIPTION OF THE INVENTION
The invention is described and explained in greater detail with the aid of the following examples.
EXAMPLE 1 (Reference Test)
From pyromellithic acid dianhydride, methacrylate acid-2-hydroxy-ethyl ester and 4,4'-diaminodiphenyl ether, a soluble preliminary polymer is prepared in accordance with U.S. Pat. Re. 30,186 in the form of a polyamido carboxylic acid methacrylate with the following structure (methacrylate resin): ##STR2##
10 parts by weight of the methacrylate resin are dissolved together with 0.5 parts by weight N-phenylmaleinimide and 0.2 parts by weight Michler's ketone in 22 parts (by volume) of a mixture of dimethylacetamide and dioxane (volue ratio 1:1). The solution is then filtered and centrifuged on aluminum foils to form uniform films. After drying for 11/2 hours at 60° C. in a vacuum, the thickness of the film is 6 μm. The films obtained in this manner are exposed with a 500-W very-high pressure mercury lamp through a contact copy. With an exposure time of 60 to 75 seconds and after development with a 1:1 mixture of γ-butyrolactone and toluene (development time 16 seconds), relief structures with sharp edges and a resolution of 10 μm are obtained. These patterns are tempered for one hour at 340° C., the resolution and the edge sharpness of the relief structures not being impaired.
EXAMPLE 2
10 parts by weight of the methacrylate resin described in Example 1 are used together with 0.2 parts by weight azidosulfonylphenyl maleinimide and 0.2 parts by weight Michler's ketone for producing films with a thickness of 6 μm in accordance with the method of Example 1. With such films, relief structures with sharp edges are obtained after an exposure time of only 30 seconds, under the exposure and development conditions given in Example 1.
EXAMPLE 3 (Reference Test)
10 parts by weight of a commercially obtainable diallylphthalate prepolymer are dissolved together with 0.75 parts by weight N-phenyl-maleinimide and 0.1 parts by weight Michler's ketone in 20 parts (by volume) of a mixture of dimethyl acetamide and dioxane (volume ratio 1:1). The solution is then filtered and centrifuged on aluminum foils to form uniform films. After the solvent is removed in a vacuum, the film thickness is 6 μm. The films obtained in this manner are then exposed with a 500-W very-high-pressure mercury lamp through a contact copy. After an exposure time of 20 to 30 seconds and development with a 1:1 mixture of 1,1,1-trichloroethane and trichloroethylene (development time 30 seconds), relief structures with sharp edges are obtained.
EXAMPLE 4
10 parts by weight of the diallylphthalate prepolymer of Example 3 are used together with 0.2 parts by weight azidophenyl maleinimide and 0.1 parts by weight Michler's ketone according to the method of Example 3 for the preparation of films with a thickness of 6 μm. With such films, relief structures with sharp edges are obtained after an exposure time of only 10 seconds, under the exposure and development conditions given the Example 3.
EXAMPLE 5
10 parts by weight of the diallylphthalate prepolymer of Example 3 are used together with 0.2 parts by weight azidosulfonylphenyl maleinimide and 0.1 parts by wieght Michler's ketone according to the method of Example 3 for the preparation of films with a thickness of 6 μm. With such films, relief structures with sharp edges are obtained after an exposure time of only 6 seconds, under the exposure and development conditions given in Example 3.
EXAMPLE 6 (Reference Test)
From pyromellithic acid dianhydride, allyl alcohol diaminodiphenyl and 4,4' diaminodiphenyl ether, a soluble preliminary polymer stage in the form of a polyamido carboxylic acid allyl ester of the following structure ##STR3## was parepared in accordance with U.S. Pat. No. 3,957,512 (allyl ester resin).
10 parts by weight of the allyl ester resin are dissolved together with 0.5 parts by weight N-phenylmaleinimide and 0.1 parts by weight Michler's ketone in 40 parts (by volume) dimethylacetamide. The solution is then filtered and centrifuged on aluminum foils to form films with a thickness of 5 μm. These films are then exposed with a 500-W very high-pressure mercury lamp through a contact copy for 11 minutes and then developed for 30 seconds with γ-butyrolactone. Structures with a resolution of 10 μm were obtained.
EXAMPLE 7
By means of a reaction solution which contains 10 parts by weight of the allyl ester resin of Example 6, 0.1 parts by weight azidosulfonylphenyl maleinimide and 0.1 parts by weight Michler's ketone, films 5 μm thick are produced on aluminum foils. With the same exposure and development conditions as in Example 6, an exposure time of only 8 minutes is required to prepare from such films relief structures with sharp edges.
EXAMPLE 8 (Reference Test)
5 parts by weight of a phenoxy resin polycinnamate, prepared from a commercially available phenoxy resin with a molecular weight of 20,000 to 25,000 by esterification with cinnamic acid chloride, are dissolved together with 0.05 parts by weight Michler's ketone in 20 parts (by volume) dioxane and the solution is centrifuged on aluminum foils to form uniform films. After the solvent is removed, the film thickness is 7 μm. Exposure with a 500-W very-high-pressure mercury lamp through a contact mask results, after an exposure time of 90 seconds, in an image which can be developed with toluene in 25 seconds. The structures so obtained have good edge sharpness.
EXAMPLE 9
When 0.2 parts by weight azidosulfonylphenyl maleinimide are added to the reaction solution according to Example 8, relief stuctures with sharp edges are obtained under the conditions there given after an exposure time of only 10 seconds.
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The invention relates to a method for making more efficient the preparation of relief structures by phototechniques from mixtures containing olefinically unsaturated polymers and azides as photo initiators. For this purpose, the invention provides the use of aromatic azidomaleinimides as photo initiators. The method according to the invention is suitable particularly for the structuring by phototechniques of insulating materials as well as of semiconductor and conductor materials.
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STATEMENT OF THE INVENTION
This invention relates to X-ray machines and more particularly concerns means for optimizing contrast among multidensity structures associated with the dental arch area on a panoramic radiograph.
CROSS-REFERENCE TO RELATED APPLICATIONS
Reference is hereby made to copending patent application of Robert H. Cushman for "Panoramic Dental X-Ray Machine Employing Image Intensifying Means", Ser. No. 053,127, filed July 20, 1978, assigned to the present assignee.
BACKGROUND OF THE INVENTION
Prior art panoramic dental X-ray machines are well known. Some provide a continuous image of the dental arch area and commonly employ an X-ray source and X-ray film both optically aligned with each other and supported on a rotatable carrying arm which orbits a patient situated in the path of the X-ray beams. The patient may remain stationary or be transported in a patient chair in accordance with various type drive mechanisms in order to simulate the generally elliptical shape of the human dental arch. The continuous image radiograph provides the dentist with a panoramic view of the teeth and associated structures and is therefore a useful diagnostic aid in many phases of dental practice.
Various other prior art apparatus provide a discontinuous, or split image panoramic radiograph which possesses certain advantages. Here, the dentist is presented with additional interpretive information since two distinctly different views of the incisors, or centrals area are provided. Additionally, overlying spinal shadows which would be cast over the central-bicuspid region are eliminated since X-rays are not generated when the spine is aligned with the X-ray source and film.
Regardless of the type radiographic image to be obtained, i.e., continuous or discontinuous, compensation is usually made for the fact that the curvature of the desired area of focus is generally not a true circle or ellipse. Thus, the rate of film travel must be varied in accordance with the rate of travel of the X-ray source about the patient's head in order that the radiological projections occupy a distance on the film equal to the linear distance of a curved structure being X-rayed, such as a typical dental arch.
In U.S. Pat. No. 2,798,958, apparatus is disclosed for varying the rate of film travel relative to the rate of travel of the X-ray source. The X-ray source and film carrier are both supported by a single member permitting both the X-ray source and film carrier to orbit the patient at an uniform rate of travel. Means are also disclosed for reorienting the patient after completion of one-half of the excursion cycle in order to relocate the center of the axis of rotation with respect to the patient's head prior to X-raying the other one-half of the dental arch in order to provide the discontinuous, or split radiographic images.
In U.S. Pat. No. 3,045,118, issued 1962 to Hollman et al., apparatus is disclosed which automatically shifts the patient in order that the line of sight between the X-ray source and film bypasses the patient's spinal column and permits X-raying of the other half of the dental arch. Apparatus is also disclosed therein for continuous moving an X-ray source and extra-oral film holder about the patient.
In U.S. Pat. No. 3,636,349, issued 1972 to Faude et al., assigned to the present assignee, structure is disclosed for revolving an X-ray source and film carrier about the head of a patient who remains fixed in position while the centerline of the orbit continuously moves through an arcuate path approximating the arch of the patient's teeth. The patent further discloses film carrier means which may be used advantageously in the practice of the present invention.
Thus, the prior art discloses various types of structure, apparatus and mechanisms for orbiting the X-ray source-X-ray film (tubehead-camera) assemblies in circular or arcuate paths; for varying film travel speed in accordance with tubehead-camera assembly movements; for shifting the patient in a chair; and for providing continuous or discontinuous type radiographic images.
Attempts have recently been made to employ image intensification devices in conjunction with associated electronic peripheral components and equipment to substantially lessen the overall radiation dosages to which a patient is subjected without any concomitant sacrifice in contrast, resolution, or physical dimensions of the final radiograph. It is appreciated that radiographs of adequate physical dimensions, i.e., about 5"×12", are considered necessary if meaningful information therefrom is to be consistently obtained by a dentist. Such full size radiographs generally required the presence of cathode ray tubes, electronic amplifiers and sweeps, synchronous circuits, and the like.
SUMMARY OF THE INVENTION
The present invention may be used advantageously with the structures, apparatus, and mechanisms described in the above discussed U.S. patents, or may be readily adpated thereto by one skilled in the art. In its simplest embodiment, the present invention proposes means whereby radiations passing through structures associated with dental arch areas are directed substantially simultaneously into three adjacent, vertically aligned image intensifying devices having radiation input faces which oppose the narrow slot in the front panel of the camera assembly (film holder assembly) which carries the light-sensitive film to be activated by photons exiting output faces of the individual image intensifiers. The image intensifiers are secured within the camera assembly against the slot in optical alignment therewith.
The present invention also contemplates a plurality of horizontally and vertically disposed matrices of miniature image intensifying devices wherein each is capable of having its electron gain individually controlled to thus yield still a more precise contrast. Such matrices may be considered an obvious extension of the teachings of the present invention.
The light-sensitive film may press delicately against the output faces of the three image intensifying devices or be disposed in very close spaced relationship thereto as the film travels in accordance with a controlled rate of speed dictated by the type of image desired, as described in the aforementioned patents or cross-referenced copending application, or by the shape of focal trough desired. Film travel speed may, of course, be made to accurately follow a predetermined speed versus location relationship to provide the desired focal trough shape.
Thus, the present invention is capable of providing full size radiographs, i.e., about 5"×12", wherein contrast among the dental arch structures of varying densities can readily be controlled to yield increased diagnostic information to a dentist. The present invention provides significant reduction in X-ray beam intensities with an accompanying dose reduction of radiation to the patient, and requires no large and expensive image intensifiers or associated auxiliary electronic equipment to produce the full size radiographs. The lesser amount of power required by the X-ray tubehead enables the size and cost of the tubehead power supply to be substantially reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an assembly view of a prior art tubehead-camera assembly of a dental X-ray machine.
FIG. 2 is a perspective view of the camera (film holder) assembly of FIG. 1 including a plurality of vertically aligned image intensifying devices positioned for use therewith.
FIG. 3 is a sectional view of an image intensifying device of FIG. 2 taken along line 3--3 thereof.
FIG. 4 is a section of the microchannel plate of the image intensifying device of FIG. 3 taken along line 4--4 thereof.
FIG. 5 is a diagrammatic perspective view of the image intensifying devices of FIG. 2 illustrating means for applying specified potentials thereto.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1, tubehead 10 includes cone 12 which focuses X-rays generated by an X-ray source or tube within the tubehead. Trunnion 14 carries yoke 16 which permits limited tubehead rotation. A camera or film holder assembly 18 contains X-ray film to be activated by the X-ray source. Film holder assembly 18 is supported by a film holder assembly support 20 which receives one end of horizontal arm 22, its other end received by trunnion 14. Horizontal arm 22 and film holder assembly support 20 maintain tubehead 10 and film holder assembly 18 a specified distance from each other and in alignment with the patient's head as tubehead 10 and film holder assembly 18 rotate about the patient. Power is supplied to the X-ray source through cable 24. The entire assembly abovedescribed is supported by an assembly support arm (not shown) which additionally supports a suitable motor (also not shown) for rotating the tubehead and camera assembly as a unit.
Film holder assembly 18 is conventional, except as modified, later described. It comprises film holder 40 (FIG. 2), film carriage 42 which travels within the film holder assembly along rollers 44 when cable 46 and retrieving spring 48 cooperate, through cable roller 50 and other means, to move film carriage 42 and its film past vertical slit diaphragm or camera slot 52 disposed centrally the front panel 53 of the film holder assembly. Slot 52, of course, permits X-rays from tubehead 10 to pass therethrough for activation of the film. Hinges 54 permit door 56 to be opened for gaining access to the interior of film holder assembly 18. Door 56 is provided with a lead shield (not shown) aligned with tubehead 10 and slot 52.
Cable 46 communicates with suitable structure for controlling the rate of travel of film carriage 42 independently of the speed of rotation of the tubehead-camera assembly. Specific means for controlling rate of film travel speed as well as means for effecting rotation of the tubehead-camera assembly form no part of the present invention. Reference however is again made to the aforementioned U.S. patents for disclosing and teaching such means. Reference is also made to the cross-referenced related patent application.
A plurality of image intensifying devices 60, light-sensitive film 62, and film guide roller assemblies 63 modify the structure of conventional film holder assembly 18. Image intensifiers 60, each in suitable vacuum envelopes, or in a common vacuum envelope, are vertically disposed and are aligned with slot 52 and secured thereagainst within the film holder assembly by suitable means, such as electrically non-conductive brackets 64. The illustrated image intensifiers will have nominal dimensions of 1 5/6"×1/2"×3/8", the 1 5/6"×3/8" dimensions defining input faces which oppose the nominal 51/8"×17/64" opening of slot 52 of the camera. Any suitable electrically non-conductive or dielectric film 65 separates each of the image intensifying devices 60.
The bundles of radiation passing through slot 52 strike the input faces 72 of lead glass microchannel plates 66 (FIGS. 3 and 4) comprising arrays of spaced parallel microchannels 68 aligned with the direction of travel of the X-rays. Microchannels 68 are hollow glass cylinders with a known resistive secondary-emission coating disposed on their interior surfaces. Interstices 70, separating the microchannels from each other, comprise a lead glass which converts the X-ray to electrons via bombardment of the lead ions in the glass by the X-rays. The microchannels are electrically connected in parallel by means of a metallic film of chromium disposed on input face 72 and output face 74 of the microchannel plate 66. Alternatively, input face 72 may be coated with a suitable conversion coating to convert the X-rays to electrons. When a potential is applied between these faces, an uniform axial electrostatic field is generated in each of the microchannels. Input faces 72 are electrically insulated from front panel 53 by suitable means. Thus, an electron entering a microchannel adjacent the input end of microchannel plate 66 will be vastly multiplied in number before exiting at output face 74 due to cascading action wherein primary electrons, initially formed by the aforementioned bombardment, collide with the secondary-emission coating material to cause secondary electrons to be emitted. These secondary electrons now assume the role of primary electrons for the next collision further down the microchannel, and so on. It is appreciated that other image intensifying techniques which will convert the X-rays to electrons, multiply them, and then provides an amplified light output may be used advantageously with the present invention.
Typically, each microchannel 68 is about 12 microns in diameter. The microchannels have a center-to-center spacing of about 15 microns. Such microchannel plate 66 is approximately 1/8" in thickness, the length-to-diameter ratio of each microchannel is about 250.
The multiplied electrons leaving output face 74 of each image intensifier 60 are accelerated by varying voltages across a gap 76 of about 0.05". The accelerated electrons are caused to impinge on a phosphor screen 78 disposed on the input side of a fiber optic face plate 80. Phosphor screen 78 converts the electrons back to photons which are transmitted through fiber optic face plate 80 to thereby activate the film 62. Film 62 comprises a single or double emulsion layer having a conventional backing plate, an emulsion layer facing the image intensifier. Intensifying screens used with conventional X-ray equipment, are not required in the practice of the present invention.
The resultant intensified images may have static and dynamic resolutions exceeding 10 and 7 line pairs/mm respectively. The radiation dosage to the patient is reduced by about 10 to 1. Experiments have confirmed 40 to 1 dosage reductions but with some increase in noise levels. Optimum results for any specific application therefore requires balancing dose reduction and noise. As aforementioned, electron gain, and hence dose reduction, may be achieved by adjusting potential applied to the image intensifiers.
Means are known for providing a sufficient voltage across gap 76 to accelerate the multiplied electrons from microchannel plate 66 to phosphor screen 78 and for vacuum sealing each image intensifying device 60 for proper operation thereof.
In FIG. 5, means for applying the potential across the input and output faces of each image intensifier is diagrammatically illustrated as a D.C. high voltage power source 90. The potential across each image intensifier is controlled by individual control means 92 associated with each power source 90. Control means 92 may be caused to automatically continuously vary the potential across the input and output faces by means of conventional feedback circuits which sense the quantum of radiation striking the film to produce control signals for continuously adjusting the gain for optimal contrast, or the gain may be varied in a predetermined cyclical manner based on data and information derived from previous experiments.
Thus, if it is desired to optimize contrast between high and low density structures, for example, such as the teeth and tissue respectively, the gain of the image intensifier receiving the radiation from the low density structure may be reduced to provide a flatter contrast, as compared to the contrast normally obtained between the two, i.e., a white image of the teeth on an almost black background representing the tissue, tongue, and the like. Similarly, a medium density structure of porous bone, such as the jaw, can be optimally contrasted with either tissue or teeth by simply controlling the gain of the proper image intensifier.
If: ##EQU1## then typical optical density values of various structures of the dental arch area are as follows:
______________________________________hard enamels .02alveolar ridge .04lamina dura .04dentin .8-1.0nutrient canal 1.5soft tissue 1.7-2.0______________________________________
Soft tissue, having an optical density, or "blackness", of approximately 2.0, provides images on a radiograph wherein only about 1/100 of light impinging directly thereon will pass therethrough (log of 100 equals 2). Thus, the image of soft tissue is normally quite dark. On the other hand, dentin has an optical density of about 1.0. The image of dentin on a radiograph transmits about 1/10 of the light (log of 10 equals 1) and hence, shows up lighter than the soft tissue.
With the abovementioned values assigned to the various components of the image intensifiers, i.e., microchannel length to diameter ratio, gap space, etc., contrast between cheek and teeth on the radiograph may readily be improved, through conventional feedback systems, for example, by decreasing potential across that image intensifier associated with the cheeks, and permitting the potential across that image intensifier associated with the teeth to remain substantially unchanged.
Alternatively, if desired, potential applied between the input and output faces of the microchannel plate of the image intensifier associated with the cheeks may remain unchanged while increasing the potential applied to the microchannel plate of the image intensifier associated with the teeth. Of course, a combination of either procedure may be used.
Contrast may be varied by varying the gain of an image intensifier. The gain of an image intensifier may be increased by increasing the difference in potential applied between its input face and output face. Dose reduction was improved from 10 to 1 to 40 to 1 when the difference in voltages was increased from 480 volts to 730 volts, i.e., when the voltages applied to input face 72 and output face 74 was changed from 5.63 kV and 5.15 kV respectively to 5.83 kV and 5.10 kV respectively.
It is appreciated that more precise control of contrast may be obtained if a greater number of image intensifiers are employed, and it is apparent that such greater number may readily be employed without departing from the spirit and scope of the present invention.
In lieu of conventional feedback systems, a "memory" system may be used which makes use of data already developed with respect to the dental arch area or object being radiographed. Such developed data may then be used to control the gains of the respective image intensifiers in order to optimize or maximize the data. For example, voltages applied to an image intensifier could be controlled by a cam operated potentiometer, or by an appropriately shaped electrical signal created by a non-linear oscillator, or the like. Thus, the memory system is frequently less expensive and simpler to use than the feedback system which requires sensing the effects being received, comparing them to a preset standard, and then fixing the input signal to thereby optimize results.
Image intensifiers 60 have an indicated depth of about 1/2" which may readily be changed by simply increasing or decreasing the depth of optic face plate 80. The nominal 1/2" depth of image intensifier 60 is accommodative to the existing film holder assembly 18 without requiring unnecessary modifications thereto. Film guide roller assemblies 63 (FIGS. 2 and 3) permit film 62 to travel unimpeded in constant light contact relationship across the output face of fiber optic face plate 80 in accordance with a rate of speed dictated by the radiographic image desired. Film guide roller assemblies 63 are rotatably mounted on brackets B, secured to bottom plate P of film holder assembly 18. Alternatively, the film guide roller assemblies may be mounted to door 56. Means for adjusting the film guide roller assemblies in order to accommodate image intensifiers of varying depths are also known and are not disclosed or illustrated herein.
Output face of fiber optic face plate 80 is provided with small radii 82 in order to prevent possible damage to film 62 as it lightly slides thereacross. Although film 62 will, ideally, contact the output face of fiber optic face plate 80, photon image scatter is within tolerable limits if distance between film 62 and output face of face plate 80 is maintained less than about 0.005".
It is understood of course that the individual fibers comprising fiber optic face plate 80 are aligned in the same direction as microchannels 68.
It is envisaged that certain structures may require a fiber optic face plate of substantially increased depth. The present inventive device may be used therewith since fiber optic face plates permit an image plane to be transmitted directly to its outer surface without the danger of generating internal reflections.
The invention is not intended to be limited to the image intensifying device shown and described. For example, X-ray detection or image intensifying devices employing scintillators, photocathodes, aluminized phosphor screens, electronic multiplier arrays of various types, etc. may be used advantageously with the present invention, with adaptation. Further, radioisotopic or radioactive sources may be used, and natural radiation from the human body may be useful for static X-ray as well as tomographic applications.
Film holder assembly 18 will be made light tight by conventional means prior to patient radiographing.
It is noted that any artifact produced on the radiograph by dielectric 65, or insulating film, barrier layer, or where the image intensifiers abut one another, is negligible since, if visible at all, will take the form of a straight line which rarely leads to a faulty diagnosis.
An embodiment of the invention constructed in accordance with the principles disclosed herein utilized an X-ray source capable of generating a continuous series of X-ray pulses for producing panoramic radiographs. The X-rays are generated by 50 to 90 kVp applied to a half-wave self-rectified tungsten anode X-ray tube, the incoming X-rays having an input energy ranging between about 20 to 40 keV effective. The sum of the image intensifiers, phosphors, etc. rise times and decay times should typically be less than 760 microseconds in order that target system resolutions will be obtained. Fast, light-sensitive dental film in the neighborhood of ASA 3000 may be used although slower film, approaching ASA 400 also have good results. Phosphor screen 78 must be spectrally matched to the film used to insure optimal activation of the photons. The photons emanating from phosphor screen 78 have a spectral radiance wavelength ranging between about 250-425 nanometers.
Panoramic techniques in current use by the assignee of the present invention employ 50 to 90 kVp at 5 mA for about 20 seconds duration. Panoramic techniques employing the principles of the instant invention require only 50 kVp maximum at 0.5 mA for the same duration. The focal spot of the X-ray tube to film 62 distance is 16.84" nominal.
The invention is not intended to be limited to panoramic dental radiography, since one skilled in the art may readily adapt the principles disclosed herein, for example, to conventional dental and medical X-ray apparatus.
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Panoramic dental X-ray machine includes a tubehead-camera assembly which employs, in its simplest embodiment, three vertically stacked image intensifiers, the totality of their radiation input faces being substantially similar in shape and dimensions to a slot in a front panel of the camera assembly, the input faces being secured against the slot and aligned therewith such that radiations passing therethrough must then pass through the image intensifiers. Means for selectively controllably varying the potential across each of the individual image intensifiers varies the electron gain of that image intensifier to thus provide optimal contrast between multi-density structures of the dental arch and surrounding areas on a full size radiograph.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Application No. 62/038,891 which was filed on Aug. 19, 2014, the contents of which are incorporated herein by reference.
BACKGROUND
[0002] Roulette is a very popular casino game. There are a few differences between how the game is played in the US and Europe, but it is a very traditional game and its modifications have been minimal over the course of many decades.
[0003] Many casinos in the world play roulette in a very traditional style with a very few modifications or side bets. Side bets are very popular for most table games. Roulette on the other hand, because of the way it is played, does not present a good environment for a side bet or modification which would attract additional players. The exception to this might be the two-wheel roulette arrangement, which is somewhat popular in European casinos.
[0004] Table games, in general, benefit from additional side bets or modified wagering for the base game by providing additional wagering options and additional game strategies, thus enhancing the game experience and possibly increasing casino revenue.
[0005] It is believed there is a need for a roulette game which would provide a wider range of winnings while not significantly changing the game environment. Such an enhancement would attract additional players to the game while simultaneously retaining existing players by not changing the game environment. Such additional or modified wagering on roulette is also thought to provide additional revenue to casinos.
SUMMARY
[0006] The disclosed embodiments have been developed in light of the above, and aspects of the invention may include a wagering game, gaming devices and systems, and methods for presenting and playing a wagering game. According to some embodiments, a casino wagering game may be referred to as “Power Pay Roulette.” In one embodiment Power Pay Roulette may be a modified wagering method for a traditional roulette game as described herein.
[0007] Embodiments of Power Pay Roulette are directed to systems and methods for operating a roulette game with a wider range of game winnings as compared to a traditional roulette game.
[0008] A method of wagering in Power Pay Roulette includes additional wagering options for a single event which provides multiple random or varied payouts in place of a single fixed payout in the standard roulette game.
[0009] The additional wagering options may provide an identical betting method as in traditional roulette. Players may bet on a specific number or a group. In traditional roulette, the payout for a single number win is generally 36:1. In Power Pay Roulette, the payout may be randomly chosen from a set of fixed payouts. In one embodiment, an average payout, however, remains 36:1 or lower.
[0010] In Power Pay Roulette, payouts may be randomly selected with predetermined probabilities. In one embodiment, a first payout may be greater than the traditional payout but have a low probability of occurring. A second payout may be lower than the traditional payout but have a high probability of occurring. According to one explanatory example, there may be a first payout of 144:1 (e.g. 144 times the wager $, such as $144 for a $1 wager) that has a probability of 1/10 and a second payout of 24:1 that has a probability of 9/10. In this example, if a player selects a winning number, he or she can win a payout or winnings of either 24:1 or 144:1 depending on which payout is selected.
[0011] The range of possible winnings may thus be wide and the highest win may be large enough to encourage players to bet in Power Pay Roulette. Payout possibilities may be modified to allow for a wide variety of outcomes. For example, payouts with probabilities of 1/3 to 1/1,000,000 may be utilized with corresponding payout amounts such that an average payout remains 36:1 or lower for a single number win. Payouts for group of numbers and other traditional roulette groups can be similarly modified to be incorporated in Power Pay Roulette.
[0012] In some embodiments, an apparatus for playing Power Pay Roulette is provided that includes a minimal set of items above that which is required for a traditional roulette table game. These items may include a display, an interface to a roulette wheel, a memory, and a processor. The processor is configured to execute instructions stored on the memory that cause the processor to recognize roulette wheel events, to display a generated single number payout for the current spin, to receive an input from the wheel interface, and to generate or receive a random event for payout generation.
[0013] Accordingly, the disclosed embodiments enhance a traditional roulette game with a set of gaming systems, apparatuses, and methods.
[0014] Further objects, features, and advantages of the present invention over the prior art will become apparent from the detailed description of the embodiments which follows, when considered with the attached figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The accompanying drawings, which are incorporated herein and constitute part of this specification, include one or more embodiments of the invention, and together with a general description given above and a detailed description given below, serve to disclose principles of the disclosed embodiments.
[0016] FIG. 1 illustrates an embodiment of a power pay game method.
[0017] FIG. 2 illustrates an embodiment of an exemplary chip sleeve.
[0018] FIG. 3 illustrates an embodiment of a video screen of an exemplary display presenting the payout multiplier for the single number bet for the current winning number.
[0019] FIG. 4 illustrates an embodiment of a system implementation of Power Pay Roulette.
DETAILED DESCRIPTION OF EMBODIMENTS
[0020] In the following description, numerous specific details are set forth in order to provide a more thorough description of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without these specific details. In other instances, well-known features have not been described in detail so as not to obscure the invention.
[0021] Reference will now be made to embodiments of apparatus, systems and methods for wagering in a roulette game referred to herein as Power Pay Roulette, examples of which are illustrated in the accompanying drawings. Details, features, and advantages of Power Pay Roulette will become further apparent in the following detailed description of embodiments thereof.
[0022] Systems, apparatuses, and methods to perform Power Pay Roulette are described herein. Any reference in the specification to “one embodiment,” “a certain embodiment,” or any other reference to an embodiment is intended to indicate that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment and may or may not be utilized in other embodiments as well.
[0023] Power Pay Roulette can be played in various environments. In a brick-and-mortar casino it may be added to or implemented at a standard roulette table. It may also be added to any variation of electronic table roulette or roulette gaming machine where a roulette wheel is controlled electronically. Power Pay Roulette can be played in a virtual environment as well, where a roulette wheel is simulated by a computer (such as at stand-alone or linked gaming machines or other gaming devices, such as in mobile or Internet environments). In any of these environments the winning number is always a result of a random event, in which the number is selected from a set of possible outcomes.
[0024] FIG. 1 illustrates an embodiment of a roulette game method 100 . Specifically, FIG. 1 shows a flowchart for a roulette game with a “power pay” betting option.
[0025] Initially, in step 102 , one or more players may have an opportunity to place wagers for a standard roulette game and/or Power Pay Roulette. The standard roulette game and Power Pay Roulette may be played simultaneously, or only wagers for the Power Pay Roulette game may be placed.
[0026] In step 104 , a power pay payout is selected. Preferably, the power pay payout is randomly selected from a set of fixed payout possibilities for the single-number win and/or any other standard roulette bet options for which a power pay betting option is defined. The payout selection is performed electronically either at the roulette table or in the back-of-house and sent to a table, or by a computer interface for any virtual environment. The payout may be generated by a random selection from a set of predefined payouts. For example, an RNG may be used to select one of the power pay payout possibilities.
[0027] In one embodiment, the statistical average value generated payouts should be equal to or less than the corresponding payout for a standard roulette win. For example, a traditional roulette payout for a single number win is 36:1. Thus, according to the Power Play Roulette, there may be one or more payout possibilities that pay lower than 36:1, and one or more payout possibilities that pay higher than 36:1. However, based on the probabilities of how often the payout possibilities occur, an average payout for the single number win may remain 36:1 or lower. Of course, the embodiments are not limited to the average payout being 36:1 or lower. The average payout may be adjusted to the preferences of a game operator taking into account any number of factors such as a desired house edge in the game.
[0028] According to one example, there may be a first payout rate of 144:1 that has a probability of occurrence of 1/10 and a second payout rate of 24:1 that has a probability of occurrence of 9/10. In this example, if a player selects a winning number, he or she can win a payout of either 24:1 or 144:1 (e.g. 24 times or 144 times their wager) depending on which payout rate is selected. The statistical expected payout value for this set of payouts is 36:1, which is typical of traditional roulette payout in many casinos.
[0029] In another example, the first payout rate may be 100:1 and have a probability of occurrence of 1/8, and second payout rate may be 24:1 and have a probability of occurrence of 7/8. In this example, the statistical expected payout value is less than 36:1. While the payout pay be represented as a ratio or spread, such as 24:1 or 100:1, it could be represented in other fashions, such as by a multiplier value. For example, the base payout might comprise a value of X and the higher payout value might be a multiplier thereof, such as 2×, 4×, 5× or the like. For example, if the base payout is 24:1 and the higher payout is 144:1, the base payout might be designated as X and the higher payout as 6×. In other embodiments, the payouts might be represented in reference to the standard payout. For example, if the standard payout is 36:1, then a base payout of 18:1 might be designed as ½× and a higher payout of 72:1 might be designated as 2×.
[0030] Of course, any number and variation of winning outcomes with different probabilities may be utilized, with the above only meant to be exemplary. For instance, while the above examples include two payout possibilities in each set, there may be more than two payout possibilities in a set. Further, while in these examples a first payout higher than the traditional payout and a second payout lower than the traditional payout have been selected, other variations could be utilized (such as 2 payouts greater than the traditional payout and 3 payouts less than the traditional payout, etc.) The probabilities for outcomes having a payout greater than a traditional game payout may vary, such as ranging from 1/3 to 1/1,000,000. The corresponding payouts for such probabilities may be adjusted accordingly.
[0031] In step 106 , an actual selection of the winning outcome is determined or performed. For a single number wager this may comprise selecting or determining the winning number. The selection event can be performed in a physical or virtual environment using a physical roulette wheel or a computer simulation. In both cases, the selection is a random process. In one embodiment, steps 104 and 106 may be performed simultaneously. That is, the random payout possibility for the Power Pay Roulette may be selected while the roulette wheel spins to select the winning outcome (such as winning number and winning color).
[0032] In steps 108 and 110 , the various wagers are resolved for the standard roulette wagers (if permitted) and the power pay wagers, respectively. Payouts are paid to players who wagered on the winning numbers selected in step 106 . Players who wagered using the power pay option receive payouts selected in step 104 . Payouts may be made in the form of chips, credits, money, etc.
[0033] In one embodiment, Power Pay Roulette is an optional wager that is made during or as part of a traditional roulette game. In a virtual environment or using chipless wagering, the ability to place a power pay wager may be implemented by modifying control instructions of a gaming machine or electronic gaming table and adding necessary items to display on the betting screen. At a traditional, physical roulette table, adding an additional power pay wager to the table layout may be achieved in at least one of the following two manners.
[0034] In one embodiment, there may be separate betting areas for standard roulette wagering and Power Pay Roulette wagering. This may be accomplished by splitting the betting areas or by adding an additional separate roulette wagering area for the power pay wagering.
[0035] In another embodiment, the power pay wagers may be placed in the same betting areas as the traditional roulette wagers. In this embodiment, different chips, for example, may be used for the power pay betting. This could be accomplished by marking some regular chips with some distinct symbol to mark the chips to be used for power pay betting or to use a simple and small chip sleeve to be used for chips wagered on Power Pay Roulette. Such sleeves could be available to players in a few places around the table. The same chip sleeves could be used by all players at the table.
[0036] FIG. 2 depicts an embodiment of a chip sleeve 200 . The sleeve's top 202 and bottom are circular disks with cutouts 204 and 206 to allow a chip to be easily inserted and removed. A side 208 of the sleeve extends along a small portion of a circumference of the sleeve 200 to allow facilitate the insertion and removal of a chip. In this way, the chip may only be inserted and removed through a sleeve opening 210 defined by the cutout 206 , and may not be removed from the cutout 204 . The illustrated sleeve 200 is just one embodiment of a holder, marker or the like for a chip (such as by covering, holding, or marking all or part of a chip).
[0037] A roulette table which offers Power Pay Roulette may be equipped with one or more displays, such as electronic video displays, to present the selected payout for the current round (generated in step 104 ). FIG. 3 illustrates an example Power Pay Roulette screen 300 , (e.g., graphical information presented on one or more displays). In one embodiment, the screen may display payout selected for the single number bet 302 for the current roulette spin. The screen may also present the winning number 304 . The screen may also display relevant information for any typical roulette wager for which a Power Pay Roulette option is available. In some embodiments, the display may depict all payout possibilities 308 for the single number bet. The display may further display the occurrence frequencies (or probabilities) for each of the payout possibilities 308 . It may also display power pay possibilities for other wagers such as for number-group wins or colors. The screen can provide additional information 306 about betting instructions on Power Pay Roulette.
[0038] It is further noted that the screen 300 may take on any other number of formats. For example, the payout for the single number bet 302 may be displayed as a base payout amount or a multiplier amount. For example, display 302 may be blank or display that the payout is a base payout when the single number wager will be paid at 24:1. However, if the payout is selected to be 144:1, the display 302 may display that the payout for this round has a 6× multiplier. Furthermore, lights, sounds, animations, or the like may be incorporated into the screen 300 when the payout that is higher than the traditional roulette game payout is awarded for a winning number, group, or color.
[0039] The Power Pay Roulette display maybe communicatively connected to a computer system which runs the required software and interacts with peripheral devices. FIG. 4 illustrates an embodiment of the Power Pay Roulette computer system 400 for a physical roulette table, which may include a memory 402 , a processor 404 , a table display 408 , a network interface 410 , a storage device 406 , and one or more communication adaptors 412 . The Power Pay Roulette computer system 400 may furthermore be coupled to a remote computer system 426 through network interface 410 .
[0040] Communication between the memory 402 , the processor 404 , the storage device 406 , the display 408 , the network interface 410 , and the communication adaptor 412 may be performed by way of one or more communication busses 414 . Those busses 414 may include, for example, a system bus, a peripheral component interface bus, and an industry standard architecture bus.
[0041] The memory 402 may include any memory device including, for example, random access memory (RAM), dynamic RAM, and/or read only memory (ROM) (e.g., programmable ROM, erasable programmable ROM, or electronically erasable programmable ROM) and may store computer program instructions and information. The memory may furthermore be partitioned into sections including an operating system partition 416 in which operating system instructions are stored, a data partition 418 in which data is stored, and a program partition 420 in which instructions for carrying out the system services are stored. The program partition 420 may store program instructions, such as for Power Pay Roulette, and allow execution by the processor 404 of the program instructions. The data partition 418 may furthermore store data such as one or more operating parameters to be used during the execution of the program instructions.
[0042] The communication adaptor 412 permits communication between the Power Pay Roulette system 400 and other devices or nodes coupled to the communication adaptor 412 such as keypad 424 and roulette wheel interface 422 . The keypad 424 (and/or one or more other input devices) allows a dealer to trigger system events or data input if required. The wheel interface 422 provides winning number data and triggers the generation of a win multiplier for every spin. The win multiplier can be generated by Power Pay Roulette services 420 or by remote computer system 426 .
[0043] It should be recognized that any or all of the components 402 - 424 may be implemented in a single machine. For example, the memory 402 and processor 404 might be combined in a state machine or other hardware based logic machine.
[0044] The Power Pay Roulette computer system 400 may be implemented along with real-chip wagering supervised by a dealer or with electronic chip-less wagering, or on a network. A network in which a Power Pay Roulette game may be implemented may be a network of nodes, which are typically processor-based devices, interconnected by one or more forms of communication media. The communication media coupling the Power Pay Roulette computer system 400 to one or more other devices or a network may include, for example, co-axial cable, optical fibers, and wireless communication methods such as use of radio frequencies.
[0045] FIG. 4 illustrates just one embodiment of a system. For example, the system 400 might include one or more detectors, such as for detecting the outcome of a roulette wheel spin (e.g. ball detectors, cameras or the like). In other embodiments, a croupier may utilize an input device to indicate the outcome of a spin of the roulette wheel.
[0046] As further indicated herein, the system might be applied to automated roulette wheels, such as wheels which are automatically spun (rather than by hand), etc.
[0047] The invention may be applied to gaming devices, such as gaming machines which are capable of presenting roulette games, such as simulated roulette games (such as where the outcome of the roulette spin is computer generated/selected and the roulette wheel spin might be represented graphically, such as on a video display). The gaming machines might be stand alone, linked with other machines, and or be associated with one or more game servers (such that the gaming machines themselves are thin clients which essentially just present the game outcomes). In such environments, a single player might play the roulette game of the invention as a gaming device. Further, while such devices might comprise traditional casino-style machines having a housing, processor, wager input device(s), player input device(s), one or more video displays and the like, such devices might comprise computers (including laptops, tablets, desk tops and the like), and even mobile computers or communication devices, such as PDAs and the like.
[0048] In one embodiment, an existing or standard roulette game (such as which offers standard or traditional wagers and associated payouts) is modified to include the power pay feature described herein. In other embodiments, it is possible for the roulette game to only offer the power pay wagering feature or the power pay wagering feature and some of the traditional roulette wagers but not all of them. For example, a game of the invention might offer only the power pay wager on single numbers, but still offer other of the traditional roulette wagers.
[0049] It will be understood that the above described arrangements of apparatus and the method there from are merely illustrative of applications of the principles of this invention and many other embodiments and modifications may be made without departing from the spirit and scope of the invention as defined in the claims.
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A modified wagering method for a traditional roulette game called Power Pay Roulette provides a wider range of game winnings as compared to the standard roulette game. A method of wagering on a Power Pay Roulette includes additional wagering options for a single event which provides multiple random payouts in place of a single payout in the standard roulette game. A game system for implementing Power Pay Roulette may include a display, a user interface and a processor. The processor executes instructions that cause the processor to recognize roulette wheel events, display winning numbers and winning payouts.
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FIELD OF THE INVENTION
The present invention relates to a device for thickening a fiber suspension, such as a cellulose slurry, through the use of a hollow filter assembly disposed within a vat containing the suspension.
BACKGROUND OF THE INVENTION
FIG. 1 depicts a conventional drum gravity thickener that may be used to thicken a fiber suspension, such as a cellulose slurry (pulp stock). A hollow filter assembly in the form of a horizontal cylindrical drum 101 is disposed within a vat 103, whereby the drum 101 may be rotated about a horizontal axis 151 through the use of a motor 152 in drivable engagement with the drum 101 via gear assembly 153. The drum 101 includes around its circumference walls made of a filter material 102. The direction of rotation of the drum 101 is indicated in FIG. 1 by an arrow 111. The interior 118 of the drum 101 includes an outlet 154 for discharging the suspension (filtrate) (162) that forms within the interior 118 of the drum 101.
Fiber suspension is supplied to the drum filter 101 and the vat 103 by means of a spray nozzle 106a or a conduit 106b, or both. At the same time, the drum 101 is rotated about its axis 151, as described previously. As the fiber suspension is sprayed from the spray nozzle 106a and/or supplied through the conduit 106b, a pool 161 of fiber suspension accumulates in the vat 103 outside the drum 101 and the drum 101 becomes at least partially submerged in the pool 161. Due to the hydrostatic pressure exerted on the fiber suspension 161 by gravity, a portion 162 of the fiber suspension 161 (including water, fine particles, etc.) is forced through the filter material 102 of the drum 101 and into the interior 118 of the drum.
Because of the filtering action of the filter material 102, the resulting fine fraction 162 within the interior 118 of drum 101 contains relatively few coarse (large) fibers. As the fine particles and water pass through the filter material 102, the fiber suspension 161 remaining on the outside of the filter material 102 thereby becomes thicker as the water and fine particles pass into the interior 118 of the drum, while coarse fibers remain in the fiber suspension 161.
Moreover, as the fiber suspension 161 is forced by hydrostatic pressure against the filter material 102, coarse fibers that are too large to pass through the filter material 102 create a dewatered mat 169 (or cake) on the exterior surface 102a of the filter material 102 of the drum 101. The creation of tight dewatered mat 169 gives rise to diminishing fine fraction flow into the drum 101, as depicted in FIG. 1 by arrows 163a and 163b. Due to the counterclockwise rotation of the drum 101 about its axis 151, along with the constant hydrostatic pressure exerted by the fiber suspension 161, the fiber suspension 161 becomes thicker as the filter material 102 is displaced through the fiber suspension 161. As the filter material 102 travels from its descending side 102b to its ascending side 102c, the fiber suspension 161 generally continues to thicken. Eventually, the thickened fiber suspension 161 travels to the overflow conduit 110a of discharge outlet 110 (at predetermined level 110b), and may be carried out of the vat 103 for further processing (not shown).
The approximate relative consistencies of the fiber suspension 161 in various locations within the vat 103 are indicated by the following reference numerals: low consistency (0.5%) 161a, medium consistency (1.5%) 161b, medium high consistency (3-5%) 161c, and high consistency (10%) 161d. The percentages indicate an approximate percent consistency. As arrows 163a indicate, the fiber suspension 161 in proximity to the filter material 102 travelling in its descending side 102b is, overall, of a relatively low consistency such that hydrostatic pressure acting on the fiber suspension 161 causes a relatively large volume of water and fine particles to pass through the filter material 102 into the interior 118 of the drum 101. In contrast, because the fiber suspension 161 continues to thicken and a thicker and denser mat forms on the filter material 102 as it travels from its descending side 102b to its ascending side 102c, less and less water and fine particles within the fiber suspension 161 are allowed to pass through the filter material 102 (depicted by shorter arrows 163b). As a result, water and fine particles within the portion of the fiber suspension 161 close to the interior wall 103a of the vat 103 remain. The fiber suspension 161 near the exterior surface 102a of the filter material 102 as it travels in its ascending side 102c becomes thicker (e.g., a high consistency 161d), but the portion of the fiber suspension 161 that reaches the overflow 110a and spills over into the discharge outlet 110 remains at only a medium high consistency 161c.
Thus, there exists a need in the art for an improved thickening system that overcomes the disadvantages discussed above, as well as other disadvantages. As described below, these and other shortcomings are effectively overcome by the teachings of the present invention.
SUMMARY OF THE INVENTION
The present invention introduces a fiber suspension thickener, particularly adapted for thickening cellulose fiber. The thickener comprises a vat; a hollow filter assembly in the form of a horizontal cylindrical drum disposed within the vat, whereby the drum may be rotated by a motor around its horizontal axis, and whereby the cirumferential walls of the drum are made of a filter material; either a spray nozzle or some other supply conduit that furnishes a fiber suspension into the interior of the vat, so that the drum becomes submerged within a pool of the fiber suspension; a discharge outlet for discharging the fiber suspension on the ascending side of the rotating drum; and a turbulence creating device, that can take many forms, for creating turbulence and mixing the fiber suspension on the ascending side of the rotating drum. The turbulence creating device prevents coarse fibers within the fiber suspension from caking or matting on the exterior of the filter material of the drum, and improves the overall thickening capability of the present invention.
SUMMARY OF THE DRAWINGS
FIG. 1 depicts a conventional thickener for thickening a fiber suspension, such as a cellulose slurry.
FIGS. 2A, 2B, 3A, 3B, 4A, 4B, 5A, 5B, 6A, 6B, 7A, 7B, 8A, 8B, 9A, and 9B depict various embodiments of the thickener of the present invention, including various embodiments of a turbulence creating (mixing) device used therein.
FIG. 10 depicts a process for implementing the thickening features of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 2A and 2B, 3A and 3B, 4A and 4B, 5A and 5B, 6A and 6B, 7A and 7B, 8A and 8B, and 9A and 9B illustrate side views and three-dimensional perspective views, respectively, of a thickener according to various embodiments of the present invention. For purposes of the description of the present invention below, like-numbered reference numerals used in the various figures correspond to identical or analogous components.
As with the prior art thickener of FIG. 1, the present invention depicted in FIGS. 2A through 9B may include a horizontal drum 101 disposed within a vat 103, whereby the drum 101 may be rotated about a horizontal axis 151 through the use of a motor 152 in drivable engagement with the drum 101 via gear assembly 153. Again, the drum 101 includes around its circumference walls made of a filter material 102, and the direction of rotation of the drum 101 is indicated by an arrow 111. The interior 118 of the drum 101 includes an outlet 154 for discharging the suspension and/or liquid (162) that forms within the interior 118 of the drum 101.
Also, like the prior art thickener, fiber suspension may be supplied to the drum filter 101 and the vat 103 by means of a spray nozzle 106a or a conduit 106b, or both. As the drum 101 is rotated about its axis 151, the fiber suspension is sprayed from the spray nozzle 106a and/or supplied through the conduit 106b, and a pool 161 of fiber suspension accumulates in the vat 103 outside the drum 101. Due to the hydrostatic pressure from gravity exerted on the fiber suspension 161, a portion 162 of the fiber suspension 161 (including water, fine particles, etc.) passes through the filter material 102 of the drum 101 and into the interior 118 of the drum 101. The above initial steps of the process of the present invention are depicted as step 1001 in FIG. 10.
As with FIG. 1, because of the filtering action of the filter material 102 in FIGS. 2A through 9B, the resulting fine fraction 162 within the interior 118 of drum 101 contains relatively few coarse (large) fibers. As the fine particles and water pass through the filter material 102 into the interior 118 of the drum 101, the fiber suspension 161 remaining on the outside of the filter material 102 thereby becomes thicker, while coarse fibers remain in the fiber suspension 161.
Additionally, like FIG. 1, as the fiber suspension 161 is forced by hydrostatic pressure against the filter material 102 in FIGS. 2A through 9B, coarse fibers that are too large to pass through the filter material 102 initially create a de-watered mat 169 (or cake) on the exterior surface 102a of the filter material 102 of the drum 101. Again, due to the counterclockwise rotation 111 of the drum 101 about its axis 151, along with the continuous loss of liquid into the interior 118 of the drum 101, the fiber suspension 161 becomes thicker as it moves through the vat 103. The above steps are depicted as step 1002 in FIG. 10.
As the fiber suspension travels from the descending side 102b to the ascending side 102c of the drum 101, the fiber suspension 161 generally continues to thicken. Eventually, the thickened fiber suspension 161 travels to the overflow 110a of discharge outlet 110, and is carried out of the vat 103 for possible further processing.
In addition to the components of the thickener described above with respect to FIGS. 2A through 9B (which generally correspond to like-numbered components of the prior art thickener of FIG. 1), the present invention also includes a turbulence creating device 260 (or devices) within the vat 103 (and outside the drum 101) in proximity to the ascending side 102c of the filter material 102. The turbulence creating device 260, which may be implemented simply and inexpensively, is designed to mix the fiber suspension 161 within the vat so as to avoid the fiber suspension discharge consistency problems associated with the prior art thickener of FIG. 1. In one embodiment, the turbulence creating device 260 may be located closer to predetermined level 110b than to the lowest part 101a of drum 101. The above steps are depicted as step 1003 in FIG. 10.
Particularly, as previously described in FIG. 1, the fiber suspension 161 in proximity to the ascending side 102c of the filter material 102 generally separates into two portions, with a medium high consistency portion 161c forming near the interior wall 103a of the vat 103, and a high consistency portion 161d forming near the exterior surface 102a of the filter material 102. Again, this undesired result causes a medium high consistency 161c, rather than a high consistency 161d, of the fiber suspension 161 to spill over into the discharge outlet 110.
Again, as with FIG. 1, and as arrows 263a indicate, the fiber suspension 161 in proximity to the filter material 102 travelling in its descending side 102b is, overall, of a relatively low consistency 261a such that hydrostatic pressure acting on the fiber suspension 161 causes a relatively large volume of water and fine particles to pass through the filter material 102 into the interior 118 of the drum 101. However, unlike the prior art thickener of FIG. 1, a thicker and denser mat does not continue to form (at least not to the same extent as in FIG. 1) as the filter material 102 travels along the ascending side 102c of the drum 101. Rather, in accordance with the teachings of the present invention, the fiber suspension 161 in proximity to the ascending filter material 102 may be mixed, or otherwise agitated, with the mat 169 by a turbulence creating device 260 so that the various consistencies within the fiber suspension 161 are made more uniform.
Thus, instead of a high consistency suspension 161d forming near the exterior surface 102a of the ascending filter material 102c while a medium high consistency suspension 161c forms near the interior 103a of vat 103 (eventually being discharged into discharge outlet 110) (as shown in prior art FIG. 1), the thickener configuration of the present invention causes the fiber suspension to be more evenly dispersed near the ascending side 102c of the drum 101, resulting in a more even distribution of fiber suspension 161 in proximity to side 102c. A thick fiber mat does not form on the exterior surface 102a of filter material 102 (shown in FIG. 1 as 161d), but instead a medium high consistency suspension 261c is dispersed fairly evenly in the vat 103 outside the drum 101. As shown in FIG. 2A, and equally applicable to FIGS. 2B and 3A through 9B, arrows 263b are of only slightly smaller length (or even equal length) as arrows 263a, indicating that more water and fine particle are allowed through on the ascending side 102c in FIGS. 2A through 9B, than on the ascending side 102c in FIG. 1. Thus, in FIGS. 2A through 9B, by the time the fiber suspension 161 reaches the discharge outlet 110, more water and fine particles have been removed than in the prior art thickener, resulting in a higher consistency suspension 261d reaching the discharge outlet 110. The above steps are depicted as step 1004 in FIG. 10.
The increase in thickening or consistency of the fiber suspension pulp 161 achieved by the present invention is quite beneficial to pulp and paper manufacturers because it is less difficult and costly to store thickened pulp, because it has a smaller volume than before it is thickened. Thickened fiber suspension also costs less to bleach--less bleaching chemicals are required because there is less fiber suspension to dilute the bleaching chemicals. Furthermore, the thickened fiber suspension of the present invention is generally cleaner as fine contaminants are removed along with water. Additionally, because of the smaller volume of the thickened fiber suspension, equipment that handles the thickened suspension may be made smaller and less expensive.
The approximate relative consistencies of the fiber suspension 161 in various locations within the vat 103 in FIGS. 2A through 9B are indicated by the following reference numerals: low consistency (0.5%) 261a, medium consistency (1.5%) 261b, medium high consistency (3-5%) 261c, and high consistency (8%) 261d. These reference numerals are essentially the same as the corresponding reference numerals in FIG. 1 (e.g., 161a, 161b, 161c, 161d), except that the high consistency fiber suspension 261d in FIGS. 2A through 9B indicates a slightly lower consistency than the high consistency fiber suspension 161d in FIG. 1. This slight discrepancy is based upon a more uniform, although possibly slightly lower consistency, of higher consistency suspension 261d that reaches the discharge outlet 110 in FIGS. 2A though 9B, in contrast to the medium high consistency suspension 161c that travels to the discharge outlet 110 in the prior art thickener of FIG. 1. In FIG. 1, the high consistency suspension 161d generally never reaches the discharge outlet 110, because it is diluted by lower consistency fiber. In any event, the overall consistency of the fiber suspension 161 that reaches the discharge outlet 110 in the present invention of FIGS. 2A through 9B is noticeably higher than that of prior art thickeners, including that depicted in FIG. 1.
FIGS. 2A through 9B depict a sampling of the various turbulence creating devices 260 that may be used for purposes of the present invention. FIGS. 2A through 9B are grouped together in pairs, whereby a numbered figure with a suffix of "A" illustrates a cut-away side view of the thickener, and the corresponding numbered figure with a suffix of "B" illustrates a three-dimensional cut-away perspective view of the same thickener. One of ordinary skill in the art will readily recognize that the various embodiments of the present invention depicted in FIGS. 2A through 9B represent merely a handful of the multitude of ways that the present invention may be implemented.
For example, FIGS. 2A and 2B illustrate turbulence devices in the form of angled projections 260a positioned along the interior wall 103a of the vat 103. In one embodiment, the angled projections 260a may be integrally molded into the vat 103, or they may be separate components attached to the interior wall 103a of the vat 103. Additionally, the angled projections 260a may be formed of the same type of material used to form the vat 103, or any other suitable material.
As shown in FIG. 2B, the angled projection 260a may preferably extend along the entire horizontal length 270 of the interior wall 103a of the vat 103, which may be substantially the same or greater than the horizontal length 271 of the drum 101. Of course, the angled projections 260a will work at other lengths as well (such as less than the length 271 of the drum 101), and need not necessarily be positioned horizontally.
FIGS. 3A and 3B depict another embodiment of the turbulence creating device 260. In FIGS. 3A and 3B, three different types of projections 260b, 260c and 260d are provided having various shapes and sizes. Again, these projections may be formed of any suitable material.
Projection 260b may be fashioned as an angled projection similar in size to angled projection 260a (FIGS. 2A and 2B), although it may be hollow inside. Similarly, projection 260c may be fashioned in the form of a cube or other hexahedron, and projection 260d may be fashioned in the shape of a cylinder. As with the angled projection 260a of FIGS. 2A and 2B, projections 260b, 260c and 260d may extend the entire horizontal length 270 of the vat 103, may extend the entire horizontal length 271 of the drum 101, may extend to any other suitable length, or may not be horizontal at all.
FIGS. 4A and 4B depict yet another embodiment of turbulence creating device 260. In FIGS. 4A and 4B, turbulence creating device 260 may take the form of a stationary member 260e attached to the end walls 103b (only one side of which is shown) of the vat 103. As illustrated in FIG. 4B, in this case the stationary member 260e is not attached to the interior wall 103a of the vat, but of course such a configuration is possible.
The stationary member 260e may include a rod 260e-1 extending along the horizontal (or a non-horizontal) length 270 of the vat 103. In one embodiment, the rod 260e-1 may include one or more vertical members 260e-2 disposed thereon. In another embodiment (not particularly shown), the rod 260e-1 may simply be a solid hexahedron (or any other suitable shape) without the attached vertical members 260e-2. Additionally, the rod may be fashioned out of any suitable material.
In FIGS. 5A and 5B, the turbulence creating device 260 may take the form of a rotating screw mechanism 260f (impeller). The rotating screw mechanism 260f may include a rod 260f-1 with helical screw blades 260f-2 attached thereto, as well as a motor 260f-3 attached to the rod 260f-1 for rotating the screw 260f-1/260f-2. As shown in FIG. 5A, the screw may be rotated in a clockwise direction when viewed from the side (indicated by arrow 260f-4), but of course any suitable direction would suffice. In this embodiment, the drum 101 rotates counter-clockwise (arrow 111), while the screw 260f-1/260f-2 rotates clockwise.
FIGS. 6A, 6B, 7A, 7B, 8A, 8B, 9A and 9B illustrate various embodiments of turbulence creating devices 260, all of which include projections and indentations on a weir 260g (dam) coupled to the vat, separating the interior of the vat 103 from the discharge outlet 110. In FIGS. 6A and 6B, the weir 260g is formed of three (or any other suitable number) U-shaped pieces 260g-1 positioned to run the length 270 of the interior wall 103a of the vat 103. The U-shaped pieces 260g-1 are stacked on top of one another as shown, with their interior indentations 260g-2 facing toward the drum 101. The weir 260g may be formed of any suitable material, and in another embodiment, may be formed integrally with the vat 103.
FIGS. 6A, 6B, 7A and 7B both depict the weir 260g as described above, except that FIGS. 6A and 6B also include the angled projections 260a described previously with respect to FIGS. 2A and 2B. In contrast, FIGS. 7A and 7B depict the weir 260g without the angled projections 260a. Both of these embodiments are provided in order to illustrate that the various embodiments of the turbulence creating device 260 shown in FIGS. 2A through 9B may be readily mixed and matched in various configurations in order to achieve the objectives of the present invention.
FIGS. 8A, 8B, 9A and 9B illustrate additional embodiments of the turbulence creating device 260 in the form of a weir 260g. In FIGS. 8A and 8B, a weir 260g is provided including pieces 260g-5 having angled projections 260g-6 extending therefrom toward the drum 101. In FIGS. 9A and 9B, a weir 260g is provided including pieces 260g-7 having angled projections 260g-8 (ridges) and angled indentations 260g-9 (valleys). Like FIGS. 6A through7B, the weirs 260g of FIGS. 8A through 9B may extend along the horizontal length 270 of the interior wall 103a of the vat (or may extend along any other horizontal or non-horizontal length--such as length 271).
It will be readily apparent to one of ordinary skill in the art that the turbulence creating devices 260 shown in FIGS. 2A through 9B are but a few of the devices that may be used to agitate or mix the fiber suspension 161 in proximity to the ascending side 102c of the filter material 102. Other devices, either stationary or moving, may also be used to create turbulence or to mix the fiber suspension so as to achieve the ends of the present invention.
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The present invention introduces a fiber suspension thickener, particularly adapted for thickening cellulose fiber. The thickener comprises a vat; a hollow filter assembly in the form of a horizontal cylindrical drum disposed within the vat, whereby the drum may be rotated by a motor around its horizontal axis, and whereby the cirumferential walls of the drum are made of a filter material; either a spray nozzle or some other supply conduit that furnishes a fiber suspension into the interior of the vat, so that the drum becomes submerged within a pool of the fiber suspension; a discharge outlet for discharging the fiber suspension on the ascending side of the rotating drum; and a turbulence creating device, that can take many forms, for creating turbulence and mixing the fiber suspension on the ascending side of the rotating drum. The turbulence creating device prevents coarse fibers within the fiber suspension from caking or matting on the exterior of the filter material of the drum, and improves the overall thickening capability of the present invention.
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FIELD OF THE INVENTION
The present invention relates to a permanent safety device for preventing the accidental firing of a weapon whose firing mechanism comprises a trigger, a hammer, a loaded spring which exerts a force along a given line of action on said hammer, retention means which hold the hammer in opposition to said spring and, inserted between the trigger and said hammer retention means, a lever which disengages these latter at the time of firing as a result of the trigger being pulled.
BACKGROUND OF THE INVENTION
Firing mechanisms of the type detailed above are well known within the firearms sector, in both hunting and military guns.
The fact these mechanisms include a safety device which can be engaged and disengaged manually is also well known.
The known manual safety devices usually used in firearms consist of catch mechanisms which, once engaged, make it impossible to move those components which are designed to disengage the hammer retention means and therefore, even if pressure is exerted on the trigger, prevent the sequence of movements that result in a shot being fired from taking place, including, in particular, the movement of the hammer which, as is known, is permanently subjected to the action of a spring.
Despite immobilizing the components mentioned above, or even the trigger, by means of the conventional safety devices found in firearms, there is still the problem—and one which can sometimes have extremely serious consequences—of the gun firing accidentally as a result of the hammer retention means being disengaged inadvertently.
As mentioned earlier, the hammer is permanently subjected to the action of a spring and is held in opposition to the latter by means which are usually in the form of a hook.
If these means should, for whatever reason—for example as a result of a violent knock to the weapon or wear of the hooking surfaces—cease to function properly, the hammer is released and the force of the spring is fully discharged onto said hammer, causing the gun to fire accidentally.
The object of the present invention is to equip the firing mechanism of a firearm of the type specified above with a permanent safety device which is independent of the conventional safety catch and which, even if the hammer retention means are released or disengaged accidentally, will not allow the hammer, even though it is subjected to the force of the spring, to receive a sufficient force to cause the gun to fire.
SUMMARY OF THE INVENTION
This object is achieved by a permanent safety device for preventing the accidental firing of a weapon whose firing mechanism comprises a trigger, a hammer, a loaded spring which exerts a force along a given line of action on said hammer, retention means which hold the hammer in opposition to said spring and, inserted between the trigger and said hammer retention means, a lever which disengages these latter at the time of firing as a result of the trigger being pulled. The permanent safety device includes a stop piece which can be moved between an interference position in which it interferes with the action of said spring and a position in which it does not interfere with said action, and vice versa, and a mechanism, connected to the trigger, which is designed to move said stop piece out of said interference position only if the trigger is pulled.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described in greater detail with reference to a number of practical embodiments thereof which are given solely by way of non-limiting example and illustrated in the appended drawings, in which:
FIG. 1 shows a perspective view of the basic elements of a firing mechanism of a firearm, especially a hunting rifle or shotgun, fitted with the permanent safety device according to the invention in a first embodiment;
FIG. 2 shows a perspective view of a component of the mechanism of the permanent safety device according to the invention, from the embodiment shown in FIG. 1;
FIG. 3 shows a diagrammatic perspective view of the permanent safety mechanism of the example shown in FIGS. 1 and 2, in the active position;
FIG. 4 shows the mechanism of the previous figure in the inactive position that immediately precedes an intentional shot;
FIG. 5 shows a second embodiment of the permanent safety device according to the invention, in its active position;
FIG. 6 shows the device of the embodiment shown in FIG. 5 in the inactive position that immediately precedes an intentional shot;
FIG. 7 shows a third embodiment of the permanent safety device according to the invention, in the active position;
FIG. 8 shows the device of the embodiment shown in FIG. 7 in the inactive position immediately prior to an intentional shot.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the abovementioned figures and in particular to FIGS. 1 to 4 , the reference 1 denotes, overall, the support frame of the firing mechanism of a firearm, for example a shotgun.
The trigger 2 pivots on the pin 3 and the hammer 4 is mounted so that it can rotate about the pin 5 .
In the example described, the hammer 4 takes the form of a cranked lever having a longitudinal portion 4 a and a transverse portion 4 b.
The latter portion terminates in a hook-shaped end 6 , the front of which engages with another hook 7 carried on the end 8 of a lever 9 which is mounted so that it can rotate about the pin 10 .
The other end 11 of the lever 9 is designed to work in conjunction with a catch element of the conventional safety system which has not been illustrated since it is not relevant to the present invention.
The back 12 of the hammer is, in the conventional manner, designed to strike the firing pin (not illustrated in the drawings) at the time of firing as a result of its rotation about the pin 5 .
The side 13 , opposite the back 12 of the hammer, carries a projection 14 which is permanently in contact with the end 15 of a cap 15 a which at least partially encloses a compressed spring, shown diagrammatically as 16 . The other end 17 of the spring 16 reacts, in the conventional manner, against the frame 1 which has not been illustrated in FIGS. 3 and 4 for the sake of simplicity and clarity.
The lever 9 , its tooth 7 and the tooth 6 of the hammer 4 that engages with the tooth 7 , constitute the retention means which hold the hammer in opposition to the thrust force exerted along the line of action X—X by the spring 16 which is in permanent contact with the projection 14 via the cap 15 a.
Inserted between the lever 9 and the trigger 2 is a lever 18 which, via its end 18 a , is hinged to the end 2 a of the trigger by means of a pin 19 .
The tip of the other end 18 b presses against the lever 9 , at a point between the pivot pin 10 and the end 8 .
This same end 18 b of the lever 18 has a projection 20 , positioned at an angle with respect to the axial extension of the lever, which engages slidably within the window 21 formed in the end 22 a of a lever 22 .
This lever 22 pivots like a rocker arm by means of the hole 10 a around the pin 10 —on which the lever 9 is also pivotably mounted—and carries a transverse piece, denoted 23 , on its other end 22 b.
The projection 20 and the window 21 form a connection means between the lever 18 and the lever 22 .
The piece 23 on the lever 22 is usually positioned such that it interferes with a zone 15 b affected by the movement of the cap 15 a containing the spring 16 , generally to the side of the line of action X—X of the force of the spring 16 , as illustrated in FIG. 3 .
In addition, the piece 23 is positioned, in the direction of the line X—X, a preset distance away from the end 15 of the cap 15 a.
This positioning means that, in the event of the teeth 6 and 7 disengaging for whatever reason—for example as a result of wear of the contact surfaces of the hooked connection or an accidental knock, but not because the trigger 2 has been pulled—the thrust force of the spring 16 , whose cap 15 a is permanently pressed against the projection 14 on the hammer, cannot be fully discharged because, beyond the preset distance, at least part of the end 15 of the cap 15 a hits the piece 23 on the lever 22 , which acts as a stop.
The spring 16 can therefore only transmit a limited thrust via the cap 15 a to the hammer 4 and this thrust is not enough to release the hammer so that it can strike the firing pin (not illustrated) with sufficient energy to fire a shot.
Only when the shot is intentional, i.e. caused by the trigger 2 being pulled, is the piece 23 on the lever 22 first moved out of the zone of displacement of the spring 16 .
The axial movement of the lever 18 and the resultant pressure exerted by the end of the latter on the lever 9 , then cause the teeth 6 and 7 to disengage.
When this happens, the hammer can then receive the full force of the spring 16 and so strike the firing pin with sufficient energy to fire the gun.
Displacement of the transverse piece 23 , which acts as a stop for the cap 15 a containing the spring 16 and limits the force of the energy discharged by the latter on the hammer, is achieved by virtue of the connection between the lever 18 and the rocker lever 22 .
This is because the axial movement of the lever 18 , which gradually causes the tooth 7 to disengage from the tooth 6 on the hammer 4 , also causes the angular movement of the lever 22 and, because of the different lengths of the arms relative to the pivot pin 10 , moves the piece 23 out of the zone 15 b of displacement of the cap 15 a , slightly before disengagement of the teeth 6 and 7 takes place.
The device of the invention therefore constitutes a permanent safety mechanism which does not need to be engaged and disengaged manually.
It is only when the gun is to be fired intentionally that, in an action consequent upon the moving of the trigger, this safety mechanism renders the spring 16 fully active and allows all its energy to be discharged onto the hammer 4 in order to fire a shot.
In all other cases, unless the trigger 2 is moved, the safety device continues to remain active, even when the teeth 6 and 7 accidentally disengage, thereby releasing the hammer.
More specifically, with reference to the embodiment of FIGS. 3 and 4, if the teeth 6 and 7 do disengage accidentally, the pressure exerted by the spring 16 , via the cap 15 a , on the stop piece 23 tends to cause the lever 22 to rotate clockwise about the pin 10 , thereby holding the piece 23 even more firmly in its operational stop position, therefore making the safety device even more effective.
With reference to the example illustrated in FIGS. 5 and 6, in which elements corresponding to those in the embodiment o f FIGS. 1 to 4 have been given the same reference numerals, it will be noted that a stop piece 123 is carried by the end 122 b of a rod 122 which is mounted on the frame of the weapon such that it can be moved axially in both directions.
The end 122 a of this rod 122 hooks onto the end 118 b of the lever 118 which, similarly to the example shown in FIGS. 1 to 4 , is actuated by the trigger 2 .
Unless the trigger 2 is moved, the stop piece 123 interferes with the action of the spring 16 and so prevents, should the teeth 6 and 7 disengage accidentally, the full elastic force of the spring from being discharged onto the hammer 4 and causing the gun to fire accidentally.
In contrast, when the trigger 2 is pulled, the lever 118 axially pushes the rod 122 while its tip acts simultaneously on the lever 9 .
Before the teeth 6 and 7 are disengaged, the rod 112 moves the stop piece 123 out of the way, thereby releasing the spring 16 .
With reference to the example illustrated in FIGS. 7 and 8, it will be noted that the permanent safety device according to the invention can also be used in a shotgun in which the barrels are on top of each other and which has a known, conventional firing mechanism.
It should be noted in this example that the spring 216 is mounted coaxial on a rod 217 whose end 217 a bears against the hammer 204 which can rotate about the pin 205 , while a portion 217 b of its opposite end passes through a wall 218 of the frame and terminates in an enlargement 219 formed, for example, by a nut screwed onto the threaded end of the rod.
When the hammer is in the cocked position, as shown in FIG. 7, in which the teeth 206 and 207 are mutually engaged, the spring 216 is compressed between the wall 218 and the flange 220 of the end 217 a.
The end 221 of a rocker lever 222 , which is mounted so that it can rotate around the pin 223 , is inserted along the portion 217 b and presses against the enlargement 219 .
The other end 224 of this lever 222 is forked, its times 225 enclosing the portion 226 of an extension piece integral with the trigger 2 .
When the components are in the position described, it is clear that, if the elements retaining the hammer 204 in position—i.e. the teeth 206 and 207 —are released, the force of the spring 216 cannot be discharged onto the hammer 204 because the rod 217 is axially immobilized by the end 221 of the lever 222 .
With reference to FIG. 8 which relates to the same embodiment, it will be noted that, when the gun is fired intentionally, the action of moving the trigger 2 causes the end 221 of the lever 222 to be moved out of the way even before the teeth 206 and 207 are disengaged, releasing the rod 217 which, as soon as the teeth 206 and 207 are disengaged, discharges the full force of the spring 216 onto the hammer 204 , thereby firing the gun.
It will be obvious that the invention described with reference to the specific embodiments detailed above can undergo various modifications, especially with regard to the shape of the mechanical parts and their physical layout within the framework of a firing mechanism, depending on the type of weapon, without thereby departing from the scope of the following claims.
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Permanent safety device for preventing the accidental firing of a weapon whose firing mechanism comprises a trigger, a hammer, a loaded spring which exerts a force along a given line of action on said hammer, retention means which hold the hammer in opposition to said spring and, inserted between the trigger and said hammer retention means, a lever which disengages these latter at the time of firing as a result of the trigger being pulled. The abovementioned firing mechanism includes a stop piece which can be moved between an interference position in which it interferes with the action of said spring on the hammer and a position in which it does not interfere with said action, and vice versa, and a mechanism, connected to the trigger, which is designed to move said stop piece out of said interference position only if the trigger is pulled.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The subject invention generally pertains to air filters and more specifically to a fabric filter for use inside an air duct.
[0003] 2. Description of Related Art
[0004] Fans or blowers are used along with ductwork to circulate air through a room or area of a building. The blower typically draws air from within the room through a return air duct and then forces the air back into the room through a supply air duct. To heat or cool the air, the blower may also force or draw the air across a heat exchanger.
[0005] To help prevent dust from accumulating on the heat exchanger, blower, and ductwork, often a conventional filter is installed at the downstream end of the return air duct. Finer, less porous filters are used where dust removal is more critical, such as in so called clean rooms or in buildings having occupants with dust-related allergies. Unfortunately, fine filters usually create a higher pressure drop that reduces the amount of airflow. To minimize the pressure drop, a filter's effective cross-sectional area can be increased in various ways, such as by adding pleats to the filter, installing the filter at an angle relative to the duct, or by forming the filter as an elongated bag that extends lengthwise into an air duct.
[0006] Some examples of filters that are elongated along the direction of airflow are disclosed in U.S. Pat. Nos. 2,853,154; 3,151,962; 3,195,296; 3,204,391; 3,204,392; 3,396,517; and 3,538,686. When mounting such filters within a return air duct, upstream of the blower, a significant distance is needed between the blower and where the filter attaches to the duct, simply due to the length of the filter. In many cases, this can be difficult or impossible to do, because of bends or elbows in the ductwork. Also, much of the ductwork is usually inaccessible, as it is often installed within the walls of the building or between the floor and ceiling. So filters in a return air duct are typically installed immediately adjacent the blower, which may prohibit the use of an elongated filter or at least significantly limit its length.
[0007] On the other hand, if an elongated air filter were installed in the supply air duct, the filter would do little in preventing dust from accumulating on the blower and the heat exchanger, because dust often originates in the room. With a filter installed in the supply air duct, dust from the room could pass across the blower and heat exchanger before ever reaching the filter.
[0008] Moreover, if elongated filters of current designs were installed within a generally cylindrical duct having a pliable fabric wall, the non-conical shape of the filter may cause the fabric of the duct to flutter, due to uneven patterns of airflow velocity. If the cross-sectional area of airflow between the exterior of an elongated filter and the interior of the cylindrical fabric duct is not circumferentially uniform, as could be the case with a flat-sided filter within a cylindrical duct, localized areas of higher velocity may exist. Also, abrupt changes in velocity along the length of a fabric duct may also cause the fabric to flutter.
SUMMARY OF THE INVENTION
[0009] In some embodiments, an air duct system includes a conical filter disposed within a cylindrical duct.
[0010] In some embodiments, an air duct system includes an inflatable conical filter with pleats.
[0011] In some embodiments, the pleats are interconnected in an alternating pattern of connection points to inhibit the filter from billowing excessively outward.
[0012] In some embodiments, an air duct system includes a blower and a heat exchanger interposed between an upstream pre-filter and a downstream conical filter, which is less porous.
[0013] In some embodiments, an inflatable fabric filter is disposed within an inflatable fabric air duct.
[0014] In some embodiments, the fabric wall of the air duct is air permeable.
[0015] In some embodiments, the integrity of a fabric air duct can be maintained regardless of whether the elongated filter is attached to the duct.
[0016] In some embodiments, a zipper removably attaches an elongated filter to a fabric air duct.
[0017] In some embodiments, a plurality of conical filters have the same length to diameter ratio even though the filters are of different diameters for various diameter air ducts.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a cutaway view of an air duct system with a fabric air duct and a conical fabric filter.
[0019] [0019]FIG. 2 is a cutaway view of an air duct system with a relatively rigid air duct and a conical fabric filter.
[0020] [0020]FIG. 3 is similar to FIG. 1, but with the fabric duct and filter deflated.
[0021] [0021]FIG. 4 is a perspective view of the filter used in the air duct system of FIG. 1.
[0022] [0022]FIG. 5 is a closer up view of the supply air duct and conical filter of FIG. 1.
[0023] [0023]FIG. 6 is similar to FIG. 5, but with the filter removed and two sections of the supply air duct zipped together.
[0024] [0024]FIG. 7 is similar to FIG. 4, but showing a fabric conical filter that is pleated.
[0025] [0025]FIG. 8 is a cross-sectional view taken along line 8 - 8 of FIG. 7.
[0026] [0026]FIG. 9 shows one of a plurality of conical air filters.
[0027] [0027]FIG. 10 is similar to FIG. 9, but showing a larger filter with the same length to diameter ratio.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] An air handling system 10 of FIGS. 1 is used to heat or cool an area 12 of a building 14 . To do this, system 10 includes a blower 16 ; a heat exchanger 18 ; a pre-filter 20 ; a finer, less porous inflatable filter 22 ; a supply air duct 24 ; and a return air duct 26 . Heat exchanger 18 is schematically illustrated to represent any device for heating or cooling air, such as by electrical resistance or by heat transfer with another fluid, such as refrigerant, water, or glycol. A housing 28 can enclose one or more of the components of system 10 .
[0029] In operation, blower 16 draws air 30 from area 12 , through return air duct 26 and across pre-filter 20 , with pre-filter 20 being any conventional filter known to those skilled in the art. Pre-filter 20 can be used to capture the larger dust particles in the air that might otherwise accumulate on heat exchanger 18 and blower 16 . Pre-filter 20 also helps prevent large dust particles from quickly plugging up the less porous filter 22 in supply air duct 24 .
[0030] After the air passes through pre-filter 20 , blower 16 draws the air across heat exchanger 18 . Blower 16 then discharges the air through inflatable filter 22 , through supply air duct 24 , and into area 12 through the pores or other openings in supply duct 24 . Filter 22 , being relatively fine, can be used to remove smaller dust particles that were able to pass through pre-filter 20 . In some embodiments, the fabric material of filter 22 is provided by 3M of St. Paul, Minn., and has a standard particle removal efficiency of 80 to 90%, at 150 to 300 cfm/ft 2 , with a static pressure drop of 0.2 inches of water.
[0031] Conical fabric filters, such as filter 22 , can be installed within various types of ducts. The supply air duct can be made of sheet metal or some other relatively rigid material, as is the case of conical filter 22 ′ in supply air duct 32 of FIG. 2, or can be made of a pliable fabric 34 , as is the case of duct 24 . With a metal air duct, air registers 36 provide one or more openings for air to discharge into area 12 . As an alternative or in addition to registers 36 , the fabric of air duct 24 may be air-permeable and/or be provided with cutouts or discharge openings 38 that deliver air to area 12 . Examples of fabric air duct 24 are disclosed in U.S. Pat. Nos. 5,655,963 and 5,769,708, which are specifically incorporated by reference herein.
[0032] In the example of FIG. 1, the fabric wall of duct 24 has a generally cylindrical or tubular shape when inflated by the discharge pressure of blower 16 . However, when the heating or cooling demand of area 12 has been satisfied, blower 16 may turn off, which deflates filter 22 and leaves the fabric walls of duct 24 hanging relatively limp, as shown in FIG. 3. Some fabric air ducts have a rigid frame that helps hold the fabric walls of the duct in a generally tubular shape even when the blower is not running. Such frame-supported ducts are also well within the scope of the invention.
[0033] Filter 22 can be installed within an air duct (metal or fabric, supply or return) in various ways. In a currently preferred embodiment, a collar 40 , made of fabric or some other material, couples filter 22 to a first segment 24 a and a second segment 24 b of fabric air duct 24 . Referring further to FIG. 4, fabric rim 42 at a base 44 of filter 22 is sewn or otherwise attached to the interior of collar 40 . Collar 40 includes two half-zippers 46 and 48 that removably interlock with mating half-zippers 50 and 52 on supply air duct 24 , as shown in FIG. 5. Half-zippers 46 and 50 comprise a first zipper 54 , and half-zippers 48 and 52 comprise a second zipper 56 . Zippers 54 and 56 allow filter 22 to be temporarily removed from duct 24 for filter cleaning or replacement. If filter 22 is removed for an extended period, half-zippers 50 and 52 may be zipped together to re-establish a continuous supply air duct, as shown in FIG. 6.
[0034] To minimize the pressure drop created by filter 22 and to extend the period between filter cleanings, filter 22 is elongated to provide a large surface area though which the air may pass. This is accomplished by having filter 22 , when inflated, be of a generally conical shape (i.e., most of its contour or outer envelope fits the shape of a cone). In some embodiments, filter 22 is in the shape of a cone (i.e., substantially all of its contour or outer envelope fits that of a cone).
[0035] To help prevent the fabric walls of duct 24 b from fluttering, the velocity and flow direction of the air between the exterior of filter 22 and the interior of duct 24 b is kept as smooth as reasonably possible. This can be achieved by installing a conical filter within a cylindrical duct to create an airflow path whose annular cross-sectional area increases gradually from an upstream to a downstream end of filter 22 .
[0036] To provide a conical filter with more surface area, a filter 58 can have a pleated fabric wall, as shown in FIGS. 7 and 8. The pleats run generally lengthwise with each pleat being connected to its two adjacent pleats in an alternating pattern of discrete points. For example, a central pleat 60 lies between a first pleat 62 and a second pleat 64 . Central pleat 60 has a central peak 60 ′ that zigzags between an adjacent first peak 62 ′ and a second peak 64 ′ of pleats 62 and 64 , respectively. Central peak 60 ′ is attached to first peak 62 ′ at points 66 , 68 and 70 . Central peak 60 ′ is also attached to second peak 64 ′ at points 72 , 74 and 76 . The alternating pattern of connection points inhibits the blower's discharge air pressure from flattening the pleats and restrains filter 58 to a generally conical shape.
[0037] To provide a plurality of conical filters that provide the same flow rate for a given area of filter material regardless of the duct's diameter, each filter's length to diameter ratio is the same. For example, in FIG. 9, a filter 78 in a first duct 80 has a diameter 82 of 24 inches, as measure along a base 84 of conical filter 78 , and has a length 94 of 120 inches, as measured from a center 86 of base 84 to an apex 88 of filter 78 . Similarly, in FIG. 10, a filter 90 in a larger duct 92 has a diameter 96 of 48 inches and a length 98 of 240 inches, whereby both filters 78 and 90 have a length to diameter ratio of five (120/24=5, and 240/48=5).
[0038] Although the invention is described with reference to a preferred embodiment, it should be appreciated by those skilled in the art that various modifications are well within the scope of the invention. Therefore, the scope of the invention is to be determined by reference to the claims that follow.
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An air duct system includes a conical fabric filter disposed within a cylindrical air duct. In some embodiments, both the filter and the air duct are inflatable. A fabric collar and a pair of zippers not only allow the filter to be readily removed for cleaning, but also allow the air duct system to continue operating with the filter removed. Pleats can provide the filter with more surface area, and the pleats can be interconnected in an alternating pattern to inhibit the filter from over inflating.
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TECHNICAL FIELD
The present invention relates to fuel cells.
BACKGROUND OF THE INVENTION
Automobiles emit hydrocarbons, nitrogen oxides, carbon monoxide and carbon dioxide as a result of the combustion process. Automobile emissions are said to be a significant contributor to pollution. In order to reduce and/or eliminate such emissions automobile manufacturers have attempted to utilize alternative transportation fuels and/or alternative sources of power, such as, for example, fuel cells. Generally, fuel cells generate electricity by electrochemically combining across an ion-conducting electrolyte a fuel, such as hydrogen, carbon monoxide, or a hydrocarbon, and an oxidant, such as air or oxygen.
A fuel cell system typically includes a “stack” of individual fuel cells that are electrically interconnected in a series configuration. Thus, the number of cells in the stack, i.e., the number of cells connected together in series, determines the voltage that is produced by the stack. Each of the individual fuel cells within the stack produces a voltage that varies dependent at least in part upon the current being drawn from that cell and/or the stack. The voltage produced by a typical single cell varies from an open circuit voltage, such as, for example, approximately 1.0 Volts (V) at low or zero current loads to a lower limit, such as, for example, approximately 0.7 V, under high current loads. If the voltage produced by a cell drops below a minimum threshold, such as, for example, 0.6 V, an undervoltage condition exists that may result in damage to the cell, such as, for example, cell oxidation.
Since the voltage produced by each cell varies dependent at least in part upon the current load upon the cell, the voltage produced by the stack also varies dependent at least in part upon the current load. More particularly, due to the series interconnection of the cells in the stack, the variation in the voltage produced by the cells is cumulative, i.e., the stack voltage will vary in a manner that reflects the sum of the voltage variations of the individual cells within the stack. This cumulative effect on the stack voltage can be relatively substantial. For example, the voltage produced by a fuel cell having sixty cells may vary from approximately sixty volts to approximately forty-two volts.
Most electrical systems are designed to operate with a supply voltage that falls within a predetermined range. As described above, the voltage produced by a fuel cell stack may vary substantially. Thus, if a fuel cell system is to be used as a power source for such an electrical system the stack voltage must typically be regulated by a voltage regulating device or devices to ensure the stack voltage supplied to the electrical system remains within the voltage range required by the electrical system, independent of the voltage produced by the stack. As the amount of variation in the voltage produced by the stack increases a correspondingly greater amount of regulation is required in order to provide a supply voltage to the electrical system that is within the specified range. In order to provide adequate regulation of such a widely-varying voltage, voltage regulation or control devices that are relatively complex, costly, sizeable, and power consuming are required.
Therefore, what is needed in the art is a fuel cell system that substantially reduces damage and/or oxidation to the cells, such as, for example, due to an under voltage condition.
Furthermore, what is needed in the art is a method and apparatus that controls the output voltage of a fuel cell system while also controlling the operation of the fuel cell such that the fuel cell operates with improved efficiency relative to unregulated operation.
Moreover, what is needed in the art is a fuel cell system that generates a controlled and/or regulated output voltage.
SUMMARY OF THE INVENTION
The present invention provides a method and apparatus for controlling the operation of a fuel cell system.
The present invention comprises, in one form thereof, the step of selectively connecting and disconnecting the fuel cell to at least one electrical load dependent at least in part upon at least one of a fuel cell voltage, a fuel cell current and a fuel cell temperature. The invention further comprises, in one form thereof, a fuel cell unit having a fuel cell stack producing a fuel cell voltage and a fuel cell current. A power conditioner electrically connected to the fuel cell unit includes a power switching device. The power switching device selectively connects and disconnects the fuel cell voltage to at least one load dependent at least in part upon an operating temperature of the fuel cell stack, the fuel cell voltage, and the fuel cell current to thereby produce an output voltage.
An advantage of the present invention is that the potential of damage and/or oxidation of the cells, such as, for example, due to an under voltage condition, is substantially reduced.
Another advantage of the present invention is the output voltage of the fuel cell system is controlled while the operation of the fuel cell is also controlled such that the fuel cell operates with improved efficiency relative to unregulated operation.
A further advantage of the present invention is the output voltage generated is substantially controlled and/or regulated.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become apparent and be more completely understood by reference to the following description of one embodiment of the invention when read in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic block diagram of one embodiment of a fuel cell system of the present invention; and
FIG. 2 is a schematic diagram of the power converter of FIG. 1 .
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplification set out herein illustrates one preferred embodiment of the invention, in one form, and such exemplification is not to be construed as limiting the scope of the invention in any manner.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, and particularly to FIG. 1 , there is shown one embodiment of a fuel cell system of the present invention. Fuel cell system 10 includes fuel cell unit 12 , power conditioner 14 and fuel cell controller 16 .
Fuel cell unit 12 includes a conventional fuel cell stack 18 constructed of a plurality of individual fuel cells (not shown), such as, for example, solid oxide fuel cells (SOFC), that are electrically interconnected in series. Fuel cell unit 12 also includes associated components, such as, for example, at least one reformer, waste energy recovery system and conduits interconnecting the components to each other and with supplies of fuel and/or air, etc (none of which are shown). Fuel cell unit 12 generates a substantially unregulated output voltage V STACK and output current I STACK .
Power conditioner 14 , in general, controls and/or conditions the voltage produced by fuel cell unit 12 to remain within a desired or predetermined voltage, and ensures fuel cell unit 12 is operated in a relatively efficient manner in each of the several operating modes thereof. Power conditioner 14 includes power converter circuitry 22 , gate drive circuitry 24 , control logic 26 , and mode controller 28 .
Converter circuitry 22 is electrically interconnected with fuel cell unit 12 , and receives therefrom V STACK and I STACK . Converter circuitry 22 is also electrically interconnected with external load 32 , such as, for example, one or more forty-two Volt loads. Converter circuitry 22 is further electrically connected, via DC/DC converter 34 , to external load 36 , such as, for example, one or more twelve Volt loads. Generally, converter circuitry 22 supplies voltage V OUT to external load 32 and DC/DC converter 34 . A schematic of an exemplary converter circuit 22 is shown in FIG. 2 .
Converter circuitry 22 includes at least one power switching device 42 ( FIG. 2 ), such as, for example, one or more power metal oxide semiconductor field effect transistors (MOSFETs), integrated gate bipolar transistors (IGBTs) or other suitable power switching devices. Power switching device 42 is electrically connected between fuel cell unit 12 and each of load 32 and DC/DC converter 34 . Generally, power switching device 42 controls the current flowing from fuel cell unit 12 to load 32 and to DC/DC converter 34 . Power switching device 42 is operated in one of three modes dependent at least in part upon the signal applied to control terminal 42 a , such as, for example, the gate, thereof. In a current blocking mode, such as, for example, an open-circuit mode, power switching device 42 disallows substantially all current flow from fuel cell unit 12 , thereby enabling fuel cell unit 12 to operate in a substantially unloaded condition. In another or a first mode of operation, such as, for example, a pulse-width modulated mode, power switching device 42 is operated in such a manner that the value of V OUT is maintained within a predetermined voltage range. In yet another or second mode of operation, such as, for example, a linear mode, power switching device 42 is operated as a series pass through device to thereby maintain the value of V OUT within a predetermined voltage range.
Converter circuitry 22 may be configured as a single power switching device 42 interconnected between fuel cell unit 12 and issuing V OUT to external loads. Preferably, however, converter circuitry 22 is configured as a conventional linear regulator integrated circuit, such as, for example, model number 1802 manufactured by Unitrode Corporation of Merrimack, N.H., model number MC78BC30 manufactured by ON Semiconductor Corporation of Phoenix, Ariz., or model number LM1723 manufactured from ON Semiconductor Corporation, that integrates onto a single chip/integrated circuit the unreferenced components, such as the diodes, capacitors, inductors, etc., shown in FIG. 2 .
Gate drive circuitry 24 , in general, interfaces control logic 26 with power converter circuitry 22 thereby enabling signals from control logic 26 to drive power converter circuitry 22 . More particularly, drive circuitry 24 is electrically connected to and receives control signal 50 from control logic circuitry 26 , and is electrically connected and issues drive signal 52 to power converter circuitry 22 . Drive signal 52 is dependent at least in part upon control signal 50 . Drive signal 52 is electrically connected to and received by control terminal 42 a of power switching device 42 . Thus, the mode in which power switching device 42 is operating is dependent at least in part upon drive signal 52 . Gate drive circuitry 24 is configured as a conventional gate drive circuit, such as, for example, model numbers IR2110 or IR2125 manufactured by International Rectifier Corporation of El Segundo, Calif.
Control logic 26 is electrically connected to gate drive circuit 24 and to mode controller 28 . Control logic 26 issues control signal 50 to drive circuitry 24 , and receives converter mode signal 54 from mode controller 28 . Control logic 26 also receives current signal 62 and voltage error signal 64 . Current signal 62 is indicative of the current being supplied by fuel cell unit 12 , i.e., I STACK , and voltage error signal 64 is indicative of the difference between V OUT and a reference voltage V REF , as determined by, for example, a comparator (not referenced). Dependent at least in part upon converter mode signal 54 , current signal 62 and voltage error signal 64 , control logic circuitry 26 issues control signal 50 to drive circuitry 24 . Control logic circuitry 26 is configured as a conventional pulse-width modulation switching and control logic circuit, such as, for example, model numbers 1802 or 1526A manufactured by Unitrode Corporation of Merrimack, N.H.
Mode controller 28 , as is described more particularly hereinafter, determines the mode in which power conditioner 14 and fuel cell unit 12 operate in order to maintain efficient operation and/or increase the efficiency thereof. Mode controller 28 receives and monitors the output voltage V OUT of power conditioner 14 . Mode controller 28 also receives V STACK and current signal 62 , which is indicative of I STACK . Mode controller 28 issues converter mode signal 54 which is indicative of the operational mode that is most efficient given the operating conditions and parameters of fuel cell unit 12 and power conditioner 14 . Mode controller 28 issues to fuel cell controller 16 a cell operational control signal 70 , which is indicative of any adjustments necessary to the output, such as, for example, I STACK and V STACK , of fuel cell unit 12 in light of instantaneous operating conditions and parameters. Mode controller 28 is configured as one or more logic gates, such as, for example, AND, OR and/or NAND gates. Preferably, mode controller 28 is configured as a microprocessor executing mode control software 72 .
Fuel cell controller 16 , such as, for example, a microprocessor-based control unit, controls the operation of fuel cell unit 12 dependent at least in part upon stack signals 74 , such as, for example, sensor signals, indicative of the operating conditions and parameters, such as, for example, the amount of reformate flow, operating temperature, etc, of fuel cell unit 12 . Fuel cell controller 16 also receives cell operational control signal 70 from, mode controller 28 , receives V OUT and I STACK signal 62 . Fuel cell controller 16 controls the operation of fuel cell unit 12 by issuing stack control signals 76 that are dependent at least in part upon stack signals 74 , cell operational control signal 70 , V OUT and I STACK signal 62 to adjust the operational parameters, such as, for example, reformate and air flow, to thereby adjust and/or control the operation of fuel cell unit 12 .
In use, fuel cell system 10 supplies output voltage V OUT to loads 32 and 36 . More particularly, power conditioner 14 in conjunction with fuel cell controller 16 control the operation of fuel cell unit 12 and maintain V OUT within a predetermined and desired voltage range, thereby rendering fuel cell system 10 suitable for use as a power source for a variety of electrical systems, such as, for example, an electrical system of a motor vehicle.
Fuel cell unit 12 has three general modes of operation, i.e., start-up, operating, and cool down modes. During the start-up mode of operation, the fuel cell unit 12 has not reached its intended operational temperature. Accordingly, current I STACK is substantially lower than a predetermined or nominal value. The difference between the start-up value of I STACK and the nominal value of I STACK is detected by mode controller 28 , which, in turn, issues mode signal 54 to control logic 26 . Control logic 26 decodes mode signal 54 and, dependent at least in part thereon, issues control signal 50 to gate drive circuitry 24 . Gate drive circuitry 24 , dependent at least in part upon control signal 50 , issues drive signal 52 . Drive signal 52 is received by power converter circuitry 22 and, more particularly, the control terminal of power switching device 42 .
Drive signal 52 , when fuel cell unit 12 is operating in the start-up mode, places power switching device 42 into a corresponding start-up mode, such as, for example, substantially an open circuit, wherein current flow from fuel cell unit 12 to loads 32 and 36 is substantially disallowed or precluded. By disallowing current flow from fuel cell unit 12 , power conditioner 14 enables fuel cell 12 to operate at the open circuit voltage, thereby reducing the duration of time fuel cell unit 12 operates in the start-up mode. Thus, power conditioner 14 expedites fuel cell unit 12 reaching its operating temperature and entering the operating mode.
When fuel cell unit 12 reaches a predetermined minimum start-up or warm-up temperature, the value of I STACK has increased and reached a predetermined start-up value. This increase in I STACK is detected and recognized by mode controller 28 of power conditioner 14 which, in response to I STACK exceeding the predetermined threshold, issues an updated mode control signal 54 . Control logic circuitry 26 decodes the revised mode control signal 54 and, in turn, issues control signal 50 to gate drive circuitry 24 . In response to the revised control signal 50 , gate drive circuitry 24 issues drive signal 52 that places power switching device 42 in a condition that allows a predetermined and relatively small amount of current I STACK to flow from fuel cell unit 12 through to loads 32 and 36 . (i.e., a current-limiting mode). This relatively small flow of I STACK enhances the pre-heating of fuel cell unit 12 and fuel cell stack 18 due to the chemical conversion therein of reformate and air to electricity, and thereby reduces the amount of time required for fuel cell unit 12 to reach its operating or use temperature.
Once fuel cell unit 12 reaches its operating or use temperature, fuel cell unit 12 exits the start-up mode and enters the operating mode. The readiness of fuel cell unit 12 to enter the operating mode is detected by mode controller 28 , through the monitoring of I STACK and V STACK , which alters mode signal 54 accordingly. Control logic circuitry 26 decodes mode signal 54 and issues a corresponding control signal 50 to gate drive circuitry 24 . Gate drive circuitry 24 issues a corresponding drive signal 52 to power converter 22 thereby causing power switching device 42 to operate in an appropriate one of the first or second modes of operation (i.e., the pulse-width modulated mode or the linear mode), typically the first or PWM mode of operation, as described above.
During shut down of fuel cell system 10 , the values of V STACK and I STACK being drawn from fuel cell unit 12 are substantially reduced relative to the warm-up and operating modes. Mode controller 28 detects this shut down condition and issues a corresponding mode signal 54 to control logic 26 . Control logic 26 decodes mode signal 54 and, dependent at least in part thereon, issues control signal 50 to gate drive circuitry 24 . Gate drive circuitry 24 , in turn, issues drive signal 52 . Drive signal 52 is received by power converter circuitry 22 thereby causing power switching device to enter the current blocking or open-circuit operating mode. With power switching device 42 in the current blocking mode, substantially no current flows from fuel cell unit 12 to loads 32 or 36 thereby ceasing the heat-emitting reaction within fuel cell stack 18 and expediting the cooling and/or shut down process thereof.
With fuel cell unit 12 in the operating or use mode, i.e., fuel cell unit 12 has reached its operating or use temperature, mode controller 28 monitors the difference between V STACK and V OUT in order to determine the most efficient operating mode of power converter 14 and fuel cell unit 12 . As described above, with fuel cell unit 12 in the operating mode power conditioner 14 operates in a first or pulse-width modulated mode when the difference between stack voltage V STACK and V OUT is relatively large, such as, for example, greater than approximately 3.0 V. Power switching device 42 is placed into the first mode of operation through the application of a corresponding drive signal 52 , such as, for example, a pulse-width modulated (PWM) signal. V STACK is controlled by controlling and/or adjusting the duty cycle of the pulse-width modulated drive signal 52 . Conversely, power conditioner 14 operates in a second or linear mode when the difference between stack voltage V STACK and V OUT is relatively small, such as, for example, less than approximately 3.0 V, and when V STACK is less than the desired nominal output voltage, such as, for example, approximately 42 V. Power switching device 42 is placed into the second mode through a corresponding drive signal 52 , such as, for example, a voltage level sufficient to bias power switching device 42 into the linear region of operation. In the linear region, power switching device 42 dissipates a relatively low amount of power and therefore operates in a relatively efficient manner.
It should be particularly noted that mode controller 28 monitors V STACK , I STACK and V OUT to detect start-up, over load and short circuit conditions. When fuel cell unit 12 is operating under any one of those conditions, mode controller 28 controls I STACK via power switching device 42 . By controlling the amount of current I STACK being drawn from fuel cell unit 12 , mode controller 28 indirectly controls the reformate flow through fuel cell unit 12 , and thereby substantially protects fuel cell unit 12 from damage.
While this invention has been described as having a preferred design, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the present invention using the general principles disclosed herein. Further, this application is intended to cover such departures from the present disclosure as come within the known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
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A method of operating a fuel cell includes the step of selectively connecting and disconnecting the fuel cell to at least one electrical load dependent at least in part upon at least one of a fuel cell voltage, a fuel cell current and a fuel cell temperature.
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[0001] This application claims the benefit of provisional application Ser. No. 60/462,316 filed Apr. 14, 2003 and provisional application Ser. No. 60/465,266 filed Apr. 25, 2003.
BACKGROUND OF THE INVENTION
[0002] Acute Respiratory Distress Syndrome (ARDS) is characterized by a rapid influx of body fluids from the capillaries to the lung alveolar spaces. ARDS can be caused by acute smoke inhalation, respiratory viral illness, acute trauma, and aspiration of stomach of stomach contents.
[0003] Severe Acute Respiratory Syndrome (SARS) is characterized by fever, chills, myalgia, and cough. Respiratory symptoms and auscultatory findings are fairly mild, compared to radiographic changes observed of the chest. A virus belonging to the family Coronaviridae was isolated from two SARS patients. By use of serological and reverse-transcriptase PCR specific for this virus, patients with SARS, but no controls, had evidence of infection with this virus. Other corona viruses are involved in causing the common cold. High concentrations of corona viral RNA (≦100 million molecules per milliliter (10 8 /ml) have been found in sputum of infected patients. Viral RNA was also detected at extremely low concentrations in plasma during the acute phase and in feces during the late convalescent phase.
SUMMARY OF THE INVENTION
[0004] According to one embodiment of the invention a method is provided for treating a SARS or ARDS patient. An effective amount of an agent selected from the group consisting of: substance P, [Met-OH 11 ]-substance P, [Met-OMe 11 ]-substance P, [Nle 11 ]-substance P, [Pro 9 ]-substance P, [Sar 9 ]-substance P, [Tyr 8 ]-substance P, Sar 9 , Met (0 2 ) 11-Substance P, and [p-Cl-Phe 7,8 ]-substance P is administered to the patient. A disease feature selected from the group consisting of: Clara cell necrosis, pulmonary alveolar macrophage number, alveolar-capillary barrier membrane damage, and 6-keto-PGF 1α and PGE 2 concentration is thereby decreased.
[0005] According to another aspect of the invention a method is provided for protecting an individual from developing SARS or ARDS. The individual has been or is expected to be exposed to a patient with SARS or ARDS. An effective amount of an agent selected from the group consisting of: substance P, [Met-OH 11 ]-substance P, [Met-OMe 11 ]-substance P, [Nle 11 ]-substance P, [Pro 9 ]-substance P, [Sar 9 ]-substance P, [Tyr 8 ]-substance P, Sar 9 ,Met (0 2 ) 11-Substance P, and [p-Cl-Phe 7,8 ]-substance P is administered to the individual. The risk of developing SARS or ARDS is thereby reduced.
DETAILED DESCRIPTION OF THE INVENTION
[0006] It is a discovery of the present inventor that Substance P and its bioactive analogs, such as Sar 9 , Met (0 2 ) 11-Substance P, is a beneficial treatment for ARDS, corona virus respiratory infections, and corona-like respiratory virus infections. Substance P and its analogs also potentiate the lung immune system's response against corona and corona-like respiratory viruses. Substance P and its analogs can be used to prophylactically treat health care workers and family members who must care for SARS patients and suspected SARS patients.
[0007] Substance P (RPKPQQFFGLM-NH 2 ; SEQ ID NO: 1) or a bioactive analog thereof such as Sar 9 , Met (0 2 ) 11-Substance P can be administered to treat ARDS, SARS, corona and corona-like respiratory virus infections. The bioactive analog can be selected from the group consisting of [Met-OH 11 ]-substance P, [Met-OMe 11 ]-substance P, [Nle 11 ]-substance P, [Pro 9 ]-substance P, [Sar 9 ]-substance P, [Tyr 8 ]-substance P, Sar 9 , Met (0 2 ) 11-Substance P, and [p-Cl-Phe 7,8 ]-substance P. Other compounds which function in the same way can be identified by their ability to compete with substance P for binding to its receptor (NK-1) or for their ability to agonize the NK-1 receptor. Routine assays for such activities are known in the art and can be used.
[0008] The substance P or analog can be administered by any method known in the art, including via aerosol inhalation. Intravenous, intratracheal, intrabronchial, intramuscular, sublingual, and oral administrations can also be used. Preferred dosages include 0.05 to 5 nanomolar substance P or analog for intravenous administration, preferably 0.1 to 2 nanomolar, and more preferably 0.5 to 1.5 nanomolar. For aerosol administration dosages include 0.05 to micromolar substance P or analog, preferably 0.1 to 2 micromolar, and more preferably 0.5 to 1.5 micromolar. Typical concentration ranges of substance P or its bioactive analog in the aerosol administered is between 0.001 and 10 μM. It can be advantageously administered as a liquid at a concentration between about 0.1 and 10 μM.
[0009] Bioactive analogs, according to the invention are those which act as competitive inhibitors of SP by binding to the SP receptor (NK-1 receptor). The analogs may be agonists of the NK-1 receptor. Other derivatives as are known in the art and commercially available (e.g., from Sigma) can be used. In addition, substance P fragments and derivatized substance P fragments may also be used. Substitution, deletion, or insertion of one to eight amino acid residues, and preferably from one to three amino acid residues, will lead to analogs which can be routinely tested for biological activity. In addition, functional groups may be modified on SP while retaining the same amino acid backbone. Again, routine testing will determine which of such modifications do not adversely affect biological activity.
[0010] Suitable devices for administering the aerosol of the present invention include nebulizers as well as hand-held aerosol “puffer” devices. Suitable treatment regimens for treatment according to the present invention include daily or multiple daily treatment by aerosol. Other modes of treatment include continual transdermal infusion, intravenous injection, intramuscular, sublingual, subcutaneous injection, and oral administration. Suitable formulations of substance P for administration are any which are pharmaceutically acceptable and in which substance P retains its biological activity. Generally, such formulations are substance P dissolved in normal sterile saline. Other formulations for changing absorption and half-life characteristics can be used, including liposomal formulations and slow-release formulations.
[0011] Disease features of ARDS and SARS include Clara cell necrosis, increased pulmonary alveolar macrophage number, neutrophil number, alveolar-capillary barrier membrane damage, and increased 6-keto-PGF 1α and PGE 2 concentrations. These disease features are reduced by the therapeutic administrations of the present invention. Decreases in the disease features of at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, or 50% are desirable. Even greater decreases are preferred.
EXAMPLE 1
[0012] We have developed a model of ARDS and SARS in rats and rabbits. We demonstrated that 30 tidal volume breaths of diesel fuel smoke caused a persistent increase in lung substance P levels of up to 60% for 24 hours post-smoke. The lung injury was also characterized by clara cell necrosis, increase in pulmonary alveolar macrophages, and increases in the prostaglandins; 6-keto-PGF 1α and PGE 2 . Treatment with intravenous (0.8 nM) Sar 9 , Met (0 2 ) 11-Substance P attenuated the clara cell necrosis, reduced pulmonary alveolar macrophage number, and decreased 6-keto-PGF 1α and PGE 2 . Such treatment attenuates damage to the alveolar-capillary barrier membrane. Thus Sar 9 , Met (0 2 ) 11-Substance P is a beneficial treatment for ARDS, corona, and corona-like respiratory viruses.
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Substance P or its analogs are useful for treating and protecting against acute respiratory syndromes including ARDS and SARS. The active agents can be administered via inhalation therapy, intravenously, intramuscularly, sublingually, or by other methods. Disease indicia are reduced by substance P treatment.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a control and method for extracting water from a clothes load within an automatic washer.
2. Description of the Prior Art
At the end of a wash cycle in an automatic washer there is a water extraction step in which normally the wash basket is rotated about its axis to cause water carried within the clothes load to be extracted by centrifugal force.
The speed at which the clothes basket is spun is a balancing of several factors. First, as high a speed as is feasible is desired in order to provide maximum extraction of the water from the clothes so that less energy is required in a subsequent drying step in the wash process. A number of factors enter into placing a ceiling or upper limit on the spin speed including the important consideration of attempting to avoid excessive wrinkling of the clothes, particularly permanent press type clothing. Wrinkling of the clothes is increased when the clothes are spun at a very high rotational rate. Automatic washing machines manufactured by Whirlpool Corporation, the assignee of the present application, have a top spin speed in the range of 600-700 rpm, in that it has been determined that higher spin speed causes excessive wrinkling.
A common prior art method of spinning the basket incorporates an AC motor which, through an appropriate transmission and gearing quickly accelerates the basket up to a constant speed level which is maintained throughout the entirety of the extraction step for a predetermined length of time.
Other types of extraction controls and methods are known in the art. U.S. Pat. No. 2,975,902 discloses a horizontal axis washer in which the spin speed is increased in small predetermined increments from a normal tumbling speed up to the speed at which the clothes become plastered against the drum wall in order to effect a desired distribution of the clothes around the drum wall. Once the clothes have become plastered against the wall, the spin speed is then increased rapidly to a maximum spin speed.
U.S. Pat. No. 3,403,538 discloses the use of a controlled spin operation in which the spin speed is prevented from rising above 300 rpm during a first phase of spin, but is permitted to increase to a speed between 300 rpm and 1000 rpm during a second phase of spin if an unbalanced load was not detected as the spin tub passed through its critical speed. If an unbalanced condition is detected as the spin tub passes through critical speed, the spin speed is maintained below 300 rpm.
U.S. Pat. No. 3,425,559 discloses an automatic washer having a single speed motor and a two-speed transmission, along with control means for maintaining the transmission and low speed setting during the initial portion of the spin to reduce the load of the motor. Once the motor speed reaches a certain percentage of its maximum speed, the transmission is shifted into its high speed mode, thereby increasing the spin speed to its maximum. This is done to prevent stalling of the motor at the start of a spin cycle of operation.
U.S. Pat. No. 3,526,105 discloses the desirability of keeping the spin speed low to maintain good performance when laundering permanent press fabrics. The disclosed control operates a pump at high speed during an extraction portion of the wash cycle and operates the motor, which effects rotation of the fabric basket, at a high speed until a portion of the liquid has been removed, which is sensed by a level sensing switch, at which time the motor will be energized at a slower speed through the remainder of the extraction portion of the cycle. It is stated that the full tube of water prevents high rotation speed of the inner basket when the motor is energized at a high speed.
U.S. Pat. No. 4,513,464 discloses the idea of providing controlled acceleration to the drum of a centrifugal extractor to minimize unbalance problems. In particular, the speed of the drum is held constant until the amount of load unbalance drops below a certain level, after which the speed is increased and the unbalance is again measured. This patent also discloses the idea of measuring the difference between successive unbalance measurements, for the purpose of controlling the speed of the drum.
SUMMARY OF THE INVENTION
The present invention provides a method and control for extracting water in an automatic washer in which the speed of rotation is started out at a low level and is incrementally increased, to reduce the amount of wrinkling in the clothes load while eventually obtaining as high or higher level of moisture extraction as has been common in the past. In a preferred embodiment, the basket is spun at a low speed level until all of the moisture extractable at the low speed level has been extracted and then the basket is spun at a somewhat higher speed level, again until all of the moisture that can be extracted at the higher speed level has been extracted. This process of incrementally increasing the spin speed is continued until a desired level of moisture extraction has occurred.
The extent of liquid extraction at each speed level is measured by sensing and comparing successive basket acceleration times. That is, at each speed level, the basket is caused to accelerate and decelerate repeatedly, between a low limit speed and a high limit speed, and the duration of each successive acceleration step is measured, while a constant motor torque is applied to the basket. The amount of water extracted since the previous acceleration is indicated by a difference in the time required to achieve the high limit speed, the difference in times between successive steps being caused by a difference in the inertia of the clothes load, and the change of inertia being directly related to the amount of water extracted. Thus, when acceleration times are equal between successive acceleration steps, no additional water will have been extracted. When equal acceleration times are sensed, the control then causes the motor to operate at the next higher rotational speed level or range, between a preset lower limit and a preset upper limit speed. Again, the motor is periodically accelerated from the low limit to high limit speeds and is caused to decelerate again to the low limit speed so that successive acceleration times may be measured.
By use of the present invention, the force applied to the clothes within the basket during spin is considerably reduced, particularly during the early stages of the spin cycle thus providing enhanced performance and reduced wrinkling.
By use of the present invention, the spin cycle can be terminated when the desired level of water extraction has been sensed, which time is related specifically to the particular clothes load being laundered rather than a preset and predetermined time period. Thus, by use of the present invention, a water extraction level equal to the presently achievable extraction level can be obtained while applying a substantially lower force on the clothes load thus resulting in considerably less wrinkling of the clothes. Further, a higher level of extraction can be achieved than is available in the present commercial production models while again applying a lesser force on the clothes load and thus a reduction in the wrinkling.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an automatic washer in which the principles of the present invention can be employed.
FIG. 2 is a schematic illustration of the inertia loads in the drive system of the washer of FIG. 1.
FIG. 3 is a graphic illustration of rotational speed of the basket during an extraction process embodying the principles of the present invention.
FIG. 4 is a schematic illustration of an automatic washer control for operating a motor in accordance with the principles of the present invention.
FIG. 5 is a flow chart illustration of the steps undertaken in a method embodying the principles of the present invention.
FIG. 6 is a graphic illustration comparing basket rotational speed, force applied to the clothes load and water extraction between the present available commercial washing machines and a washing machine embodying the principles of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1 there is illustrated a vertical axis washer generally at 10 having an outer cabinet 12 enclosing a washer mechanism supported on legs 14. The washer mechanism includes an imperforate wash tub 16 with a concentrically carried perforate wash basket 18 and a central vertical axis agitator 20. The agitator 20 and basket 18 are driven by means of an electric motor 22 through an appropriate transmission 24.
The interior of the wash basket 18 is accessed through an openable lid 26 and a plurality of manually operated controls 28 are provided on a console 30 at a top rear of the washer 10. During a water extraction portion of the wash cycle the perforate basket 18 is rotated about its vertical axis to cause water contained within the clothes load to be forced outwardly through the perforate wall of the basket by centrifugal force.
FIG. 2 schematically illustrates sources of inertia in the moving parts of the washer during the spin extraction portion of the wash cycle. Box 32 signifies the inertia of the motor and drive shaft of the motor. Boxes 34 represent drive friction primarily in the bearings of the motor and drive shaft. Boxes 36 represent the gears connecting the motor with the basket which can comprise either a direct gear connection or a belt and pulley connection. Boxes 38 represent bearing friction associated with the basket and agitator and box 40 represents the inertia of the machine, that is inertia of the basket, agitator and spin tube. Finally, box 42 represents inertia of the load carried within the basket. During a spin operation, the inertia of the elements represented by boxes 32 through 40 remains constant at any given rotational speed. Only the inertia of the load, represented by box 42, changes during a spin operation. This inertia changes because the amount of water retained in the load decreases during spin. If the inertia of the load 42 does not change within a given time period then this means that the amount of water extracted has not changed.
The present invention utilizes this changing inertia of the load as a means for detecting the amount of water extracted during any given time period.
FIG. 3 illustrates one embodiment of the invention in a graphic form depicting rotational speed of the basket versus time. A first low limit speed W1 and a first high limit speed W2 for the basket are predetermined. The motor is energized to accelerate the basket up to the first lower limit speed W1 as an initial starting point. Then, the basket speed is accelerated from the first low limit speed W1 to the first high limit speed W2 and the time required to accelerate to the first high level speed W2 is measured. This is represented by times T o as the initial time and T 1 as the final time. The basket speed is then allowed to declerate down to the initial low limit speed W1 and, upon achieving that speed, is again accelerated up to the high limit speed W2. Again the time required for such acceleration is measured, this being the time between points T 2 and T 3 . The two time periods, that is T 3 - T 2 and T 1 - T o are compared and, if significantly different, the basket is caused to decelerate again to the initial low limit W1 where it is again accelerated up to the high limit W2 and the time required for acceleration measured. The new time period T 5 - T 4 is compared with the most recent measured time period, that is T 3 - T 2 and, if there is a significant difference, the same steps would be repeated.
In the illustration of FIG. 3, the two time periods T 5 - T 4 and T 3 - T 2 are substantially identical, thus indicating that the acceleration time is the same and, therefore indicating that the inertia of the load is the same. This is known because the torque applied by the motor during each acceleration step is held constant. The basket is then caused to accelerate up to a new low limit speed W3 as an initial point from where it is accelerated up to a new high limit speed W4 and the time required for such acceleration, T 7 - T 6 is measured. Again, the basket is then caused to decelerate to the new low limit speed W3 from where it is caused to reaccelerate up to the high limit speed W4. The same steps are repeated as were done during the extraction at the first speed range, that is, the acceleration times compared for successive accelerations between the low limit speed and high limit speed until two successive speeds are detected that are not significantly different. When such a determination occurs the motor accelerates the basket to a third speed range defined between a low limit speed W5 and a high limit speed W6 and the same steps are again undertaken.
In this manner, the clothes load is first rotated at a relatively low first speed level until virtually all of the moisture extractable at that rotational speed level has in fact been extracted. Only then is the basket accelerated up to a second speed level and maintained at that level, until virtually all of the moisture extractable at that speed level has been extracted. Such an incremental increase in speed levels is continued until a predetermined speed level is attained which represents a desired level of moisture extraction. Once it has been determined that all of the moisture has been extracted at the predetermined highest speed level, then the spin step of the wash cycle is terminated.
FIG. 4 illustrates circuitry which can be utilized as a control for achieving the various levels of low limit and high limit speeds of the motor as illustrated in FIG. 3. A source of alternating current is supplied to lines 50, 52 which are connected to a full wave bridge rectifier 54 to provide a DC voltage on line 56 to a motor 58. A diode 60 is provided on a bypass line 62 to prevent a reverse current flow through the DC motor.
It is desired during the operation of the motor to rotate the motor shaft at a series of preselected speeds defining a speed range at various speed levels. Further, it is desired to supply a fixed current to the motor at any given speed level so that the torque of the motor is held constant to permit a consistent measurement of acceleration times of the motor. The control of the motor is provided by use of a pulse width modulator control circuit 64 such as Model CS-5560 produced by Cherry Semiconductor of East Greenwich, R.I.
To provide a desired current level, a voltage source V limit DAC is applied at line 66 to one leg of a comparator 68 while the other leg of the comparator is connected to a line 70 which, through a relatively small resistance 72 thereby measuring the current flowing to the motor. The comparator 68 acts as a switch and, the output signal of the comparator is supplied to port 11 of the control circuit 64 which is a current limiting port which affects the output of the control circuit at port 14. The voltage supplied at line 66 can be set at a relatively high amount to initiate the spinning program in order to overcome the initial at rest inertia of the wash basket and clothes load to bring the wash basket up to a first minimum rotational speed. Thereafter, the voltage can be reduced such that a lower current is supplied to the motor for the various acceleration steps. It is not necessary that the current supplied to the motor at various speed levels be maintained constant, however it is necessary for the current level supplied to the motor to remain constant at a given speed level.
A reference voltage V cc is utilized at a number of locations in the circuit, being supplied to port 1 as a reference voltage for the control circuit 64, through a resistance to port 15 and to provide an internal voltage at line 74 to a potentiometer 76 used in determining the rotational speed of the motor shaft. In the embodiment of the circuit illustrated in FIG. 4, a voltage V tach , which may be obtained as an output voltage of a tachometer attached to the motor shaft, is applied to line 78 and which passes through an amplifier and filter circuit 80 and is summed with the reference voltage V offset at comparator 82. An alternate means of measuring the speed of the motor can be to tap directly into the back EMF of the motor rather than utilizing a separate tachometer.
A second leg of comparator 82 is supplied with a voltage V set DAC which is a voltage designed to set the particular rotational speed to be obtained by the rotating motor shaft. Thus, during operation at a given speed level, this voltage will be at a relatively low level when the motor is to be operating at the low limit rotational speed, and then when acceleration is to occur, the voltage level will be increased to represent the high limit speed at that level. Once the high limit speed is achieved, the voltage would be returned to the low limit value. This back and forth changing of the voltage limit would continue until the acceleration times have been determined to be approximately equal and then the voltage would be increased to the new, higher low limit value for the next highest speed level range. The output of comparator 82 is fed to feedback port 3 of the control circuit 64. The output of control circuit 64 comes from port 14 and is used to drive a powered darlington amplifier 84 which in turn drives a power transistor 86 to provide the current flow to the motor.
The entire control circuit 64 can be turned off by an appropriate signal on line 88 to port 10.
Thus, the circuitry of FIG. 4 illustrates one embodiment of a means for controlling the motor speed to operate the motor at various speed levels, between high and low limit speeds at those levels through an appropriate voltage signal V set DAC and to control the current to the motor through an appropriately selected voltage signal V limit DAC. An external circuit such as a micro computer with a timer is utilized to measure the time required to accelerate from a given low limit speed to a given high limit speed at each speed level and is utilized to provide the desired voltage signals V set DAC and V limit DAC.
FIG. 5 is a flow chart diagram illustrating the steps undertaken during the method disclosed herein. In control unit 100 a clock is started at a time zero. The speed level set points are set for M representing a minimum speed at 1 and N representing a maximum speed at 2. A current level I is set at a maximum limit and a counter P is set at 1.
Control is then passed to control unit 102 where armature voltage is set at a level equal to current I times resistance of the armature Ra plus a voltage E equal to the back EMF voltage of the motor. Motor speed is then read and stored as variable W which equals the back EMF voltage E divided by a motor speed constant K v . Control is then passed to control unit 104 where the read motor speed W is compared to a minimum speed W(M) plus or minus a predetermined range limit. If the read speed is not substantially equal to the minimum speed W(M) then control is passed back to control unit 102 for a repetition of the reading until the minimum speed is attained. When the minimum speed is attained, control is passed to control unit 106 where it is determined if the motor speed W is greater than or equal to the maximum speed of the motor W max . If the motor speed is greater or equal to the maximum speed then control is passed to control unit 108 where the speed is held until a maximum spin time limit T max is reached.
As long as motor speed is below maximum speed, then control is passed to control unit 110 where the time at the minimum speed set point is stored as T(M), current I is set at an acceleration current I a and voltage is set at the current times the armature resistance plus the back EMF voltage of the motor. Control is then passed to control unit 112 where the motor speed W is read, as was done in control unit 102. Control is then passed to control unit 114 which compares the read motor speed with a maximum speed set point W(N) plus or minus a predetermined limit range. If the maximum speed set point has not been attained, control is passed back to control unit 112 for a repetition of steps in control unit 112 and 114 until the maximum speed set point is attained. Then control is passed to control unit 116 where the time at the maximum speed set point is stored as T(N). Control is then passed to control unit 118 in which acceleration at the current counter level P is calculated by the difference between the maximum speed set point W(N) minus the minimum speed set point W(M) divided by the time difference of the time at the maximum speed set point T(N) minus the time at the minimum speed set point T(M). The counter is then incremented by 1 and control is passed to control unit 120 which compares the current acceleration A(P) with the most recent acceleration A(P-1) to determine if the current acceleration is greater than a predetermined limit amount. If the difference is greater than the limit then control is passed to control unit 122 where current is set to a current level during deceleration I d and control is passed back to control unit 102 to repeat the above described steps.
However, if the current acceleration is within the predetermined limit amount of the most recent acceleration, then control is passed to control unit 124 where the minimum and maximum set points are incremented to the next higher level. Then control is passed back to control unit 102 to repeat the above steps for the new levels.
It is thus seen that the control will first bring the basket up to an initial speed and start a timer and then will cause the basket to accelerate and decelerate in a first speed range until accelerations of the basket in two successive acceleration steps are substantially the same. Then the control will increment the speed range to a next higher level and again there will be a repetition of acceleration and decelerations until a substantially constant acceleration is sensed.
FIG. 6 graphically illustrates the significant improvement in operation provided by the present invention. This graphic illustration compares basket rotational speed, force on the clothes load and amount of water extraction which occurs in a presently available washing machine with identical parameters in a washing machine embodying the principles of the present invention.
Specifically, in the presently available washing machine the speed of the basket, which is illustrated by the line designated 126, is caused to rapidly accelerate from zero up to some predetermined constant rate of approximately 700 rpm and the speed remains relatively constant during the entire extraction cycle. The force on the clothes load is illustrated by line 128 and it is seen that it accelerates rapidly up to a peak amount just short of 300 lbs. from where it slowly tapers down to a level still above 250 lbs. The peak in the force curve occurs when the speed of the basket reaches its highest level and it slowly decreases due to water being extracted from the clothes load. That is, as more water is extracted, the force on the clothes decreases.
The amount of water extracted, in pounds, is illustrated by curve 130 which shows a fairly rapidly increasing amount of water being extracted as the speed of the basket accelerates towards its fixed upper speed and then the amount of incremental or additional water being extracted slowly tapers off until, at about 200-240 seconds, all of the water that is extractable has been extracted and the curve remains level. In the presently available washing machines, the extraction step is continued for a predetermined period of time, independent of the moisture retaining quality of the clothes load. Thus, as illustrated, often the cycle continues despite the fact that no additional moisture is being extracted.
The same parameters are illustrated for a washer incorporating the principles of the present invention. A speed curve is illustrated by a dashed line at 132 which shows a first acceleration up to a first speed range with a repetition of accelerations and decelerations resulting in a saw tooth speed curve at a first level, then an acceleration up to a second level with a second saw tooth representation and finally an acceleration up to a third level again with a saw tooth representation.
The force on the clothes load, as measured during tests of a washer supplied with a control similar to that described above resulted in relatively low force loads on the clothes, that is below a hundred pounds, up until the speed had achieved the third or highest level as illustrated by a dashed line 134.
The amount of water extracted is illustrated by dashed curve 136 which shows that the amount of water extracted accelerates fairly rapidly and then begins to taper off during the first speed level. When the speed is increased to the second speed level it again accelerates and then tapers off and, as the basket speed is moved to the highest level, the amount of water extracted again accelerates upwardly and tapers off as the speed is held in the third speed range.
A surprising result obtained by use of the present invention, and illustrated in this comparison is that although the speed of the basket is maintained below that of a speed attained in presently available washers, the amount of water extracted is actually higher while the force on the clothes load is held considerably below that of presently available machines. In the presently available machines the force on the clothes load remains at a very high level even when the water has been extracted to a large degree. However, by use of the present invention, the force is held at a relatively low level even though speed of the basket is increased to a relatively high level. This seemingly inconsistent difference in results is explained because in presently available machines, as the speed of the basket is rapidly accelerated to its final, constant level, the clothes are pressed against the basket wall by the weight of the water still remaining in the basket and, as a wet mass are virtually molded or plastered against the sidewalls of the basket. Even though the additional water is removed from the clothes, the clothes remain pressed tightly against the wall of the basket and, even after the basket has stopped rotating at the end of the cycle, the clothes are still pressed against the outside wall of the basket and must actually be peeled away from the basket wall. However, in a wash cycle embodying the principles of the present invention, most of the water is extracted from the clothes without the clothes being pressed tightly against the basket wall and thus, the force on the clothes never attains the high level experienced in present washers. An empirical observation of the appearance of the clothes within the basket at the end of the cycle shows that the clothes are not plastered against the sidewall of the basket, but look fluffier. This corresponds to a much lower force on the clothes load which translates into wrinkling of the clothes.
It can be appreciated that various other embodiments of the invention can be undertaken to provide the advantageous results described. For example, although the above embodiment is described as utilizing a permanent magnet brush motor (FIG. 4) in which the back EMF of the motor is sensed (FIG. 5), thereby requiring no external controls, the invention could also be incorporated by using a tachometer feedback. Also, an induction motor or an electronically commutated motor could be utilized instead of the permanent magnet motor described.
Also, a control could be employed to cause the basket to accelerate to a first rotational speed for a given time period, then accelerate to a second speed level for a predetermined time period and to higher levels of speed for given time periods in accordance with empirically predetermined test results to achieve a result substantially identical to that described above although exact precision would not be attained in assuring that all of the moisture had been extracted at a given speed level or that termination of the operation occurred as soon as the maximum amount of moisture had been extracted for the highest speed level. A further embodiment of the invention would be one in which the speed of the basket is slowly but constantly accelerated so that again most of the water would be extracted from the wash load at a relatively low basket speed, while permitting maximum moisture extraction by having a relatively high maximum basket rotational speed.
An alternative control could provide constant acceleration to the motor and measure the torque differences, rather than as discussed above by providing a constant torque and measuring the acceleration.
As is apparent from the foregoing specification, the invention is susceptible of being embodied with various alterations and modifications which may differ particularly from those that have been described in the preceeding specification and description. It should be understood that we wish to embody within the scope of the patent warranted hereon all such modifications as reasonably and properly come within the scope of our contribution to the art.
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A method and control for an automatic washer is provided in which moisture extraction from a fabric load is controlled by extracting the moisture at increasingly faster levels of basket rotation. Initially the basket is rotated relatively slowly and it is subsequently rotated at successively faster speed levels, each increase occurring after substantially all of the moisture has been removed which is removable at a given speed level. Inertia of the fabric load is measured to determine the amount of incremental moisture removal. Use of such a method substantially reduces the force applied to the fabric load during the centrifugal extraction resulting in less wrinkling of the fabrics.
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This is a continuation of application Ser. No. 765,394, filed Sep. 20, 1991, now abandoned which is a continuation of Ser. No. 638,034 filed Jan. 7, 1991, now abandoned which is a continuation of Ser. No. 540,405 filed Jun. 19, 1990, now abandoned which is a continuation of Ser. No. 290,054 filed Dec. 23, 1988, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to a method of adjusting the weighting coefficients corresponding to N successive stages of a transversal filter according to the least means squares algorithm, in which method signal samples are supplied to the filter in succession, differences between output signals of the filter and a reference are determined, which output signals each result from a respective group of N of said samples being weighted by said weighting coefficients, and a respective correction derived from the product of a said difference and the current content of a stage of the filter is applied to each said weighting coefficient. The invention also relates to a modification of such a method in which inter alia the transversal filter is replaced by a decision feedback filter. Moreover the invention relates to arrangements for implementing such methods.
It is often required that the weighting coefficients of a transversal filter be adjusted in order to render the filter characteristic closer to that currently required. For example, such a filter may be employed as a so-called "equaliser" for compensating for distortion to a transmitted signal caused by the imperfect nature of a transmission channel. If the channel characteristics vary with time then, in order that satisfactory equalisation continues to be achieved, it is necessary that the filter characteristic be updated either effectively continuously or periodically to take into account the changed channel characteristics. To this end methods of the general kind defined in the first paragraph are well-known, the "least mean squares algorithm" being one of several algorithms which could be employed for the adjustment process. In the known methods each coefficient is adjusted once for every sample applied to the filter according to the formulae: ##EQU1## where C 1 (k), C 2 (k) . . . C N (k) are the weighting coefficients corresponding to the N successive stages of the filter for a given sample period k of the input signal, μ is a constant which is usually less than 0.1, e(k) is the difference between the output of the filter and the reference for the given sample period k, and V 1 (k), V 2 (k), . . . V N (k) are the respective contents of the N successive stages of the filter for the given sample period k. This adjustment of every coefficient once for every sample period gives theoretically optimum results in respect of speed of acquisition of the required characteristic. However, the large amount of computation required in order to achieve this implies a relatively large power consumption, which can be a disadvantage in many applications.
SUMMARY OF THE INVENTION
It is an object of the invention to mitigate the afore-described disadvantage of the prior art.
According to one aspect of the present invention a method as defined in the first paragraph is characterised in that the filter includes at least one further stage which succeeds the N successive stages and the weighting coefficient corresponding to which is set to zero for the production of each said output signal, in that each of the N coefficients is adjusted only once for each n samples applied to the filter, where n is greater than unity, and in that each correction is derived from the output of the filter after the entering of values representative of a plurality of said differences into the filter as respective weighting coefficients and the setting of any remaining weighting coefficients to zero.
It has now been recognised that the quantity C x (k) on the right-hand side of each of the above formulae is itself given by a similar formula in which the corresponding quantity on the right-hand side is itself given by a similar formula, etc. etc. Thus, for example, the formula C 1 (k+1)=C 1 (k)+μe(k) V 1 (k) can be expanded as follows ##EQU2## etc. Once this has been done it becomes apparent that C 1 may be adjusted, for example, once for every two sample periods of the input signal using the expression
C.sub.1 (k+1)=C.sub.1 (k-1)+μ[e(k-1) V.sub.1 (k-1)+e(k) V.sub.1 (k)],
provided that the quantities inside the square brackets are known at the relevant time. In fact the quantity V 1 (k-1) will still be present in the filter, because V 1 (k-1)=V 2 (k) so that the only quantity which needs to be saved is e(k-1). Similarly C 1 could be adjusted only once for every three samples of the input signal using the relevant expression quoted above provided that the quantities e(k-2) and e(k-1) are saved (and assuming that the filter comprises at least three stages so that the quantity V 1 (k-2)=V 3 (k) is still present). Moreover, it will be noted that the quantity inside the square brackets above (and the corresponding quantity if C 1 were adjusted more infrequently than once for every two sample periods) is in "sum of products" form. This is exactly the form of calculation performed by a transversal filter. Thus, for example, the filter itself can be made to evaluate the quantity inside the square brackets above by the simple expedient of substituting the quantities e(k) and e(k-1) for the weighting coefficients C 1 and C 2 respectively, and setting any other weighting coefficients to zero.
If, for example, the weighting coefficient C N is treated in a similar way, we have ##EQU3## etc. In this case it will be noted that, if the filter were to have exactly N stages, although the quantity V N (k) would be present in the filter for the sample period k, the quantities V N (k-1), V N (k-2) etc. will have dropped out of the end. Therefore, if one of the above formulae is to be applied then, if C N is to be adjusted once for every n sample periods of the input signal and a respective said output signal is produced for each signal sample applied to the filter, the filter will have to be provided with at least n-1 further stages succeeding the N stages so that the quantities V N (k-1) . . . V N (k-(n-1)) do not drop out until they are no longer needed. Provided that this is done the quantity [e(k)V N (k)+e(k-1) V N (k-1)+. . . +e(k-(n-1)) V N (k-(n-1))] may be evaluated by means of the filter in a similar way to that set forth above, i.e. by substituting the quantities e(k), e(k-1) . . . e(k-(n-1)) for the coefficients C N , C N+1 , . . . C N+n-1 respectively and setting the remaining coefficients to zero. It should be noted however that in some cases satisfactory results may still be obtained if less than n-1 further stages are provided, so that the corrections for the coefficients which correspond to at least some of the N successive stages are derived using less than the total amount of information which would otherwise be available, the "oldest" of this information being in fact that which is not used.
In order to minimise the amount of calculation carried out serially for each sample period it may be arranged, if a respective said output signal is produced for each signal sample applied to the filter, that n=N and one correction for a coefficient is derived for each sample applied to the filter. However, it may as an alternative be preferred in some circumstances and if N is even, to choose for example n=N/2 and derive two corrections for respective coefficients for each sample applied to the filter. This can allow the total number of stages in the filter to be reduced.
The aforesaid one aspect of the present invention can be employed to adjust the weighting coefficients of a so-called "decision feedback" filter if it is arranged that the input signals to the filter are in multiplexed form. More specifically, it may be arranged that a respective said output signal is produced for each pair of signal samples applied to the filter and that alternate ones of said signal samples are derived from a said output signal via a decision element, and from an external signal source respectively.
According to another aspect the invention provides a method of adjusting the weighting coefficients corresponding to N stages of a decision feedback filter arrangement according to the least mean squares algorithm, said filter arrangement comprising first and second transversal filters having a common output which is coupled to the input of the second filter via a decision element, X successive stages of the first filter and Y successive stages of the second filter together constituting said N stages, in which method signal samples are supplied to the first filter in succession, differences between output signals appearing at said common output and corresponding signals appearing at the decision element output are determined, and a respective correction derived from the product of a said difference and the current content of a stage of a said filter is applied to each said weighting coefficient, each said output signal appearing at said common output resulting from a respective group of X of said samples and Y of the signals derived from the decision element output which are applied to the second filter being weighted by said weighting coefficients, characterised in that the first filter includes at least one further stage which succeeds said X successive stage and the second filter includes at least one further stage which succeeds said Y successive stages, the weighting coefficients corresponding to said further stages being set to zero for the production of each said output signal appearing at said common output, in that each of the N coefficients is adjusted only once for each n samples applied to the first filter, where n is greater than unity, in that each correction for a weighting coefficient corresponding to one of the X stages of the first filter is derived from the output of the first filter after the entering of values representative of a plurality of said differences into the first filter as respective weighting coefficients and the setting of any remaining weighting coefficients therein to zero, and in that each correction for a weighting coefficient corresponding to one of the Y stages of the second filter is derived from the output of the second filter after the entering of values representative of a plurality of said differences into the second filter as respective weighting coefficients and the setting of any remaining weighting coefficients therein to zero.
The invention also provides transversal and decision feedback filter arrangements for implementing the aspects of the invention defined above.
BRIEF DESCRIPTION OF THE DRAWING
Embodiments of the invention will now be described, by way of example, with reference to the accompanying diagrammatic drawings, in which:
FIG. 1 is a block diagram of a first embodiment of the transversal filter arrangement of the present invention,
FIG. 2 illustrates the time relationship between some control signals occurring in the embodiment of FIG. 1,
FIG. 3 illustrates some information signals occurring in the embodiment of FIG.1,
FIG. 4 illustrates some information signals occurring in a modified version of the embodiment of FIG. 1,
FIG. 5 illustrates some information signals occurring in another modified version of the embodiment of FIG. 1,
FIG. 6 illustrates some information signals occurring in yet another modified version of the embodiment of FIG. 1, and
FIG. 7 is a block diagram of another embodiment of the invention in the form of a decision feedback filter using interconnected essentially duplicate transversal filter arrangements illustrated in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIG. 1 of the drawing, a transversal filter arrangement comprises a conventional transversal filter 1 in the form of a delay line or shift register 2 having (N+n-1) stages, a multiplier array 3 comprising a respective multiplier corresponding to each stage of the register 2, and an adder 4 which adds together the outputs of all the multipliers of the array 3 and produces the result on an output 5. Each multiplier of the array 3 has a first input coupled to an output of the corresponding stage of the register 2 and a second input fed from a respective group of bit-lines of a multiple input 6 and multiplies the content of the corresponding stage of the register 2 by a (digital) quantity applied in operation to the respective group of bit lines of the input 6. The serial input 7 of the shift register 2 is also multibit, as is the storage capacity of each stage of the register 2. The input 6 is fed from the parallel outputs of a first auxiliary register 8 and a second auxiliary register 9 as alternatives via a two-position multiplexer 10. Each of the registers 8 and 9 contains a multibit storage stage corresponding to each multiplier of the array 3 and, when the multiplexer connects the parallel output of the relevant register 8 or 9 to the input 6, the content of each stage is applied to the bit lines of the input 6 which feed the corresponding multiplier. Thus the contents of the stages of the register 2 are weighted by the contents of the corresponding stages of the register 8 or 9 and the results are added together by the adder 4. The input 7 of the (clocked) shift register 2 is fed from an input terminal 11 via a correspondingly clocked sampling analog-to-digital converter 12. Input terminal 11 is connected to the output of an external signal source (not shown). Input 7 is therefore fed with a succession of samples V in digital form of an analogue input signal applied to terminal 11, these samples being clocked through the register 2 in succession and giving rise to corresponding filtered signal samples in digital form at the output 5.
Output 5 is connected, via a two position demultiplexer 12, as alternatives to either the input of a multiplier 14 or to both the input of a decision element 15 and a first input of a subtractor 16. The output of decision element 15 feeds both an output 17 and also the second input of the subtractor 16. In a known manner decision element 15 takes, on the basis of the potentially distorted signals fed to its input from the output 5, decisions on what these signals would ideally be in the absence of such distortion and produces the results of these decisions on its output, whence they are fed to the output 17. The decisions may be taken, for example, on the basis of a reference to all the possible values which the output signals of converter 12 could have in the absence of distortion or, as another example, on the basis of a reference to the undistorted form of a standard signal a potentially distorted version of which is periodically received on the input terminal 11. The difference e between the successive output signals of decision element 15 and the corresponding signals appearing at the output 5 of filter 1 are calculated by subtractor 16 and are clocked in succession into a shift register 18 via its serial input 19. Shift register 18 has n stages, and its parallel output 20 is connected to the parallel input 21 of the right-hand n stages of register 8, the remaining N-1 left-hand stages of register 8 being loaded with zeros on a permanent basis. The right-hand n stages of register 8 correspond to the n multipliers at the right-hand end of array 3.
Multiplier 14 multiplies the signals fed to it from the filter output 5 by a fixed constant value μ, and applies the result to one input 22 of an adder 23. The other input 24 of adder 23 is fed with the contents of a selected one of the N left-hand stages of register 9 via an N-position multiplexer 25, these N left-hand stages corresponding to the N multipliers at the left-hand end of the array 3 (which contains N+n-1 multipliers in all). The remaining stages of register 9 are loaded with zeros on a permanent basis. The output of adder 23 is fed to the input of a selected one of the N left-hand stages of register 9 via an N-position demultiplexer 26, the stages selected by (de)multiplexers 25 and 26 at any given time being the same. Each of the said N left-hand stages also has a respective load signal input (not shown), and that stage which is at any given time selected by demultiplexer 26 also has its load signal input connected through demultiplexer 26 to a further bit input 27 of demultiplexer 26. Control or selection signal inputs 28 and 29 of the (de)multiplexers 25 and 26 respectively are fed from the output 30 of a counter 31 which has a capacity N. A "borrow" signal output 32 of counter 31 is connected to a parallel load input 34 of register 8. Register 8 is therefore loaded each time (decremented) counter 31 is changed to a state in which it controls (de)multiplexers 25 and 26 to select the Nth stage of register 9.
The components 2, 10, 12, 13, 18 and 31 are supplied with clock/control signals from outputs A, B, C, D and E of a clock/control signal generator 35 as shown. The time relationship between these signals is indicated in FIG. 2 of the drawings. Signal A is applied to a sampling control signal input 36 of analog-to-digital converter 12 and to a clock signal input 37 of delay line or shift register 2, so that each time a rising edge occurs in the signal A, a sample is taken of a signal applied to input 11, is converted to digital form, and is clocked into the first stage of register 2. Signal B is applied to select signal inputs 38 and 39 of the (de)multiplexers 10 and 13. A high level in this signal causes multiplexer 10 to connect the parallel output of register 9 to input 6 and demultiplexer 13 to connect output 5 to decision device 15 and subtractor 16, these (de)multiplexers taking up their other selection state when signal B is low. Signal C is supplied to the clock signal input 40 of shift register 18 so that the output of subtractor 16 is loaded into the first stage of register 18 each time a rising edge occurs in signal C. Signal D is applied to the clock signal input 41 of (cyclic) counter 31, so that the content of counter 31 is decremented on each rising edge of signal D. Signal E is applied to the bit line input 27 of demultiplexer 26 so that the stage of register 9 currently selected by demultiplexer 26 is loaded with the output of adder 23 each time a rising edge occurs in the signal E.
In operation successive digital samples V of a signal applied to input 11 are clocked into shift register or delay line 2 under the control of signal A. During the first half of each sample period (signal B high) the corresponding output I of filter 1, using the contents of register 9 as the respective weighting coefficients C, appears on output 17 after processing by the decision element 15. Moreover, the difference (e)=I-V between the input signal V to and the output signal I from decision element 15 is clocked into shift register 18 under the control of signal C. It will be noted that only the samples in the first N stages at most of register 2 contribute to the signal at output 17, because the contents of the stages of register 9 which correspond to the remaining stages of register 2 are permanently zero. The arrangement therefore operates effectively as an N-tap filter, even though register 2 comprises more than N stages.
During the second half of each sample period (signal B low) the contents e of register 8 are used for the filter weighting coefficients (only the samples in the last n stages at most of register 2 contributing to the resulting signal applied to multiplier 14 because the contents of the stages of register 8 which correspond to the remaining stages of register 2 are permanently zero). The resulting output of multiplier 14 is used to correct, under the control of signal E, the weighting coefficient contained in that stage of register 9 which is currently being selected by (de)multiplexers 25 and 26 under the control of counter 31. Because counter 31 is clocked by signal D once for every sample period the N coefficients stored in register 9 are corrected in turn, one per signal sample period, on a cyclic basis, the contents of register 8 being set to the current contents of register 18 prior to each correction of the nth coefficient. It will be apparent from a consideration of the time relationship between the various signals that each of the N coefficients in register 9 is corrected once for every N sample periods in a manner given by the formulae derived above. If n=N the maximum number of signal samples and errors is taken into account for the correction of each coefficient although, as mentioned previously, in some cases satisfactory results may be obtained if less than this number is taken into account, at least for the correction of some coefficients. In other words, in some cases satisfactory results may be obtained if n is less than N.
As an example FIG. 3 illustrates for four successive sample periods k, k+1, k+2, k+3, the contents V of the stages of the shift register 2 and, beneath each one, the corresponding weighting coefficients employed during the first and during the second halves of the relevant sample period, for N=n=3. V 1 (k) is the content of the first stage of the register during the sample period k and e(k)=I(k)-V(k) is the corresponding output of subtractor 16 during the first half of that sample period. It will be seen that during the second half of sample period k the output of multiplier 14 is μ[e(k) V 1 (k-2)+e(k-1) V 1 (k-3)+e(k-2) V 1 (k-4)], i.e. the required correction for the weighting coefficient C 3 for the third stage of the register. Similarly, during the second half of sample periods k+1, k+2 and k+3 the outputs from multiplier 14 are the required corrections for the weighting coefficients for the second (C 2 ), first (C 1 ) and third (C 3 ) stages of register 2, as required.
It should be noted that an integrated circuit having an architecture corresponding to the combination of the items 1, 8, 9 and 10 is commercially available from Inmos under the type number A100, and such an integrated circuit may be used to implement these components. If this is done the arrangement of the clock/control signal generator 35, (de)multiplexers 25 and 26, and counter 31 will have to be modified somewhat to take into account that with this integrated circuit the various stages of the registers 8 and 9 have to be accessed by applying appropriate address signals to the circuit.
As described so far, one of the N coefficients in register 9 is adjusted for each sample period of the signal applied to input 11. In fact, if desired, more than one coefficient may be adjusted for each said period, enabling the excess of the number of stages of register 2 over N to be reduced while still taking into account the maximum amount of information for the adjustment of each coefficient, albeit at the expense of having to carry out more operations during each sample period. FIG. 4 is a diagram, similar to FIG. 3, showing how it may be arranged that two of the N coefficients are adjusted during the latter part of each sample period. Again in this example register 2 has five stages, but now N=4 and each coefficient is adjusted once for every n=2 sample periods. During the sample period k, after the error signal e(k) has been derived from the output of the filter it is used as the weighting coefficient for the fourth stage of register 2 and e(k-1) is used as the weighting coefficient for the fifth stage. The output of multiplier 14 is therefore μ[e(k) V 1 (k-3)+e(k-1) V 1 (k-4)], i.e. the required correction for weighting coefficient C 4 for the fourth stage of register 2. The error signals e(k) and e(k-1) are now used, still during the sample period k, as weighting coefficients for the third and fourth stages of register 2 respectively resulting in the required correction for the weighting coefficient C 3 for the third stage of register 2. During the next sample period, after the error signal e(k+1) has been derived from the output of the filter, the error signals e(k) and e(k-1) are again used as weighting coefficients for the third and fourth stages respectively of register 2, resulting in the required correction for the weighting coefficient 2 for the second stage of register 2. The error signals e(k) and e(k-1) are then used, still during the sample period k+1, as weighting coefficients for the second and third stages respectively of register 2, giving the required correction for the weighting coefficient C 1 for the first stage of register 2. During the next sample period C 4 and C 3 are corrected once again, and so on. It will be evident that the arrangement of FIG. 1 and various timing interrelationships therein will have to be modified slightly in order to achieve the operations illustrated in FIG. 4 but the modifications required will be readily apparent to a person skilled in the art.
Obviously it is preferable to adjust, as described, each weighting coefficient C immediately as the required correction therefor has been calculated, in order to minimise the settling time of the filter. However in some circumstances satisfactory results may still be obtained if, instead, a plurality of coefficients is adjusted every m sample periods, where m is greater than one. For example, the embodiment of FIG. 1 could be modified so that all the N coefficients in register 9 are adjusted as a group each time the contents of register 18 are written into register 8.
The invention has been described so far in the context of a simple linear filter. It will be evident that it may also be employed, for example, in a filter of the decision feedback type as illustrated in FIG. 7. To this end the filter 1 of FIG. 1 together with items 8-10, 14, 23, 25, 27 and 31 and their interconnections (collectively designated as transversal filter circuit block 42 in FIG. 1) may be duplicated, (duplicate parts being shown with the same reference numeral but with a prime symbol) the duplicate circuit block 42' forming part of the feedback element of the decision feedback filter arrangement. More specifically, the input 7' of the duplicate shift register 2' may be fed from the output 17 via a sign reverser 43, and the signal path from one input to the output of a further added 44, may be included between the output 5 and input of demultiplexer 13 in FIG. 1. That output of duplicate demultiplexer 13' (which corresponds to the one which in FIG. 1 is connected to decision element 15 and subtractor 16) is connected to the other input of the further adder 44, and the output of register 18 is also connected to the parallel input of duplicate register 8'. The counters 31 and its duplicate are in such a case arranged to run in step, so that their contents are always equal to each other; these counters could be replaced by a single common counter if desired. Because of the provision of the sign reverser 43, during the first half of each input signal sample period the appropriately weighted N previous signals I at output 17 are now subtracted in the further adder 44 from the suitably weighted N most recent input signal samples now present in register 2, and the result is applied, as a common output 45 of filter 1 and its duplicate, to decision element 15 and subtractor 15 via multiplexer 13 as required. During the second half of each signal sample period a coefficient in register 9 is adjusted exactly as previously. Moreover a coefficient in the duplicate of register 9 is adjusted in the same way, the same error values e being used as the coefficients for the array 3 and its duplicate. For illustration, FIG. 5 shows on successive lines, for a given sample period k corresponding to the first sample period illustrated in FIG. 3, the respective contents V and V' of register 2 and its duplicate (side by side), the respective weighting coefficients C and C' employed in the array 3 and its duplicate during the first half of the sample period, and the respective weighting coefficients e employed in the array 3 and its duplicate during the second half of the sample period, where V 1 '(k)=-I(k-1). In this example a value of three has been chosen for N and n for both filter 1 and its duplicate although it will be evident that other values may be used and that N may be different from n. Indeed the value of N (=X say) chosen for filter 1 may be different to the value of N (=Y say) chosen for the duplicate of filter 1, X+Y forming the number N of coefficients which are adjusted altogether.
It will be evident that two coefficients could alternatively be adjusted in both filter 1 and its duplicate for each input signal sample period, in the manner described above with reference to FIG. 4. Moreover, instead of including a sign reverser between the output 17 and the input of the duplicate of filter 1, the signs of the coefficients C' may themselves be reversed.
If desired the decision feedback filter arrangement described above may be modified so that only a single transversal filter 1 is employed, albeit of double length and albeit at the expense of having to increase the lengths of registers 8 and 9 and to carry out more operations serially during each input signal sample period. To this end, instead of connecting the output 17 of FIG. 1 to a duplicate of filter 1 via a sign reverser it may be connected, via the sign reverser and one input and the output of a multiplexer, to the input 7 of filter 1, the output of the analog-to-digital converter being connected to the other input of this multiplexer. In such a case this multiplexer may be controlled to connect the output of converter 12 to input 7 during a first portion of each sample period of the input signal and to connect the output 17 to input 7 during a second portion of each period, shift register 2 now being clocked at double rate so that input signal samples V and the resulting output signals I are clocked into the register alternately, producing a content of register 2 as illustrated in the first line of FIG. 6 at a specific time, where V'(k)=-I(k-1). While this content is present it is now arranged that the two sets of weighting coefficients illustrated on the second and third lines of FIG. 3 are employed in succession while demultiplexer 13 connects output 5 to items 15 and 16, and to multiplier 14, respectively. Thus during the first of these periods I(k) is produced at output 17 and e(k) is produced by subtractor 16, and during the second of these periods multiplier 14 produces the correction for coefficient C 3 '. Register 2 is now clocked (fourth line of FIG. 6) while maintaining the weighting coefficients the same (fifth line) and demultiplexer 13 in the state in which it connects output 5 to multiplier 14. Thus multiplier 14 now produces the correction for C 3 . Register 2 is now clocked once again (sixth line of FIG. 6) and the two sets of weighting coefficients illustrated on the seventh and eighth lines of FIG. 6 are employed in succession while demultiplexer 13 connects output 5 to items 15 and 16 and to multiplier 14 respectively. Thus during the first of these periods I(k+1) is produced at output 17 and e(k+1) is produced by subtractor 16, and during the second of these periods multiplier 14 produces the correction for C 2 '. Analogous operations are performed subsequently, resulting in the generation of the correction for C 2 , I(k+2) and e(k+2), the corrections for C 1 ' and C 1 , and I(k+3) and e(k+3), after which the new errors are loaded into register 8 and the cycle repeats as from the third line of FIG. 6. It will be noted that one of the N=6 coefficients is adjusted for each signal sample applied to the filter, so that each is adjusted once for every n=6 samples, that each correction is derived from n/2=3 error signals, and that n-2=4 further stages are provided in the filter subsequent to the first N stages.
Obviously some modifications will have to be made to the arrangement of FIG. 1, and especially to the control pulse generator 35, to achieve the succession of operations described with reference to FIG. 6, but these will be readily apparent to a person skilled in the art. Again, instead of including a sign reverser between the output 17' and the multiplexer supplying the input 7 of filter 1 the signs of the coefficients C' may themselves be reversed.
From reading the present disclosure, other modifications will be apparent to persons skilled in the art. Such modifications may involve other features which are already known in the design, manufacture and use of filter arrangements and component parts thereof and which may be used instead of or in addition to features already described herein. Although claims have been formulated in this application to particular combinations of features, it should be understood that the scope of the disclosure of the present application also includes any novel feature or any novel combination of features disclosed herein either explicitly or implicitly or any generalisation thereof, whether or not it relates to the same invention as presently claimed in any claim and whether or not it mitigates any or all of the same technical problems as does the present invention. The applicants hereby give notice that new claims may be formulated to such features and/or combinations of such features during the prosecution of the present application or of any further application derived therefrom.
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The weighting coefficients in the coefficient array (3) of a transversal filter (1) are corrected in accordance with the least mean squares algorithm by adding to each coefficient a correction derived from the product of the content of a stage of the filter shift register (2) and the difference between a signal at the filter output (5) and the output signal of a decision element (15). Each coefficient is corrected only once for each n sample periods of a signal applied to the filter input (7), where n is greater than unity, in order to reduce the amount of computation required during each sample period. Each correction is derived from the output of the filter by inserting n of said differences into the coefficient array as respective weighting coefficients and setting any remaining coefficients to zero.
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PRIORITY CLAIM
[0001] This application is a continuation of, claims priority to and the benefit of U.S. patent application Ser. No. 10/624,116 filed Jul. 21, 2003, which is a non-provisional of, claims priority to and the benefit of U.S. Provisional Application Ser. No. 60/423,822 filed on Nov. 5, 2002, the entire contents of which are incorporated herein.
BACKGROUND
[0002] The present invention relates to sporting equipment shafts and in particular to shafts suitable for use in high-impact, high-velocity, and high wear and tear sports such as ice hockey, street hockey, in-line skate hockey, ringuette, field hockey, lacrosse and other such sports. The present invention, by way of example only, will be described hereinafter in relation to ice hockey sticks, but it is understood that the invention herein described and claimed may be suitably adapted to other shaft applications and in particular to other sports.
[0003] At present, hockey sticks may be generally broken down into two broad categories, namely wooden hockey sticks, which shafts are generally made of wood such as any suitable hardwood, for example hickory, maple, etc., and composite sticks, which shafts are made of composite materials, such as carbon fiber, Kevlar™, fiberglass, and other such materials or combination of materials which are embedded in any one of a number of resins. The present invention relates to composite hockey sticks.
[0004] Composite hockey stick shafts are in many ways superior to conventional wooden shafts in that they may be stronger and lighter, thus allowing a player to deliver more strength to the puck during play, such as during slapshots, wrist shots, any hard shot and during passing. In addition, composite hockey stick shafts, depending on their method and materials of construction, may exhibit superior characteristics with respect to torsional resistance, bending-moment resistance, shear resistance and are often preferred by both amateur and professional players alike. However, composite hockey stick shafts may exhibit poor or sub-standard resistance to direct impacts thereon which stick shafts are often subjected to during play, in particular when compared to wood shafts. For example, composite hockey stick shafts which receive a direct hit thereon, from either another stick, a puck, or which are hit against the boards, against the ice or against any other object have been known to crack, shatter, delaminate, or break apart. This results from a characteristic of some composite hockey shift shafts in that they are brittle, exhibit little ductile deformation characteristics and have poor impact-absorbing ability.
[0005] It is therefore an object of the present invention to provide for a composite hockey stick shaft having a particular construction which enables the shaft to better absorb impacts and resist deformation resulting from impact loading thereon.
[0006] It is a further object of the present invention to provide composite hockey stick shafts wherein the materials and method of construction thereof allow for impact dissipation such that the forces of impact are spread up and down the length of the shaft and are not localized.
[0007] It is a further object of the present invention to provide a composite hockey stick shaft comprising a viscoelastic layer which provides for improved impact-absorption characteristics such that energy generated by an impact may be dissipated away from the localized area of the impact, thus reducing the stress transferred on the composite materials at the point of impact.
[0008] It is a further advantage of the present invention to provide a composite hockey stick shaft having increased strength and durability along the shaft thereof.
SUMMARY
[0009] The present invention generally provides for a composite hockey stick shaft wherein the structure of the shaft, the fibers in the resin matrix known as the constraining layer, is overlaid by an outer layer of viscoelastic material disposed thereon which acts to dampen and absorb the shocks and impacts which are administered to the shaft during play. In particular, the viscoelastic material may be disposed over substantially the whole length of the shaft, and cover all four sides of the shaft, or alternatively, it may be disposed over only part of the length of the shaft, and may cover one or more of the four sides of the shaft.
[0010] In a further embodiment, the viscoelastic layer may itself be overlaid with a base layer of composite materials whose function may be to provide protection to the viscoelastic layer against mechanical wear and tear (damage) of the viscoelastic layer. The base layer may be hardened and may be thin, i.e. thinner so as to minimize weight. The base layer may overlay the whole of the viscoelastic layer or only a portion thereof.
[0011] In accordance with a general aspect of the present invention, the constraining layer may be assembled and manufactured in accordance with any number of well-known methods of fabricating composite hockey stick shafts. For example, the shaft may be thin-walled, hollow or may be full or may comprise any combination of materials and constructions. The constraining layer may provide reinforcement and stiffness to the shaft structure, while acting as an anchor for the viscoelastic layer. As may be understood, in accordance with a general aspect, the constraining layer is the core of the shaft and may provide all, i.e. substantially all of the structural strength, of the shaft.
[0012] Over the constraining layer, there is provided a viscoelastic layer, whose purpose is to shear or flex under impact loading. In accordance with one aspect, the constraining layer may be a soft flexible material which dissipates impact energy away from an impact zone, thus minimizing localized damage to the underlying constraining layer. As may be understood, the viscoelastic layer may act as a shock absorber to reduce the amount of impact energy transferred to the constraining layer. In particular, the constraining layer acts to dissipate the energy of an impact over a wider area of the underlying constraining layer, thus preventing the energy transferred to the constraining layer from reaching above the breaking point of the material of a particular localized area of the constraining layer. Thus, the viscoelastic layer may allow for localized impact protection. The viscoelastic layer may further allow a composite hockey stick shaft to strain or deflect at higher rates without cracking, breaking, delaminating or otherwise damaging the composite material resin matrix of the constraining layer.
[0013] In accordance with a further embodiment of the present invention, the viscoelastic layer may overlay the whole of the constraining layer, i.e. from one end of the shaft to the other end. Alternatively, the viscoelastic layer may be provided over a particular portion of the shaft, i.e. for example over the area or areas of the shaft which are subjected to the greatest impact or the greatest stress, i.e. for example near the middle of the shaft. In a further alternative embodiment, the viscoelastic layer may be provided over two or more separate and distinct areas of the shaft so as to provide maximum protection and minimizing any additional weight. In addition, the viscoelastic layer may be provided on all four faces of the shaft, or alternatively, on one or more of the faces, i.e. for example the faces of the shaft which are subjected to most wear and tear during play.
[0014] In addition to the above two layers, the present invention may provide for a composite hockey stick shaft wherein a base layer overlies the viscoelastic layer so as to provide protection therefor. In accordance with a particular embodiment, the base layer may be a thin, tough and stiff shell structure which may protect against mechanical damage to the viscoelastic layer caused by impacts, scrapes, bumps and other contact damage administered to the shaft during play. As may be understood, the base layer overlies the viscoelastic layer and may serve to protect it, therefore if the viscoelastic layer is not continuous over the constraining layer, the base layer may also not be continuous.
[0015] As may be understood, the expression <<viscoelastic material>> is meant to include any material which exhibits a high or very high elongation to failure characteristic. Further, <<viscoelastic material>> is also meant to include any material which has a damping property, for example which will dissipate or absorb the energy of an impact, or allow the shear forces to deform said material without destroying its structural integrity. In accordance with a particular embodiment, the viscoelastic material may be a thermoplastic rubber modified adhesive. In accordance with a further embodiment, the viscoelastic material may be one sold by 3M Corporation under the trademark SCOTCH DAMP, or under the trademark Viscoelastic Damping Film 110P, 122P and 130P. In addition, the viscoelastic material may be selected from the group comprising polyester (PET), Urethane, Polyurethane, Mylar, Tedlar, Silicone and Epoxy films.
[0016] In accordance with a further embodiment of the present invention, there may be provided a composite hockey stick shaft which utilizes a constraining-layer damping technology wherein the shaft may be constructed using an outer layer and an inner layer of composite materials, which layers sandwich therebetween a layer of viscoelastic material, damping material or rubberized material or any other material which may act to dampen impact forces and deflections which are applied to the shaft during play. In accordance with this embodiment, the outer and inner layers may be substantially the same thickness and are each designed to provide strength, stiffness and load carrying capacity to the shaft in approximately equal proportion. Alternatively, one of the layers may be thinner than the other, may even be substantially thinner, for example the outside layer. Thus, by nesting a viscoelastic layer between two layers of composite materials, i.e. such as fibers disposed in a resin matrix, a greater deformation of the shaft during play can be tolerated before reaching the breaking point of the composite materials. In effect, the relatively brittle composite material or the inner and the outer layer are made to deform less, while more of the deformation is taken up by the viscoelastic material, for example, as a result of bending moment. As may be understood, when a hockey stick is in use, for example, during a slapshot, the shaft may deflect up to between 6 and 9 inches. The use of a viscoelastic material nested, i.e. disposed between an inner and an outer layers of composite material may allow for greater deformation thereof.
[0017] The thickness of the viscoelastic layer, in particular of the viscoelastic layer disposed between an equal thickness inner and outer layer, may be in the range of about 5 to 25 thousandths of an inch. In accordance with a further aspect, the thickness may be in the range of about 10 to 22.5 thousandths of an inch and may further be about 20 thousandths of an inch thick. As may be understood, the viscoelastic material may be manufactured as a thin film or sheet which may be delivered from the manufacturer thereof on a roll. When it is to be applied, for example onto the inner layer, it is cut into strips and disposed onto the outside surface of the inner layer. The viscoelastic strip may be cut in size so that it may be applied lengthwise onto the inner layer, i.e. in the direction of the length of the shaft, or alternatively the viscoelastic strip may be rolled circumferentially about the inner layer, i.e. for example at an angle to the length of the shaft. As may be understood, more than one strip of viscoelastic material may be used to create the damping layer, and each strip may be applied in a different manner onto the outside surface of the inner layer. Further, more than one layer of viscoelastic material may be applied, one on top of another, each having, for example similar or different damping characteristics.
[0018] In accordance with a particular embodiment of the present invention, the viscoelastic layer may simultaneously be in contact with the inner and the outer layer of composite materials. Thus, the viscoelastic layer may act as a bridge, transferring forces therebetween, such as bending moment and shear forces from the outer layer to the inner layer and vice versa. In the process of transferring forces, the viscoelastic layer deforms more than the outer and inner layers. Thus the viscoelastic layer may be act as an internal damper. By providing a layer which can take more of the deformation, stresses and loads will necessarily accumulate there, and not in the more brittle inner or outer layers, therefore avoiding or delaying failure thereof.
[0019] In accordance with a further embodiment of the present invention, there may be provided a hockey stick shaft having more than two layers of composite materials and one layer of viscoelastic material disposed therebetween. For example, there may be provided with a first (innermost) layer of composite materials onto which is applied a layer of viscoelastic material onto which is applied a second layer of composite materials, onto which is applied a further layer of viscoelastic material onto which is applied a further layer of composite materials. It is understood that each of the composite material layer may be different in materials used and in size, and that each of the viscoelastic material layer may also be different from the other. It is understood that two, three or more layers of viscoelastic materials may be used in this manner to construct a shaft as described.
[0020] In accordance with an embodiment of the present invention, there is provided for a
composite hockey stick having an elongated shaft body having opposed first and second ends, said shaft body having a constraining inner layer comprising a thin-wall composite fibers construction disposed in a matrix material said constraining layer being overlaid with a coating of viscoelastic material.
[0024] In accordance with a further embodiment of the present invention, there is provided for a
composite hockey stick shaft having an elongated body having four side wall members, at least one said side wall members comprising an inner layer of fibers disposed within a matrix material, a layer of viscoelastic material anchored onto to the outside surface of said inner layer, an outer layer of fibers disposed within a matrix material, said outer layer being disposed on and abutting the outside of said layer of viscoelastic material.
DETAILED DESCRIPTION OF THE DRAWINGS
[0029] Other applications and advantages of the present invention may be made clear by the following detailed description of several embodiments of the invention. The description makes reference to the accompanying drawings in which:
[0030] FIG. 1 is a three-dimensional illustration of a hockey stick having a composite hockey stick shaft in accordance with the present invention.
[0031] FIG. 2 is an illustration of a cross-sectional view of the shaft along section lines A-A of FIG. 1 .
[0032] FIG. 3 is a close-up of a portion of the wall of the shaft along view lines B-B of FIG. 1 .
[0033] FIG. 4 is a further close-up of the wall of the shaft of the hockey stick along view lines B-B showing the stick being deformed when subjected to an impact force.
[0034] FIG. 5 is an alternative embodiment of the shaft construction of the present invention.
DESCRIPTION
[0035] FIG. 1 is an illustration of a hockey stick 1 comprising a shaft which is attached to a blade. As may be understood, shaft 4 is made of composite materials and blade 2 may either be made of composite materials or of wood-fiberglass construction.
[0036] FIG. 2 illustrates a close-up of the cross-section of shaft 4 along section lines A-A of FIG. 1 . As shown, the shaft construction is comprised of a number of layers, namely an inner layer 9 comprising an inside surface 5 and an outside surface 6 . Further, the wall construction of shaft 4 comprises a viscoelastic layer 13 disposed adjacent to and abutting inner layer 9 . Further, an outer layer 11 is disposed on an abutting viscoelastic layer 13 . Viscoelastic layer 13 is shown contacting both the inner layer 9 and the outer layer 11 .
[0037] As illustrated, viscoelastic layer 13 is applied to surface 6 of inner layer 9 once inner layer 9 has been constructed. As may be understood, final curing of inner layer 9 may not have been completed prior to the application thereon of viscoelastic layer 13 . Further, outer layer 11 is applied onto viscoelastic layer 13 once said viscoelastic layer 13 has been applied. It is understood that the curing of inner layer 9 and outer layer 11 , or the final curing of inner layer 9 and outer layer 11 may be completed subsequent to the assembling of the wall structure illustrated in FIG. 2 .
[0038] Inner layer 9 and outer layer 11 are shown as being substantially of the same thickness, and further illustrated as having the same thickness on all four faces. Further, viscoelastic layer 13 is illustrated as having substantially the same thickness on each of the four faces of shaft 4 . It is understood, however, that the thickness of viscoelastic layer 13 may not be the same on all four faces of shaft 4 , for example on one or more faces of shaft 4 , namely on opposed faces 12 and 14 , the viscoelastic layer 13 may be thicker. It is understood that viscoelastic layer 13 may not have a constant thickness along the length of the shaft, but may have a different thickness, i.e. may be thicker at one or more points along the shaft where loading requirements, impact and stress transfer requirements may be greater. It is further understood that viscoelastic layer 13 may vary in thickness along the length of the shaft so as to provide additional damping ability where it may be most required, i.e. for example in the middle of the shaft.
[0039] FIGS. 3 and 4 illustrate a close-up of shaft 4 along view line B-B of FIG. 1 . As may be understood, only one wall of shaft 4 is illustrated. The uppermost extremity 15 of shaft 4 is shown. As may be understood, the scale has been exaggerated for ease of viewing.
[0040] FIG. 4 illustrates the close-up of FIG. 3 undergoing a deformation caused by the application of force 21 . The scale of the deformation has been exaggerated for ease of viewing. As may be understood, the application of force 21 may occur along any length of shaft 4 , and even though force 21 is illustrated in FIG. 4 as being a pointlike application, it is understood that shaft 4 may be subjected to different types and combinations of loads.
[0041] As illustrated, shaft 4 is shown being deflected upwardly in the direction of force arrow 21 . As shown, outer layer 11 is shown having been deflected upwardly a distance similar to the deflection incurred by inner layer 9 . However, said deflection of outer layer 11 may be smaller than the deflection of inner layer 9 since the viscoelastic layer 13 may also have deformed. Since viscoelastic layer 13 may deform more than either of inner layer 9 or outer layer 11 , more of the load 21 may be taken up, i.e. absorbed, i.e. dissipated by the deformation of viscoelastic layer 13 than by either of inner layer 9 or outer layer 11 . As a result, viscoelastic layer may, for example, flatten and become thinner, thus allowing outer layer 11 to deform less than inner layer 9 .
[0042] In addition to the above, a beam-like structure, such as a hockey stick shaft, will under cantilever and other types of loading, exhibit bending moment forces. Such bending moment forces occur horizontally, i.e. are translated inside the structure horizontally, i.e. at roughly 90 degrees to the direction of the force applied. Bending moment forces are illustrated by force arrows 25 and 27 , namely substantially horizontal forces which are incurred by shaft 4 by a deformation at end 15 in the direction of motion arrow 21 .
[0043] As each of inner layer 9 and outer layer 11 are relatively stiff and unyielding, the endmost portion 10 of, for example, inner layer 9 , will under the loading conditions of force 21 remain substantially at 90 degrees to surfaces 5 and 6 . Similarly, endmost portion 12 of outer layer 11 will also remain substantially at 90 degrees. However, the viscoelastic layer 13 can deform due to its material properties, the whole as shown by reference number 16 . Thus, as may be understood, bending moment force arrows 25 and 27 cause the deformation of viscoelastic layer 13 , such that in the illustrated example, angle 18 is less than 90 degrees and angle 20 is greater than 90 degrees. This deformation of the viscoelastic layer 13 uses up some of the energy of force 21 , which energy is absorbed by the material of viscoelastic layer 13 when it deforms. Said deformation is illustrated by distance 23 , namely the difference between endmost portions 10 and 12 , which is indicative of the ability of viscoelastic layer 13 to deform and absorb impact forces.
[0044] FIG. 5 illustrates an alternative embodiment of the wall construction of FIG. 3 , wherein three composite layers 33 , 35 and 37 , are spaced apart by two viscoelastic layers 41 and 39 . As illustrated, composite layer 33 is thicker than composite layer 35 while viscoelastic layer 41 is made up of a different material than viscoelastic layer 39 .
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The present invention discloses a composite hockey stick shaft having an elongated body having four side wall members, at least one said side wall members comprising an inner layer of fibers disposed within a matrix material, a layer of viscoelastic material anchored onto to the outside surface of said inner layer, an outer layer of fibers disposed within a matrix material, said outer layer being disposed on and abutting the outside of said layer of viscoelastic material.
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CONTINUITY
[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 61/137,876, which was filed on Aug. 4, 2008, the entirety of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention generally relates to diagnosis of a large class of diseases, which affect the microstructure of tissues, the size and shape of cells, and the arrangement of cells. Alterations of tissues and cells have been reported for cardiac diseases, e.g., hypertrophy, infarction and ischemia, which are the leading cause of death in most developed countries.
BACKGROUND
[0003] Currently, magnetic resonance (MR), ultrasonic (US) and computer tomographic (CT) imaging techniques are major tools for clinical diagnosis of diseases and evaluation of therapeutic interventions. Confocal microscopic imaging techniques constitute a state-of-the-art approach to study progression of diseases in ex vivo preparations of tissue and cells of animal models and to evaluate potential treatments, including stem cells, pharmaceuticals and device implants.
[0004] Confocal microscopy is an indispensable tool in cell biology because the optical sectioning ability of confocal microscopic imaging enables the study of molecular and morphologic changes in thick biologic specimens with sub-micrometer resolution. Typically, confocal microscopy has not been used to examine living tissue because of the need for close association between microscope instrumentation and the imaged tissue, toxic or expensive fluorescent dyes for image contrast, and relatively long image acquisition times. Despite these challenges, confocal microscopy techniques have been shown to provide valuable diagnostic information for various disease states. Studies with biopsy specimens suggest that confocal imaging can provide useful diagnostic information about the presence of precancerous lesions; confocal images of normal and dysplastic cervical biopsy specimens obtained with a confocal reflectance microscope showed a strong correlation between nuclear morphologic features extracted from confocal images and histopathologic diagnosis.
[0005] Confocal microscopic imaging techniques create high resolution images and differs from conventional optical microscopy in that it uses a condenser lens to focus illuminating light of specific wavelengths from a light source, e.g. laser, into a very small, diffraction limited spot within a specimen, and an objective lens to focus the light emitted from that spot onto a small pinhole in an opaque screen. A detector, which is capable of quantifying the intensity of the light that passes through the pinhole at any instant, is located behind the screen. Because only light from within the illuminated spot is properly focused to pass through the pinhole and reach the detector, any stray light from structures above, below, or to the side of the illuminated spot are filtered out. The image resolution is therefore greatly enhanced as compared to other conventional approaches.
[0006] In a scanning confocal microscopic imaging system, a coherent image is built up by scanning point by point over the desired field of view and recording the intensity of the light emitted from each spot, as small spots are illuminated at any one time. Scanning can be accomplished in several ways, including for example and without limitation, via laser scanning. Confocal microscopic imaging system are commercially available through entities such as Carl Zeiss, Nikon, and Olympus. An exemplary confocal is described in U.S. Pat. No. 6,522,444 entitled “Integrated Angled-Dual-Axis Confocal Scanning Endoscopes,” which is assigned to Optical Biopsy Technologies Inc.
[0007] The ability to obtain confocal images of normal and diseased tissue in vivo is limited by the ability to bring the tissue of interest in close proximity to the microscope objective. Flexible confocal microscopic imaging systems incorporating either a solitary optical fiber or a fiber optic imaging bundle are needed to facilitate in vivo imaging of less accessible organ sites. However, a major obstacle for application of confocal microscopic imaging techniques is related to the introduction of fluorescent dyes into biological tissue. Commonly, introduction of dye is performed by infusion or systemic needle injection. Disadvantages of these methods include, for example, the high dosing requirements, washout and inhomogeneous distribution of the fluorescent dye.
SUMMARY OF THE INVENTION
[0008] The present invention relates to a catheter that is configured for the use with a confocal microscopic imaging system including conventional and those based on fiber-optics. The catheter is adapted for the study of tissue at locations within a body wherein one or more fluorescent dyes are selectively introduced into the tissue region under observation.
[0009] In one embodiment, the catheter system comprises a fiber-optic bundle disposed therein at least a portion of a catheter sheath and a carrier of fluorescent dye that is operatively coupled to a distal end of the fiber-optic bundle. In one exemplary aspect, the carrier of fluorescent dye can comprise one or more fluorescent dyes that are loaded therein the carrier at a predetermined concentration and weight per volume of the carrier. The proximal end of the fiber-optic bundle is operatively coupled to a confocal microscopic imaging system, as known in the art and as exemplarily described above.
[0010] In operation, the distal end portion of the catheter is steered through blood vessels or body cavities to a location adjacent to a tissue of interest. Subsequently, the dye carrier is brought in contact with the desired vessel or cavity surfaces, respectively. After contact of the dye carrier with the surfaces, the fluorescent dye(s) are allowed to diffuse from the dye carrier into the tissue. The fluorescent dye is then excited by a light source, such as a focused laser beam, of appropriate wavelength to emit light of a different wavelength for transmission through the fiber optics bundle of the catheter. As one will appreciate, scanning through tissue by exciting the dye and measuring intensities of emitted light allows for two- and three-dimensional imaging.
[0011] According to one embodiment, a method for producing an image of a tissue comprises generating light at a desired wavelength, transmitting the light into a fiber-optic bundle toward a distal end of the fiber-optic bundle and through the dye carrier onto a portion of the tissue of the subject that has been introduced with the one or more fluorescent dyes to excite the fluorescent dye therein the selected tissue. Subsequently, light of a different wavelength is emitted by the excited fluorescent dye and is received therethrough the dye carrier and into the distal end of the fiber-optic bundle, which is operatively coupled to a confocal microscopic system. From the measured intensities of emitted light, two-dimensional images of the tissue and stacks of those images are acquired with imaging techniques in the confocal microscopic system.
[0012] According to another embodiment, a method for producing an ECG-triggered image is described, wherein a reference point of an ECG signal taken from the subject triggers initiates each image acquisition. The imaging comprises generating light at a desired wavelength, repeatedly transmitting the light into a tissue at a desired location within the subject, receiving emitted light from the excited fluorescent dye at the desired location as a result of each light transmission, and processing the received emitted light to form an image or image stack. In one exemplary aspect, a high resolution fast multi-spectral confocal mapping technique and apparatus can be used.
[0013] Other apparatus, methods, and aspects and advantages of the invention will be discussed with reference to the figures and to the detailed description of the preferred embodiments.
BRIEF DESCRIPTION OF THE FIGURES
[0014] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects described below and together with the description, serve to explain the principles of the invention. Like numbers represent the same elements throughout the figures.
[0015] FIG. 1 shows a schematic view of an embodiment of a catheter having a catheter sheath, a fiber-optic bundle, and a dye carrier coupled to a distal end of the fiber-optic bundle. In operation, the dye carrier positioned in contact with a tissue of interest allows dye to diffuse from the dye carrier into portions of the tissue of interest.
[0016] FIG. 2 shows a schematic view of the principle of dye injection and imaging. Diffusion underlies the release of dye from the carrier and dye transport in the tissue of interest. Excitation and emitted light is transmitted through the fiber-optic bundle and the dye carrier.
[0017] FIG. 3A shows a schematic view of an experimental setup up to study the dynamics of dye diffusion.
[0018] FIG. 3B shows the results from the diffusion study schematically shown in FIG. 3A . In the experimental study, the dye carrier (a hydro-gel pad loaded with fluorescent dye Alexa 488 conjugated to dextran) was brought in contact with the surface of a rabbit papillary muscle. As shown in the time lapsed photographs, diffusion is capable of transporting dye from the carrier into the tissue region of interest. The resulting concentration of dye therein the region of interest is sufficient for confocal imaging.
[0019] FIG. 4 is a series of confocal microscopic images of tissue microstructure at different depths through a rabbit's left ventricular muscle. In this study, the dye (Alexa 488 conjugated to dextran) penetrated the epicardium and was diffused into the tissue region of interest.
[0020] FIG. 5 shows an enlarged portion of a confocal microscopic image from the rabbit's left ventricular muscle. The exemplary images allow for the identification of ventricular myocytes and their transverse tubular system, the interstitial space, and blood vessels.
[0021] FIG. 6 shows an exemplary confocal microscopic image of tissue microstructure of a rabbit papillary muscle. The image is from a stack of 100 images and shows a dense arrangement of myocytes.
[0022] FIG. 7 shows the absorption profile of fluorescein isothiocyanate (FITC) in green and the absorption profile of Alexa Fluor 546 in red.
[0023] FIG. 8 is an exemplary experimental setup for confocal imaging of cardiac tissue, according to one embodiment.
[0024] FIG. 9 is a schematic view of an exemplary experimental and processing method for confocal imaging.
[0025] FIG. 10 is an image taken during an exemplary experiment with catheter-based confocal microscopy system (Leica FCM 1000) showing (a) M/30 confocal microprobe with hydrogel carrier loaded with dye; (b) Image of atrial tissue acquired with catheter-based confocal microscopy system and the modified microprobe. Scale: 5 mm in (a) and 50 μm in (b).
[0026] FIG. 11 is exemplary raw XY images from a three-dimensional stack of a trial tissue. The images are from the (a) epicardial surface and a depth of (b) 10 μm, (c) 20 μm, and (d) 30 μm into the myocardium. Scale: 50 μm in (a) applies to (a)-(d).
[0027] FIG. 12 is exemplary raw XY images from a three-dimensional stack of entricular tissue. The images are from the (a) endocardial surface and a depth of (b) 10 μm, (c) 20 μm, and (d) 30 μm into the myocardium. Also shown are (e) a zoomed view of region marked by white box in (c) and (f) a processed image from region marked by white box in (c). The white arrows indicate cross-sections of transverse tubules. Scales: 50 μm in (a) applies to (a)-(d), 2 μm in (e) applies also to (f).
[0028] FIG. 13 is exemplary segmentation of a single cardiac myocyte in (a) XY, (b) XZ and (c) YZ images of a trial tissue. Also shown in (d) is a three-dimensional model of myocyte created by manual segmentation and thresholding. Scale: 20 μm applies to (a)-(c).
[0029] FIG. 14 is a three-dimensional model of a trial tissue shown (a) from epicardial surface, (b) in fiber direction, and (c) from lateral side. Also shown in (d) is a model overlaid with exemplary confocal images in three orthogonal planes. The model includes 17 complete and 21 partial myocytes. Scale: 50 μm applies to (a)-(c).
[0030] FIG. 15 is a three-dimensional model of ventricular tissue shown from endocardial surface. The model includes 11 complete myocytes and 11 partial myocytes. Scale: 50 μm.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The present invention can be understood more readily by reference to the following detailed description, examples, drawing, and claims, and their previous and following description. However, before the present devices, systems, and/or methods are disclosed and described, it is to be understood that this invention is not limited to the specific devices, systems, and/or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
[0032] The following description of the invention is provided as an enabling teaching of the invention in its best, currently known embodiment. To this end, those skilled in the relevant art will recognize and appreciate that many changes can be made to the various aspects of the invention described herein, while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those who work in the art will recognize that many modifications and adaptations to the present invention are possible and can even be desirable in certain circumstances and are a part of the present invention. Thus, the following description is provided as illustrative of the principles of the present invention and not in limitation thereof.
[0033] As used throughout, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a dye,” can include two or more such dyes unless the context indicates otherwise.
[0034] Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
[0035] As used herein, the terms “optional” or “optionally” mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0036] By a “subject” is meant an individual. The term subject can include humans and can also include small or laboratory animals as well as primates. A laboratory animal includes, but is not limited to, a rodent such as a mouse or a rat. The term laboratory animal is also used interchangeably with animal, small animal, small laboratory animal, or subject, which includes mice, rats, cats, dogs, fish, rabbits, guinea pigs, rodents, etc. The term laboratory animal does not denote a particular age or sex. Thus, adult and newborn animals, as well as fetuses (including embryos), whether male or female, are included.
[0037] As used herein and without limitation, “tissue” can refer to an aggregate of cells of a particular kind, together with their intercellular substances, that forms a solid or fluid material. In one aspect, at least one portion of the tissue of interest must be accessible to the device. In one exemplary non-limiting aspect, the tissue can be cardiac tissue. Other tissues suitable for use with this invention include pulmonary, gastrointestinal, urogynecologic, endocrine, neural or vascular tissue.
[0038] Referring to FIGS. 1 and 2 , in one embodiment, a catheter is provided for use with a conventional confocal microscopic imaging system that is configured to develop a confocal image of a portion of a desired tissue of a subject. In one aspect, and as described in more detail below, the confocal microscopic imaging system can comprise a processor. In a further aspect, the catheter can comprise a fiber-optic bundle and a dye carrier.
[0039] In one aspect, the fiber-optic bundle has a distal end and an opposed proximal end. In this aspect, the proximal end of the fiber-optic bundle is placed in operable communication with the confocal microscopic imaging system. In a further aspect, the dye carrier comprises at least one fluorescent dye and is operatively coupled to the distal end of the fiber-optic bundle. In yet another aspect, the catheter can include a catheter sheath that is configured to selectively and at least partially enclose a distal end portion of the fiber-optic bundle. It is also contemplated that the catheter sheath can be configured to selectively and at least partially enclose at least a portion of the dye carrier.
[0040] In a further aspect, the fiber-optic bundle is in communication with a source of light that is configured for selective generation of light at a desired wavelength. As one skilled in the art will appreciate, this allows for light of selected wavelengths to be selectively transmitted down the fiber-optic bundle and through the dye carrier positioned at the distal end of the fiber-optic bundle. In a further aspect, the catheter can comprise a means for positioning a portion of the dye carrier in contact against a tissue region of interest to selectively diffuse the at least one fluorescent dye into the tissue region of interest. Optionally, it is contemplated that the means for positioning a portion of the dye carrier in contact against a tissue region of interest can comprise a means for steering the catheter sheath within the subject to position the dye carrier against the tissue region of interest.
[0041] In another aspect, the dye carrier comprises a light transparent matrix and at least one fluorescent dye. It is further contemplated that the at least one florescent dye can be suspended in a conventional buffer solution such that the at least one florescent dye in its buffer solution can be diffused therein at least a portion of the light transparent matrix of the dye carrier at a predetermined desired concentration. In one example, the at least one fluorescent dye and its buffer solution comprise at least 95% of the dye carrier by weight. In various other exemplary aspects, it is contemplated that the at least one fluorescent dye and its buffer solution can comprise at least 10% of the dye carrier by weight, alternatively, at least 50% of the dye carrier by weight, and, optionally, at least 75% of the dye carrier by weight. In a further aspect, the dye carrier can further comprise at least one conjugated agent, for example and not meant to be limiting, an antibody.
[0042] In various experiments, which are not meant to be limiting but rather serve as exemplary examples, the dye carrier was formed from a hydro-gel having a thickness of between about 30 to about 100 μm and that was configured to have an area in contact with the selected portion of the tissue that ranged from between about 1 to about 4 mm 2 . In these tests, the formed hydro-gel dye carrier comprised about 5% agar and about 95% water.
[0043] Prior to application of the formed hydro-gel dye carrier to the tissue region of interest, between about 0.1 to about 0.5 mg of fluorescent dye in its conventional buffer solution was loaded on the hydro-gel dye carrier and was allowed to diffuse into the dye carrier for approximately 1 min. Fluorescent dyes that were tested include dextran conjugated Alexa 488 and dextran conjugated Texas Red (both from Invitrogen).
[0044] As one skilled in the art will appreciate, the system and methods described herein rely on fluorescence as an imaging mode, primarily due to the high degree of sensitivity afforded by the confocal imaging technique coupled with the ability to specifically target structural components and dynamic processes in chemically fixed as well as living cells and tissues. Many fluorescent probes have been constructed around synthetic aromatic organic chemicals designed to bind with a biological macromolecule (for example, a protein or nucleic acid) or to localize within a specific structural region, such as the cytoskeleton, mitochondria, Golgi apparatus, endoplasmic reticulum, and nucleus. Other fluorescent probes are employed to monitor dynamic processes and localized environmental variables, including concentrations of inorganic metallic ions, pH, reactive oxygen species, and membrane potential. Fluorescent dyes are also useful in monitoring cellular integrity (live versus dead and apoptosis), endocytosis, exocytosis, membrane fluidity, protein trafficking, signal transduction, and enzymatic activity. Despite the numerous advances made in fluorescent dye synthesis during the past few decades, there is very little solid evidence about molecular design rules for developing new fluorochromes, particularly with regard to matching absorption spectra to available confocal laser excitation wavelengths. As a result, the number of fluorophores that have found widespread use in confocal microscopy is a limited subset of the many thousands that have been discovered.
[0045] Fluorophores chosen for confocal applications generally are selected to exhibit a excitability, intensity of emitted lights, and signal persistence sufficient for the instrument to obtain image data that does not suffer from excessive photobleaching artifacts and low signal-to-noise ratios. In widefield fluorescence microscopy, excitation illumination levels are easily controlled with neutral density filters, and the intensity can be reduced (coupled with longer emission signal collection periods) to avoid saturation and curtail irreversible loss of fluorescence. Excitation conditions in confocal microscopy are several orders of magnitude more severe, however, and restrictions imposed by characteristics of the fluorophores and efficiency of the microscope optical system become the dominating factor in determining excitation rate and emission collection strategies.
[0046] In confocal microscopy, excitation of the fluorophores with a focused laser beam at high power densities increases the emission intensity up to the point of dye saturation, a condition whose parameters are dictated by the excited state lifetime. In the excited state, fluorophores are unable to absorb another incident photon until they emit a lower-energy photon through the fluorescence process. When the rate of fluorophore excitation exceeds the rate of emission decay, the molecules become saturated and the ground state population decreases. As a result, a majority of the laser energy passes through the specimen undiminished and does not contribute to fluorophore excitation. Balancing fluorophore saturation with laser light intensity levels helps to achieve a desired signal-to-noise ratio in confocal applications.
[0047] The number of fluorescent probes currently available for confocal microscopy runs in the hundreds, with many dyes having absorption maxima closely associated with common laser spectral lines. An exact match between a particular laser line and the absorption maximum of a specific probe is not always possible, but the excitation efficiency of lines near the maximum is usually sufficient to produce a level of fluorescence emission that can be readily detected. For example, in FIG. 7 the absorption spectra of two common probes are illustrated, along with the most efficient laser excitation lines. The green spectrum is the absorption profile of fluorescein isothiocyanate (FITC), which has an absorption maximum of 495 nanometers. Excitation of the FITC fluorophore at 488 nanometers using an argon-ion laser produces an emission efficiency of approximately 87 percent. In contrast, when the 477-nanometer or the 514-nanometer argon-ion laser lines are used to excite FITC, the emission efficiency drops to only 58 or 28 percent, respectively. One skilled in the art will appreciate that, in this example, the 488-nanometer argon-ion (or krypton-argon) laser line is the most efficient source for excitation of this fluorophore.
[0048] The red spectrum in FIG. 7 is the absorption profile of Alexa Fluor 546, a bi-sulfonated alicyclic xanthene (rhodamine) derivative with a maximum extinction coefficient at 556 nanometers, which is designed specifically to display increased quantum efficiency at significantly reduced levels of photobleaching in fluorescence experiments. The most efficient laser excitation spectral line for Alexa Fluor 546 is the yellow 568-nanometer line from the krypton-argon mixed gas ion laser, which produces an emission efficiency of approximately 84 percent. The next closest laser spectral lines, the 543-nanometer line from the green helium-neon laser and the 594-nanometer lines from the yellow helium-neon laser, excite Alexa Fluor 546 with an efficiency of 43 and 4 percent, respectively.
[0049] Instrumentally, and as one skilled in the art will appreciate, fluorescence emission collection of the confocal microscopic imaging system can be optimized by careful selection of objectives, detector aperture dimensions, dichromatic and barrier filters, as well as maintaining the optical train in precise alignment. In most cases, low magnification objectives with a high numerical aperture should be chosen for the most demanding imaging conditions because light collection intensity increases as the fourth power of the numerical aperture, but only decreases as the square of the magnification. However, resolution can be improved with high magnification objectives. Generally, it is appropriate to focus on restrictions imposed by the physical properties of the fluorophores themselves.
[0050] The choice of fluorescent probes for confocal microscopy generally should address the specific capabilities of the instrument to excite and detect fluorescence emission in the wavelength regions made available by the laser systems and detectors. Although the current lasers used in confocal microscopy produce discrete lines in the ultraviolet, visible, and near-infrared portions of the spectrum, the location of these spectral lines does not always coincide with absorption maxima of popular fluorophores. In fact, it is not necessary for the laser spectral line to correspond exactly with the fluorophore wavelength of maximum absorption, but the intensity of fluorescence emission is regulated by the fluorophore extinction coefficient at the excitation wavelength (as discussed above). The most popular lasers for confocal microscopy are air-cooled argon and krypton-argon ion lasers, the new blue diode lasers, and a variety of helium-neon systems. Collectively, these lasers are capable of providing excitation at ten to twelve specific wavelengths between about 400 and 650 nanometers.
[0051] In a further aspect, the fluorescent dyes for the method and system described herein can be selected based on their molecular weight. Studies have shown that fluorescent dyes having a given molecular weight may not be able to diffuse through particular tissues of interest. For example, Andries and Brutsaert demonstrated that fluorescent dyes that are conjugated to dextran with a molecular weight of 40 kDa did not diffuse through either endocardial endothelium or capillary endothelium, but those with 10 kDa did diffuse easily. Thus, it is desirable to select a molecular weight fluorescent dye that can be introduced and/or diffused into the tissue on interest within a desired time period. See Andries L J, Brutsaert D L. Endocardial endothelium in the rat: junctional organization and permeability. Cell Tissue Res. 1994 September; 277(3):391-400.
[0052] In exemplary non-limiting examples, introduction of fluorescent dyes via the formed hydro-gel dye carrier that have a molecular weight of between about 3 to about 10 kDa were quasi instantaneously available for tissue imaging. In various aspects, it is contemplated that the molecular weight of the at least one fluorescent dye can be less than 40 KDa, alternatively, less than 20 KDa, and, optionally, less than 10 KDa.
[0053] As exemplarily discussed above, the at least one fluorescent dye can comprise an Alexa Fluor dye. The Alexa Fluor dyes produced by Molecular Probes (Alexa Fluor is a registered trademark of Molecular Probes) are sulfonated rhodamine derivatives that exhibit higher quantum yields for more intense fluorescence emission than spectrally similar probes, and have several additional improved features, including enhanced photostability, absorption spectra matched to common laser lines, pH insensitivity, and a high degree of water solubility. The resistance to photobleaching of Alexa Fluor dyes is high enough that even when subjected to irradiation by high-intensity laser sources, fluorescence intensity generally remains stable for some periods of time even in the absence of antifade reagents. This feature enables the water soluble Alexa Fluor probes to be readily utilized for both live-cell and tissue section investigations, as well as in traditional fixed preparations.
[0054] As one skilled in the art will appreciate, the Alexa Fluor dyes are available in a broad range of fluorescence excitation and emission wavelength maxima, ranging from the ultraviolet and deep blue to the near-infrared regions. Alphanumeric names of the individual dyes are associated with the specific excitation laser or arc-discharge lamp spectral lines for which the probes are intended. For example, Alexa Fluor 488 is designed for excitation by the blue 488-nanometer line of the argon or krypton-argon ion lasers, while Alexa Fluor 568 is matched to the 568-nanometer spectral line of the krypton-argon laser. Several of the Alexa Fluor dyes are specifically designed for excitation by either the blue diode laser (405 nanometers), the orange/yellow helium-neon laser (594 nanometers), or the red helium-neon laser (633 nanometers). Other Alexa Fluor dyes are intended for excitation with traditional mercury arc-discharge lamps in the visible (Alexa Fluor 546) or ultraviolet (Alexa Fluor 350, also useful with high-power argon-ion lasers), and solid-state red diode lasers (Alexa Fluor 680). Because of the large number of available excitation and emission wavelengths in the Alexa Fluor series, multiple labeling experiments can often be conducted exclusively with these dyes.
[0055] Alexa Fluor dyes are commercially available as reactive intermediates in the form of maleimides, succinimidyl esters, and hydrazides, as well as prepared cytoskeletal probes (conjugated to phalloidin, G-actin, and rabbit skeletal muscle actin) and conjugates to lectin, dextran, streptavidin, avidin, biocytin, and a wide variety of secondary antibodies. In the latter forms, the Alexa Fluor fluorophores provide a broad palette of tools for investigations in immunocytochemistry, neuroscience, and cellular biology. The family of probes has also been extended into a series of dyes having overlapping fluorescence emission maxima targeted at sophisticated confocal microscopy detection systems with spectral imaging and linear unmixing capabilities. For example, Alexa Fluor 488, Alexa Fluor 500, and Alexa Fluor 514 are visually similar in color with bright green fluorescence, but have spectrally distinct emission profiles. In addition, the three fluorochromes can be excited with the 488 or 514-nanometer spectral line from an argon-ion laser and are easily detected with traditional fluorescein filter combinations. In multispectral (x-y-1; referred to as a lambda stack) confocal imaging applications, optical separation software can be employed to differentiate between the similar signals. The overlapping emission spectra of Alexa Fluor 488, 500, and 514 can be segregated into separate channels and differentiated using pseudocolor techniques when the three fluorophores are simultaneously combined in a triple label investigation.
[0056] Fluorophores designed to probe the internal environment of living cells have been widely examined by a number of investigators, and many hundreds have been developed to monitor such effects as localized concentrations of alkali and alkaline earth metals, heavy metals (employed biochemically as enzyme cofactors), inorganic ions, thiols and sulfides, nitrite, as well as pH, solvent polarity, and membrane potential. These probes bind to the target ion with a high degree of specificity to produce the measured response and are often referred to as spectrally sensitive indicators. Ionic concentration changes are determined by the application of optical ratio signal analysis to monitor the association equilibrium between the ion and its host. The concentration values derived from this technique are largely independent of instrumental variations and probe concentration fluctuations due to photobleaching, loading parameters, and cell retention.
[0057] As noted above, a confocal microscopic imaging system includes a processor that is coupled to a control subsystem and a display, if needed. A memory is coupled to the processor. The memory can be any type of computer memory, and is typically referred to as random access memory “RAM,” in which the system software, and image reconstruction software resides. The confocal microscopic imaging system's image reconstruction software controls the acquisition and processing of the received emitted light and allows the confocal microscopic imaging system to display a two-dimensional or three-dimensional confocal image, as desired. In one aspect, the system software and image reconstruction software, can comprise one or more modules to acquire, process, and display data from the confocal microscopic imaging system. The software comprises various modules of machine code which coordinate the confocal microscopic imaging subsystems.
[0058] Data is acquired from emitted light of the excited tissue regions of interest. The emitted light can be communicated to the confocal microscopic imaging system via the fiber-optic bundle, where the emitted light is measured and processed to form images, and then, if desired, displayed on a display. The system software and image reconstruction software, allow for the management of multiple acquisition sessions and the saving and loading of data associated with these sessions. Post processing of the image data also enabled through the system software and the image reconstruction software.
[0059] As one skilled in the art will appreciate, the confocal microscopic imaging system can be implemented using a combination of hardware and software. The hardware implementation of the system can include any or a combination of the following technologies, which are all well known in the art: discrete electronic components, a discrete logic circuit(s) having logic gates for implementing logic functions upon data signals, an application specific integrated circuit having appropriate logic gates, a programmable gate array(s) (PGA), a field programmable gate array (FPGA), and the like.
[0060] The software of confocal microscopic imaging system comprises executable instructions for implementing control and processing functions, and can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, apparatus, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, apparatus, or device and execute the instructions.
[0061] In the context of this document, a “computer-readable medium” can be any means that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. The computer readable medium can be, for example but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, device, or propagation medium. More specific examples (a non-exhaustive list) of the computer-readable medium would include the following: an electrical connection (electronic) having one or more wires, a portable computer diskette (magnetic), a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or Flash memory), a digital versatile disc (DVD), and a portable compact disc read-only memory (CDROM). Note that the computer-readable medium could even be paper or another suitable medium upon which the program is printed, as the program can be electronically captured, via for instance optical scanning of the paper or other medium, then compiled, interpreted or otherwise processed in a suitable manner if necessary, and then stored in a computer memory.
[0062] The memory can include the image data obtained by the confocal microscopic imaging system and can also include raw data representative of the acquired light. A computer readable storage medium can be coupled to the processor for providing instructions to the processor to instruct and/or configure the processor to perform steps or algorithms related to the operation of the confocal microscopic imaging system. The computer readable medium can include hardware and/or software such as, by way of example only, magnetic disks, magnetic tape, optically readable media such as CD ROM's, and semiconductor memory such as PCMCIA cards. In each case, the media may take the form of a portable item such as a small disk, floppy diskette, cassette, or it may take the form of a relatively large or immobile item such as hard disk drive, solid state memory card, or RAM provided in the support system. It should be noted that the above listed example mediums can be used either alone or in combination.
[0063] The confocal microscopic imaging system can include a control subsystem to direct operation of various components of the confocal microscopic imaging system. The control subsystem and related components may be provided as software for instructing a general or special purpose processor or as specialized electronics in a hardware implementation. The control subsystem is connected to the light source to transmit the desired light at the desired wavelength to the fiber-optic bundle.
[0064] The confocal microscopic imaging system includes an image construction subsystem for converting the electrical signals generated by the received emitted light to data that can be manipulated by the processor and that can be rendered into an image. In various exemplary aspects, the imaging system can provide images with a resolution of between about 0.5 μm to 100 μm. The image construction subsystem can be directed by the control subsystem to operate on the received emitted light data to render an image. In a further exemplary aspect, the control subsystem can also comprise a motor control subsystem that is configured to provide a motor control signal to a motor to control the movement of the distal portion of the catheter to a desired a location on the subject.
[0065] In one embodiment, a subject is connected to electrocardiogram (ECG) electrodes to obtain a cardiac electrical signal from the subject. In one aspect, the cardiac signal from the electrodes can be transmitted to an ECG amplifier to condition the signal for provision to a confocal microscopic imaging system. It is recognized that a signal processor or other such device can be used instead of an ECG amplifier to condition the signal. If the cardiac signal from the electrodes is suitable as obtained, then use of an amplifier or signal processor could be avoided entirely.
[0066] In this aspect, the confocal microscopic imaging system can include an ECG signal processor that, if necessary, is configured to receive signals from an ECG amplifier. The ECG signal processor can be configured to provide signals to the control subsystem. The ECG signal can be used to trigger transmission by the source of light, e.g., a laser, of a single or a number of pulses of light (a pulse train). The confocal microscopic imaging system transmits and receives emitted light data, can provide an interface to a user to control the operational parameters of the confocal microscopic imaging system, and, in an exemplary aspect, can processes data appropriate to formulate an ECG-triggered image.
[0067] In one example, the confocal microscopic imaging system detects a trigger signal from the ECG signal processing module. The trigger signal is based on a subject's ECG signal, which is provided to the ECG signal processing module though use of ECG electrodes and, if necessary, the ECG amplifier. The ECG processing module of the confocal microscopic imaging system can be configured to automatically detect for instance the peak of the R-wave, a fixed and repeatable point on the ECG signal trace from which the transmission of raditation therethrough the catheter to the tissue of interest is triggered. Of course, other ECG features or signals of the subject's cardiac activity, such as, for example and without limitation, acoustic signals or measured with ultrasound can also be used to trigger the imaging system. For example, the P-wave, Q-wave, S-wave, and T-wave or features thereof can be used to trigger the light transmission. Each feature referred to above can represent a reference point, which can trigger the image acquisition or provide a marker for selection of images.
[0068] In another aspect, it is contemplated that an ECG trace can comprise a first and a second, or more of the above described wave peaks. Each peak can provide a reference point of the ECG signal for triggering transmission of radiation energy. When a peak of a given wave type is selected to trigger the transmission of light, subsequent peaks of the same wave type can be used to trigger subsequent transmissions of light.
[0069] In operation, it is contemplated that the distal end portion of the catheter is steered through blood vessels or body cavities to a location adjacent to a tissue of interest. Subsequently, the dye carrier is brought in contact with the desired vessel or cavity surfaces, respectively. After contact of the dye carrier with the surfaces, the florescent dye(s) are allowed to diffuse from the dye carrier into the tissue. The fluorescent dye is then excited by a light source, such as a focused laser beam, of appropriate wavelength to emit light of a different wavelength for transmission through the fiber optics bundle of the catheter. As one will appreciate, scanning through tissue by exciting the dye and measuring intensities of emitted light allows for two- and three-dimensional imaging via a confocal microscopic imaging system.
[0070] According to one embodiment, a method for producing an image of a tissue comprises generating light at a desired wavelength, transmitting the light into a fiber-optic bundle toward a distal end of the fiber-optic bundle and through the dye carrier onto a portion of the tissue of the subject that has been introduced with the one or more fluorescent dyes to excite the fluorescent dye therein the selected tissue. Subsequently, emitted light of a different wavelength is emitted by the excited fluorescent dye and is received therethrough the dye carrier and into the distal end of the fiber-optic bundle, which is operatively coupled to a conventional confocal microscopic system. From the measured intensities of emitted light, one-, two- or three-dimensional images of the cardiac tissue are created.
[0071] According to another embodiment, a method for producing an ECG-triggered image comprises generating light at a desired wavelength, repeatedly transmitting the light into a subject at a desired location within the subject, wherein a reference point of an ECG signal taken from the subject triggers each sequential light transmission, receiving emitted light emitted from the excited fluorescent dye at the desired location as a result of each light transmission, and processing the received emitted light data to form the confocal image. In one exemplary aspect, a high resolution fast multi-spectral confocal mapping technique and apparatus can be used.
Experimental Data
[0072] In one experimental procedure, adult rabbits were anesthetized with pentobarbital (30 mg/kg) and anticoagulated with heparin (2500 USP units/kg). Following thoracotomy, the rabbit hearts were quickly excised and placed in a modified oxygenated Tyrode's solution (in mM: 126 NaCl, 11 Dextrose, 0.1 CaCl2, 13.2 KCl, 1 MgCl2, 12.9 NaOH, 24 HEPES) at room temperature. The hearts were dissected into tissue sections of three types: right ventricular papillary muscle (˜1 mm×1 mm×5 mm), subepicardial ventricular (≈6 mm×2 mm) and atrial tissue (≈6 mm×2 mm). The sections were secured to a polycarbonate holder with sutures as shown in FIG. 8 and stored in the solution until imaging.
[0073] The images were obtained within 6 h of heart isolation. Tissue sections were covered by oxygenated Tyrode's solution during the imaging ( FIG. 8 ). Tissue sections were imaged on an 8-bit BioRad MRC-1024 laser-scanning confocal microscope (BioRad, Hercules, Calif.) with a 40× oil-immersion objective lens (Nikon, Tokyo, Japan). Three-dimensional image stacks with a spatial resolution of 200×200×200 nm were obtained with a field of view (X×Y) of 204.8×153.6 μm extending up to 80 μm into the myocardium (Z direction). The Z-axis was substantially parallel to the laser beam direction.
[0074] Thin hydrogel slices (4 mm×4 mm×40 μm thick) were created using 6.5% agar (GenePure LE Agarose, ISC BioExpress, Kaysville, Utah) in water. These slices were placed in solutions of fluorescent dyes and the dye was allowed to diffuse into the agar hydrogel. Dextran-conjugated, lysinefixable Texas Red with a molecular weight of 3 kDa and excitation/emission wavelengths of 595/615 nm was used at concentrations of 6-12 mg/mL (Molecular Probes, Eugene, Oreg.). This dye and other dextran-conjugated dyes allow for specific labeling of the extracellular space. An imaging chamber was created by cutting an aperture from the bottom of a polystyrene weighing dish and gluing a size #0 glass slide over the opening. The dye-loaded hydrogel slice was placed on the glass slide and dye was delivered by gently pressing the tissue onto the slide. Precautions were taken to ensure that the tissue sample was not compressed in the imaged region. Image regions with a distance of at least 10 μm between the glass slide and tissue surface were used. As shown in FIG. 8 , images were acquired by imaging through the glass slide and hydrogel.
[0075] Image stacks were deconvolved with the iterative Richardson-Lucy algorithm using a measured point spread function (PSF). Briefly, the response g of an imaging system to given sources can be described by convolution of the source image f with the point spread function h:
[0000] g ( x )=( f*h )( x )=∫∫∫ −∞ ∞ f ( x ′) h ( x−x ′) dx′
[0076] The iterative Richardson-Lucy algorithm was used to reconstruct the source image f:
[0000]
g
n
+
1
=
g
n
(
g
0
g
n
*
h
⊗
h
)
[0077] with the cross-correlation operator and g 0 ≡g. The three dimensionalPSF was characterized by imaging 100 nm fluorescent beads embedded in agar. Images of fifteen beads were extracted, aligned and averaged to obtain the PSF, which allowed us to quantitatively characterize our imaging approach. Finally, the PSF was filtered by applying an average filter and re-sampled with a resolution of 200 nm×200 nm×200 nm. The PSF was applied to deconvolve the image stacks.
[0078] Signal-to-noise ratios in the raw images were estimated to characterize image stacks. Regions of 300 voxels were sampled inside myocytes to calculate variances of signal intensity and in the extracellular space to calculate mean signal intensity. The signal-to-noise ratio was calculated from the mean signal intensity divided by the variance. Raw image stacks were processed using a combination of C++ and MatLab software (MathWorks, Natick, Mass.) to remove background signals and correct for depth-dependent attenuation ( FIG. 9 ). The background signal was estimated by averaging signals in small regions where the expected intensity is zero (i.e. inside myocytes). Depth-dependent attenuation of signal intensity was calculated by selecting lines in the Z-axis (laser beam) direction with the smallest standard deviation of the associated intensity. Intensities along these lines were fit to an exponential function using least square optimization to obtain a slice-wise scaling factor as a function of depth.
[0079] Myocytes were segmented by manually deforming a surface mesh followed by iterative thresholding. As shown in FIG. 13 , an initially ellipsoid-shaped mesh comprised of 5120 triangles was wrapped around each myocyte in the field of interest. Histograms of voxel intensities were created for the volume enclosed by each mesh to calculate the mode and standard deviation of voxel intensities. The threshold values were chosen independently for each myocyte based on the calculated mode and standard deviation to distinguish between intra-myocyte and extracellular spaces.
[0080] After thresholding, geometric analysis was performed on the extracted whole myocytes. Principal component analysis (PCA) was used to determine the principal axis of each segmented myocyte. A bounding box was created around each myocyte based on the PCA as illustrated in FIG. 13( d ). The bounding box dimensions in direction of the first, second and third principal axis were considered to be the myocyte length, width and height, respectively. Myocyte volume was calculated by counting the intra-myocyte voxels. Average cross-sectional area was determined by dividing cell volume by length. The volume fraction of tissue occupied by myocytes was determined by sampling random volumes of 300×300×30 voxels within regions of the image stack where all myocytes were segmented. Myocyte density was defined as mean of the myocyte volume fraction (MVF) divided by the volume of each cell (Vi):
[0000]
Myocyte
Density
=
1
n
∑
MVF
V
i
[0081] For some imaging studies, excised hearts were mounted and perfused with the modified Tyrode's solution at 8 mL/min retrogradely through the aorta using the Langendorff method. Two-dimensional images with a field of view of 176.3×124.9 μm and a lateral resolution of 0.48 μm were acquired from the Langendorff preparation with a catheter based confocal system (FCM1000, Leica, Wetzlar, Germany) and a microprobe (M/30). The microprobe tip diameter was 4.2 mm and the working distance was 30 μm. A hydrogel dye carrier was configured as an agar sheath that fit over the catheter tip as shown in FIG. 3( a ).
[0082] Upon pressing the tissue sections onto the hydrogel carrier, the dextran-conjugated Texas Red dye diffused rapidly through the endo- or epicardial layers and into the myocardium. The dye was immediately available in sufficient concentration for confocal imaging of the cardiac microstructure. Exemplary two-dimensional images of atrial and ventricular tissue sections acquired with the BioRad confocal microscope are shown in FIGS. 11( a ) and 12 ( d ), respectively. These images originate from three-dimensional stacks covering approximately 1 μm outside of the tissue surface and up to 80 μm into the myocardium.
[0083] Fluorescence appeared to be associated with clefts between cells (interstitial space), collagen fibers, transverse tubules and capillary vessels; whereas darker regions appeared to be associated with cells. Image slices through the epicardial and endocardial network of thin collagen fibers in atrial and ventricular tissue are shown in FIGS. 11( a ) and 12 ( a ), respectively. The fibers are brighter than their surroundings and appear to be, to some degree, orientated parallel to the myocytes. The image through the ventricular endocardium ( FIG. 12( a )) includes endothelial cells.
[0084] Image slices into atrial and ventricular myocardium are presented in FIGS. 11( b )-( d ) and FIGS. 12( b )-( d ), respectively. These image slices are from depths of 10, 20 and 30 μm into the myocardium with respect to the epicardial or endocardial surface layer ( FIGS. 4( a ) and 5 ( a )). The density of the network of collagen fibers appeared to be larger in the endo- and epicardium than within the myocardium. Furthermore, images extending further into the myocardium exhibited less overall fluorescence.
[0085] Optical properties of the BioRad confocal microscopy system were characterized by measurement of PSFs as described above. The PSF exhibited full widths at half maximum of 0.30 μm in the XY plane (transverse to the laserbeam) and 1.85 μm in the Z direction (parallel to the laser beam).
[0086] In another experiment, images were also acquired with a catheter based confocal microscope (FCM1000, Leica, Wetzlar, Germany). The dye carrier was attached to the catheter tip and gently pressed on the epicardial surface of the atria and ventricles of a Langendorff-perfused heart. An exemplary two-dimensional image of atrial tissue is shown in FIG. 10( b ). The dye was readily available for imaging. High and low fluorescence intensities were associated with the extra- and intracellular spaces, respectively.
[0087] Methods of digital image processing and analysis were applied to quantitatively describe and model cardiac tissue microstructure from three-dimensional image data. For this purpose, 19 image stacks were acquired from a total of 9 rabbits for subsequent analysis. Fourteen of these stacks were rejected from analysis due to low signal-to-noise ratios, discontinuities within the image stack by motion and/or poor tissue quality. Signal-to-noise ratios below 3 were considered low. Background signals were removed, corrected for depth-dependent attenuation, and deconvolved the image stacks. FIGS. 12( e ) and ( f ) illustrate the effect of this processing on the image stacks. Processed image stacks exhibit fine details of myocytes such as the transverse tubular system ( FIG. 12( f )), which were difficult to identify in the unprocessed image data ( FIG. 12( e )).
[0088] Individual myocytes were segmented from three-dimensional image stacks ( FIG. 13 ), which allowed for subsequent spatial modeling ( FIGS. 14 and 15 ) and quantitative analysis of myocytes (Tables I and II). Segmentation was performed on 50 atrial myocytes and 36 ventricular myocytes. Quantitative analysis was only performed on whole myocytes, which included 28 atrial myocytes and 20 ventricular myocytes.
[0089] An exemplary segmentation of a single myocyte from a three-dimensional stack of atrial tissue is shown in FIG. 13 . The manually deformed surface mesh is illustrated in three orthogonal planes in FIGS. 13( a )-( c ). Threshold values to distinguish between intra-myocyte and extracellular space were chosen to be the mode plus 2 standard deviations of signal intensity for each segmented myocyte. FIG. 13( d ) shows the segmented myocyte after thresholding and in a bounding box aligned to the principal axes of the myocyte. The dimensions of the bounding box determined the length, width and height of the myocyte. Three-dimensional spatial models of segmented myocytes from three-dimensional stacks of atrial and ventricular tissue are shown in FIGS. 14( a ) and 15 , respectively. FIG. 14( d ) shows a three-dimensional visualization of the atrial model overlaid with orthogonal confocal images.
[0090] Quantitative analysis revealed mean and standard deviation (mean±sd) of lengths, widths and heights of atrial myocytes to be 105.0±10.6, 13.1±1.7 and 9.7±1.6 μm, respectively, and ventricular myocytes to be 112.3±14.3, 18.4±2.3 and 14.1±2.7 μm, respectively. Average volumes of atrial and ventricular myocytes were 4901±1713 and 10,299±3598 μm 3 , respectively. Furthermore, the myocyte volume fractions for atrial and ventricular tissue were 72.4±4.7% and 79.7±2.9%, respectively. Myocyte density was 165,571±55,836 and 86,957±32,280 cells/mm 3 for atrial and ventricular tissue, respectively. Principal component analysis demonstrated that the long (first principal) axis of myocytes was parallel to the surface of atrial and ventricular tissue ( FIGS. 14 and 15 ) within 6° and 3° deviation to the surface plane, respectively.
[0091] Furthermore, the majority of ventricular myocytes (70%) had their second principal axis approximately parallel (<25°) to the tissue surface. In contrast, atrial tissue did not show parallel orientation of the second principal axis with respect to the surface.
[0092] Although several embodiments of the invention have been disclosed in the foregoing specification, it is understood by those skilled in the art that many modifications and other embodiments of the invention will come to mind to which the invention pertains, having the benefit of the teaching presented in the foregoing description and associated drawings. It is therefore understood that the invention is not limited to the specific embodiments disclosed herein, and that many modifications and other embodiments of the invention are intended to be included within the scope of the invention. Moreover, although specific terms are employed herein, they are used only in a generic and descriptive sense, and not for the purposes of limiting the described invention.
[0093] Various publications are referenced in this document. These publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed system and method pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.
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A system and method for confocal imaging of tissue in vivo and in situ, e.g., for minimally invasive diagnosis of patients. A catheter is provided that has a dye carrier coupled to the distal end of a fiber optics bundle, which allows for the introduction of at least one fluorescent dye therein the dye carrier into a portion of the tissue of interest of a subject or patient when the dye carrier is selectively brought into contact with the portion of the tissue of interest. The resulting confocal images permit the acquisition of diagnostic information on the progression of diseases at cellular/tissue level in patients. Furthermore, a system for ECG-triggered image acquisition is provided.
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TECHNICAL FIELD
This invention relates to water-based medical and dental cements.
BACKGROUND OF THE INVENTION
Fluoroaluminosilicate glass cements (also known as “glass ionomer cements”) are used extensively in restorative dentistry. Two major classes of such cements are in current use. The first class is known as conventional glass ionomers. Conventional glass ionomers typically employ as their main ingredients a homopolymer or copolymer of an α,β-unsaturated carboxylic acid (e.g., poly acrylic acid, copoly (acrylic, itaconic acid), etc.), a fluoroaluminosilicate (“FAS”) glass, water, and chelating agent such as tartaric acid. Conventional glass ionomers typically are supplied in powder/liquid formulations that are mixed just before use. The mixture will undergo self-hardening in the dark due to an ionic reaction between the acidic repeating units of the polycarboxylic acid and cations leached from the glass.
The second major class of glass ionomer cements is known as resin-modified glass ionomer (“RMGI”) cements. Like a conventional glass ionomer, an RMGI cement employs an FAS glass. However, the organic portion of an RMGI is different. In one type of RMGI, the polycarboxylic acid is modified to replace or end-cap some of acidic repeating units with pendent curable groups and a photoinitiator is added to provide a second cure mechanism, e.g., as in U.S. Pat. No. 5,130,347. Acrylate or methacrylate groups are usually employed as the pendant curable group. A redox cure system can be added to provide a third cure mechanism, e.g., as in U.S. Pat. No. 5,154,762. In another type of RMGI, the cement includes a polycarboxylic acid, an acrylate or methacrylate-functional monomer and a photoinitiator, e.g., as in Mathis et al., “Properties of a New Glass Ionomer/Composite Resin Hybrid Restorative”, Abstract No. 51, J. Dent Res., 66:113 (1987) and as in U.S. Pat. Nos. 5,063,257, 5,520,725, 5,859,089 and 5,962,550. Photoinitiator cure systems have been said to be preferred (see, e.g., U.S. Pat. Nos. 5,063,257 and 5,859,089). Conventional peroxide oxidation agents have been noted to be unstable in ionomer cements (see, e.g., U.S. Pat. No. 5,520,725). Some patents exemplify RMGI cements that include a polycarboxylic acid, an acrylate or methacrylate-functional monomer and a redox or other chemical cure system (see, e.g., U.S. Pat. Nos. 5,520,725 and 5,871,360). Various monomer-containing or resin-containing cements are also shown in U.S. Pat. Nos. 4,872,936, 5,227,413, 5,367,002 and 5,965,632. RMGI cements are usually formulated as powder/liquid or paste/paste systems, and contain water as mixed and applied. They harden in the dark due to the ionic reaction between the acidic repeating units of the polycarboxylic acid and cations leached from the glass, and commercial RMGI products typically also cure on exposure of the cement to light from a dental curing lamp.
There are many important benefits of using glass ionomer cements. Fluoride release from glass ionomers tends to be higher than from other classes of cements such as metal oxide cements, compomer cements (anhydrous light-curable single-part paste systems containing FAS glass, as shown in Published PCT Application No. WO 97/18792 and U.S. Pat. Nos. 5,859,089, 5,962,550 and 6,126,922) or fluoridated composites, and thus glass ionomer cements are associated with cariostatic behavior. Although differences exist between commercial brands of glass ionomer cements, in general it is believed that high fluoride release leads to better cariostatic protection. Another important reason for using glass ionomer cements is the very good clinical adhesion of such cements to tooth structure, thus providing highly retentive restorations. Because conventional glass ionomers do not need an external curing initiation mode, they can be placed in bulk as a filling material in deep restorations, without requiring layering. However, conventional glass ionomers are rather technique sensitive (e.g., the performance can depend on the mixture ratio and the manner and thoroughness of mixing) and are quite brittle as evidenced by their low flexural strength. Thus restorations made from conventional glass ionomer cement mixtures tend to undergo fracture quite readily. Cured RMGIs have increased flexural strength and are less prone to mechanical fracture than conventional glass ionomer cements.
SUMMARY OF THE INVENTION
Photocurable RMGIs typically are placed in layers to overcome the light attenuation that accompanies increased thickness. This attenuation can be offset somewhat by instead or in addition employing a dark-curing chemical cure mechanism (such as the three-way cure mechanism shown in the above-mentioned U.S. Pat. No. 5,154,762 or the two-way or three-way cure mechanisms shown in the above-mentioned U.S. Pat. Nos. 5,520,725 and 5,871,360). However, for highly viscous RMGI cement mixtures it usually is necessary to perform a preliminary tooth priming or conditioning step in which a low viscosity aqueous-organic conditioner or primer is applied to the tooth prior to placement of the RMGI mix. Thus an additional step is required to obtain a clinically desirable restoration.
Neither conventional glass ionomers nor RMGIs have entirely satisfactory properties, and further improvements in the performance and ease of use of glass ionomer cements would be desirable.
The present invention provides, in one aspect, a glass ionomer cement comprising a mixture of a polymer having a plurality of acidic repeating units but being substantially free of polymerizable vinyl groups (“Polymer A”) and a polymer having a plurality of acidic repeating units and a plurality of polymerizable vinyl groups (“Polymer B”). Preferably the cements of the invention comprise:
a) Polymer A;
b) Polymer B;
c) FAS glass;
d) redox cure system that can initiate dark cure of the vinyl groups; and
e) water.
The invention also provides methods for making and using glass ionomer cements.
Preferred embodiments of the cements of the invention can be used without requiring a preliminary tooth priming or conditioning step and without requiring a curing lamp. The cements offer ease of mixing, convenient viscosity, convenient cure, good flexural strength, good adhesion to dentin and enamel, and high fluoride release, even when cured in thick sections and in the dark.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a graph showing fluoride release vs. time for a cement of the invention and two comparison cements.
DETAILED DESCRIPTION
As used in connection with this invention, the term “polymer” includes molecules whose backbone is derived from one monomer (viz. a homopolymer) or from two or more monomers (viz., a copolymer). A polymer typically has a weight average molecular weight of at least about 2000.
Polymer A has a plurality of acidic repeating units but is substantially free of vinyl groups, that is, Polymer A has a sufficiently small number of vinyl groups so that it will not harden when combined with the redox cure system and water. Preferably, Polymer A contains less than about 1 mole percent vinyl groups. The acidic repeating units in Polymer A can be carboxyl or other acid groups (e.g., oxyacids of atoms such as boron, phosphorus and sulfur) that in the presence of water and the FAS glass will react with cations eluted from the glass and form a hardened cement composition. Polymer A need not be entirely water-soluble, but it should be at least sufficiently water-miscible (e.g., at least 2 weight percent or more) so that Polymer A does not undergo substantial sedimentation when combined with the other liquid ingredients of the cement. Polymer A can be formed in a variety of ways, from a variety of materials. A preferred form of Polymer A comprises a polymer of an α,β-unsaturated carboxylic acid. Such polymers include but are not limited to polymers of acrylic acid, 2-chloroacrylic acid, 2-cyanoacrylic acid, aconitic acid, citraconic acid, fumaric acid, glutaconic acid, itaconic acid, maleic acid, mesaconic acid, methacrylic acid, tiglic acid and mixtures or copolymers thereof. Suitable Polymer A materials are also available from a wide variety of commercial sources, and many are found in currently available glass ionomer cements such as KETAC-FIL™ (3M ESPE Dental Products), FUJI II™ and FUJI IX™ (G-C Dental Industrial Corp.) and CHEMFIL™ Superior (Dentsply International). Preferably, Polymer A comprises polyacrylic acid, an acrylic acid:itaconic acid copolymer or an acrylic acid:maleic acid copolymer. The substitution or addition of polymers or copolymers of other carboxylic acids can provide altered toughness and altered set time. Copolymers of α,β-unsaturated carboxylic acids with small amounts of other non-acidic monomers, e.g., N-vinyl pyrrolidone, or with various acrylate-terminated polyethers, or with esters of α,β-unsaturated carboxylic acids (e.g., methyl methacrylate) and the like may also be used. As will be appreciated by those skilled in the art, Polymer A should have a molecular weight sufficient to provide good storage, handling and mixing properties. A preferred molecular weight for Polymer A is about 3000 to about 300,000 weight average molecular weight as evaluated using gel permeation chromatography and a polystyrene standard, with about 10,000 to about 150,000 being most preferred. The cement should contain a sufficient quantity of Polymer A in order to provide the desired setting or hardening rate and desired overall properties following hardening. Preferably the mixed but unset cements of the invention contain about 0.5 to about 30 percent by weight, more preferably about 0.5 to about 20 percent by weight, and most preferably about 1 to about 10 percent by weight of Polymer A, based on the total weight (including water) of the mixed but unset cement components.
Polymer B has a plurality of acidic repeating units and a plurality of polymerizable vinyl groups. The acidic repeating units can be like those described above for Polymer A. The vinyl groups enable Polymer B to polymerize in the presence of the redox cure system. Polymer B need not be entirely water-soluble, but it should be at least sufficiently water-miscible (e.g., at least 5 weight percent or more) so that it does not undergo substantial sedimentation when combined with the other liquid ingredients of the cement. Polymer B can be formed in a variety of ways, from a variety of materials. One convenient method for forming Polymer B involves partially reacting a material suitable for use as Polymer A (or suitable for use as a Polymer A precursor such as a polymeric acid anhydride) with a monomer containing an acid- or acid anhydride-reactive group and containing one or more vinyl groups that will provide the desired polymerizable functionality in Polymer B. The acid- or acid anhydride-reactive group reacts with acid units on Polymer A (or with anhydride units in a polymeric acid anhydride precursor to Polymer A) to provide pendant vinyl groups in the resulting reaction product. Another convenient method for forming Polymer B involves copolymerizing a suitable α,β-unsaturated carboxylic acid and a suitable α,β-unsaturated monomer containing one or more such pendant vinyl groups. Preferably the Polymer B vinyl groups are acrylate or methacrylate groups. Most preferably the Polymer B vinyl groups are linked to the polymer backbone through an amide linkage of other suitable organic linking group. Other suitable groups include but are not limited to styryl (CH 2 :CHC 6 H 5 ) groups, allyl (CH 2 :CHCH 2 —) groups and other groups that will be familiar to those skilled in the art. Preferably, the number of acidic repeating units and vinyl groups is adjusted to provide an appropriate balance of properties in the cement, both during and after cement hardening. Polymers containing about 70 to about 90 mole % acidic repeating units and about 10 to about 30 mole % vinyl groups are preferred. Suitable embodiments of Polymer B include but are not limited to those described in U.S. Pat. Nos. 4,872,936, 5,130,347 and 5,227,413. Suitable Polymer B materials can be found in currently available RMGI cements such as VITREMER™ and VITREBOND™ (3M ESPE Dental Products). These cements contain Polymer B but no Polymer A. Preferably, Polymer B comprises an acrylic acid:itaconic acid copolymer that has been partially reacted with isocyanatoethyl methacrylate as shown in U.S. Pat. No. 5,130,347. As will be appreciated by those skilled in the art, Polymer B should have a molecular weight sufficient to provide good storage, handling and mixing properties. A preferred molecular weight for Polymer B is about 3000 to about 300,000 weight average molecular weight, with about 10,000 to about 150,000 being most preferred. The cement should contain a sufficient quantity of Polymer B in order to provide the desired curing rate and desired overall properties following cure. Preferably the mixed but unset cements of the invention contain about 1 to about 30 percent by weight, more preferably about 1 to about 25 percent by weight, and most preferably about 5 to about 20 percent by weight of Polymer B, based on the total weight (including water) of the mixed but unset cement components.
The FAS glass preferably contains sufficient elutable cations so that a hardened cement will form when the glass is mixed with Polymer A and water. The glass also preferably contains sufficient elutable fluoride ions so that the hardened cement will have cariostatic properties. The glass can be made from a melt containing fluoride, alumina and other glass-forming ingredients using techniques familiar to those skilled in the FAS glassmaking art. The FAS glass preferably is in the form of particles that are sufficiently finely-divided so that they can conveniently be mixed with the other cement components and will perform well when the resulting mixture is used in the mouth. Preferred average particle diameters for the FAS glass are about 0.2 to about 15 micrometers, more preferably about 1 to 10 micrometers, as measured using, for example, a sedimentation analyzer. Suitable FAS glasses will be familiar to those skilled in the art, and are available from a wide variety of commercial sources, and many are found in currently available glass ionomer cements such as VITREMER™, VITREBOND™, RELY X™ LUTING CEMENT and KETAC-FIL™ (3M ESPE Dental Products), FUJI II™ and FUJI IX™ (G-C Dental Industrial Corp.) and CHEMFIL™ Superior (Dentsply International). The FAS glass can optionally be subjected to a surface treatment. Suitable surface treatments include but are not limited to acid washing (e.g., treatment with a phosphoric acid), treatment with a phosphate, treatment with a chelating agent such as tartaric acid, and treatment with a silane or an acidic or basic silanol solution. Desirably the pH of the treating solution or the treated glass is adjusted to neutral or near-neutral, as this can increase storage stability of the cement. The resulting treated glass can be used in cements containing FAS glass, Polymer A and Polymer B, and can also be used in cements containing FAS glass and Polymer A alone, or FAS glass and Polymer B alone.
The cement should contain a sufficient quantity of FAS glass in order to provide the desired curing rate and desired overall properties following cure. Preferably the mixed but unset cements of the invention contain less than about 90%, more preferably about 25% to about 85%, and most preferably about 45% to about 75% by weight of FAS glass, based on the total weight (including water) of the mixed but unset cement components.
The redox cure system promotes cure of the vinyl groups on Polymer B when the cement components are mixed. The cure is a dark reaction, that is, it not dependent on the presence of light and can proceed in the absence of light. A variety of redox cure systems can be employed in the invention. Typically these systems employ a reducing agent and an oxidizing agent. The reducing agent and oxidizing agent preferably are soluble in the combination of liquid components of the mixed cement. Useful reducing agents and oxidizing agents include but are not limited to those shown in “Redox Polymerization”, G. S. Misra and U. D. N. Bajpai, Prog. Polym. Sci., 8, 61-131 (1982). The reducing agent and oxidizing agent preferably are also sufficiently shelf-stable and free of undesirable colorization to permit their storage and use under typical dental conditions. Suitable reducing agents will be familiar to those skilled in the art, and include but are not limited to ascorbic acid, cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, various amines, hydroxylamine (depending upon the choice of oxidizing agent), oxalic acid, thiourea, and derivatives of oxyacids of sulfur at an oxidation state of V or less. Derivatives of oxyacids of sulfur at an oxidation state of IV are particularly useful. Suitable oxidizing agents will also be familiar to those skilled in the art, and include but are not limited to cobalt (III) chloride, tert-butyl hydroperoxide, ferric chloride, hydroxylamine (depending upon the choice of reducing agent), perboric acid and its salts, and salts of a permanganate or persulfate anion. Hydrogen peroxide can also be used, although it may interfere with a photoinitiator if present in the cement. In some instances oxygen (e.g., from adventitious air) can act as the oxidant, particularly if the reducing agent comprises at least one oxyacid of sulfur IV or its derivative. It may also be desirable to use more than one oxidizing agent or more than one reducing agent. Small quantities of transition metal compounds may also be added to accelerate the rate of redox cure. The amount of reducing agent and oxidizing agent should be sufficient to provide the desired degree of polymerization of Polymer B. Preferably the mixed but unset cements of the invention contain a combined weight of about 0.01 to about 10%, more preferably about 0.2 to about 5%, and most preferably about 0.5 to about 5% of the reducing agent and oxidizing agent, based on the total weight (including water) of the mixed but unset cement components. The reducing agent or the oxidizing agent can be microencapsulated as described in U.S. Pat. No. 5,154,762. This will generally enhance shelf stability of the cement parts and if necessary permit packaging both the reducing agent and oxidizing agent together. For example, through appropriate selection of an encapsulant, both the oxidizing agent and reducing agent can be combined with the FAS glass and kept in a storage-stable state. Likewise, through appropriate selection of a water-insoluble encapsulant, the reducing agent and oxidizing agent can be combined with Polymer A, Polymer B and water and maintained in a storage-stable state. Preferably the encapsulant is a medically acceptable polymer and a good film former. Also, the glass transition temperature (Tg) of the encapsulant preferably is above room temperature.
Photoinitiators can also be added to the cement but are not required. The photoinitiator should be capable of promoting polymerization of the vinyl groups on Polymer B (e.g., capable of promoting free-radical crosslinking of an α,β-unsaturated group) on exposure to light of a suitable wavelength and intensity. The photoinitiator preferably is sufficiently shelf-stable and free of undesirable coloration to permit its storage and use under typical dental conditions. Visible light photoinitiators are preferred. The photoinitiator preferably is water-soluble or water-miscible. Photoinitiators bearing polar groups usually have a sufficient degree of water-solubility or water-miscibility. The photoinitiator frequently can be used alone but typically it is used in combination with a suitable donor compound or a suitable accelerator (for example, amines, peroxides, phosphorus compounds, ketones and alpha-diketone compounds). Suitable visible light-induced and ultraviolet light-induced initiators will be familiar to those skilled in the art. Combinations of an alpha-diketone (e.g., camphorquinone) and a diaryliodonium salt (e.g., diphenyliodonium chloride, bromide, iodide or hexafluorophosphate) with or without additional hydrogen donors (such as sodium benzene sulfinate, amines and amine alcohols) are particularly preferred. If employed, the photoinitiator should be present in an amount sufficient to provide the desired rate of photopolymerization. This amount will be dependent in part on the light source, the thickness of the cement layer to be exposed to radiant energy and the extinction coefficient of the photoinitiator. Preferably, mixed but unset photocurable cements of the invention will contain about 0.01 to about 5%, more preferably from about 0.1 to about 2% photoinitiator, based on the total weight (including water) of the mixed but unset cement components.
The cements of the invention contain water. The water can be present in the cement as sold, or (less preferably) added by the practitioner just prior to mixing and use. Unlike a compomer, appreciable water is present in the cement as applied. The water can be distilled, deionized or plain tap water. Generally, deionized water is preferred. The amount of water should be sufficient to provide adequate handling and mixing properties and to permit the transport of ions in the reaction between the FAS glass and the acidic repeating units on Polymer A and Polymer B. Preferably, water represents about 0.5% to about 40%, more preferably about 1% to about 30%, and most preferably about 5% to about 20% of the total weight of ingredients used to form the mixed but unset cement.
The cements of the invention can if desired also contain one or more solvents, diluents or α,β-unsaturated monomers. Suitable solvents or diluents include but are not limited to alcohols such as ethanol and propanol. The addition of α,β-unsaturated monomers can provide altered properties such as toughness, adhesion, set time and the like. If α,β-unsaturated monomers are employed, they preferably are water-soluble, water-miscible or water-dispersible. Water-soluble, water-miscible or water-dispersible acrylates and methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, glycerol mono- or di-methacrylate, trimethylol propane trimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, urethane methacrylates, acrylamide, methacrylamide, methylene bis-acrylamide or methacrylamide, and diacetone acrylamide and methacrylamide are preferred. Other α,β-unsaturated acidic monomers such as glycerol phosphate monomethacrylates, glycerol phosphate dimethacrylates, hydroxyethyl methacrylate phosphates, citric acid di- or tri-methacrylates and the like may also be used as reactive diluents. Mixtures of α,β-unsaturated monomers can be added if desired. Preferably, the mixed but unset cements of the invention will contain a combined weight of about 0.5 to about 40%, more preferably about 1 to about 30%, and most preferably about 5 to about 20% water, solvents, diluents and α,β-unsaturated monomers, based on the total weight (including such water, solvents, diluents and α,β-unsaturated monomers) of the mixed but unset cement components.
The cements of the invention can also contain non-fluoride-releasing fillers. These fillers can be acid-reactive or non-acid-reactive. Like the FAS glass, the non-fluoride-releasing fillers preferably are sufficiently finely-divided so that they can conveniently be mixed with the other ingredients and used in the mouth. Suitable acid-reactive fillers include but are not limited to metal oxides and hydroxides, metal salts that will react with the acidic repeating units on Polymer A or Polymer B, and non-fluoride-releasing glasses that contain an elutable multivalent cation such as strontium, calcium, zinc, aluminum, iron or zirconium. Suitable metal oxides include but are not limited to barium oxide, calcium oxide, magnesium oxide and zinc oxide and the like. Suitable metal hydroxides barium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide and the like. Suitable metal salts include but are not limited to salts of multivalent cations, for example aluminum acetate, aluminum chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum nitrate, barium nitrate, calcium nitrate, magnesium nitrate and strontium nitrate. Suitable glasses include but are not limited to borate glasses and phosphate glasses. Suitable non-acid-reactive fillers include but are not limited to fumed silica, barium aluminosilica, zirconia-silica microspheres and ground quartz. Non-acid-reactive fillers are especially useful in paste/paste formulations. Suitable acid-reactive and non-acid-reactive fillers will be familiar to those skilled in the art and are available from a variety of commercial sources. If desired, the filler can be subjected to a surface treatment such as those described above for FAS glass. The amount of filler should be sufficient to provide the desired mixing and handling properties before cure, and good performance after cure, but should not be so large as to prevent incorporation of sufficient FAS glass to provide the desired degree of cariostatic activity. Preferably, the filler represents less than about 50%, more preferably less than about 40%, and most preferably from 0% to about 30% by weight of the total weight (including water) of the unset cement components.
If desired, the cements of the invention can contain other typical ionomer adjuvants such as pigments, chelating agents, surfactants, rheology modifiers and the like. The types and amounts of such adjuvants will be apparent to those skilled in the art.
The cements of the invention can be supplied in a variety of forms including two-part powder/liquid, paste/liquid and paste/paste systems. Other forms employing combinations of two or more parts each of which is in the form of a powder, liquid, gel or paste are also possible. In such multi-part systems, Polymer A and B could be contained in separate parts of the cement or contained in only one part of the cement. As an example of a multi-part system, the FAS glass and Polymer A or Polymer B can be included in a first anhydrous part, and water can be included in a second part. For example, in a powder/liquid system, a powder containing the FAS glass and optionally containing a lyophilized (e.g., freeze-dried) or other anhydrous form of Polymer A or Polymer B (or both Polymer A and Polymer B) can be combined with a liquid containing Polymer B, Polymer A, (or both Polymer B and Polymer A) and water. The redox cure system can be added to one or both of the powder and the liquid, and encapsulated as needed to prevent premature reaction. Typically the cement will be sold in the form of a sealed kit containing the cement ingredients packaged in suitably-designed containers, together with instructions for use of the cement and optionally one or more suitably-designed auxiliary devices (e.g., mixing or dispensing devices) that help a practitioner to prepare and use the cement.
As an example of a paste/liquid system, the paste can contain the FAS glass and the liquid can contain water. For instance, the paste can contain the FAS glass and a suitable α,β-unsaturated monomer or reactive oligomer and the liquid can contain Polymer A, Polymer B, water and optionally a suitable α,β-unsaturated monomer or oligomer. The redox cure system can be added to one or both of the paste and the liquid, and encapsulated as needed to prevent premature reaction.
As an example of a paste/paste system, the FAS glass can be included in the first paste and Polymer B can be included in the second paste. For instance, the first paste can include the FAS glass and a suitable α,β-unsaturated monomer, and the second paste can include Polymer A, Polymer B, water, a non-acid-reactive filler and optionally a suitable α,β-unsaturated monomer. The redox cure system can be added to any or all of such pastes, and encapsulated as needed to prevent premature reaction.
The cements of the invention can be mixed and clinically applied using conventional techniques. A curing light is not required or desired (unless a photoinitiator has been included in the cement). The cements can provide the convenience of conventional self-cure glass ionomers yet provide the improved physical properties characteristic of light-cure or tri-cure glass ionomers. The cements can provide very good adhesion to dentin and enamel, without requiring hard tissue pretreatment. The cements can also provide very good long-term fluoride release. Hence the cements of the invention provide glass ionomer cements that can be cured in bulk without the application of light or other external curing energy, do not require a pre-treatment, have improved physical properties including improved flexural strength, and have high fluoride release for cariostatic effect. The cements will have particular utility in clinical applications where cure of a conventional light-curable cement may be difficult to achieve. Such applications include but are not limited to deep restorations, large crown build-ups, endodontic restorations, attachment of orthodontic brackets (including pre-coated brackets, where for example a paste portion could be pre-applied to the bracket and a liquid portion could later be brushed onto a tooth), bands, buccal tubes and other devices, luting of metallic crowns or other light-impermeable prosthetic devices to teeth, and other restorative applications in inaccessible areas of the mouth. The combination of an ionic hardening reaction between the FAS glass and acidic repeating units on Polymer A and Polymer B, plus a separate redox curing dark reaction involving the vinyl groups on Polymer B, facilitates thorough, uniform cure and retention of good clinical properties. The cements of the invention thus show good promise as a universal restorative.
The cements can also be provided in the form of preformed cured articles that can be ground or otherwise formed into a custom-fitted shape by the dentist or other user.
The cements of the invention are further described in the following illustrative examples, which show various powder/liquid systems. The manner in which other systems would be prepared will readily be understood by those skilled in the art. In formulating any such systems, care should be taken to avoid combinations that might cause premature curing reactions to take place during storage of the components prior to mixing and use. The examples shown below employ a relatively large portion of FAS glass, and thus are relatively viscous. These relatively viscous formulations may be especially useful for use in an atraumatic restorative technique (“ART”, see “Atraumatic Restorative Treatment”, J. Frencken, T. Pilot, Y. Songpaisan, P. Phantumvanit, Journal of Public Health Dentistry, 56, No. 3 (Special issue 1996) or a minimal intervention (“MI”) restorative technique (see M. Tyas, K. Anusavice, J. Frencken, G. Mount, “Minimal Intervention Dentistry—a Review”, FDI Commission Project 1-97, International Dental Journal, 50:1-12 (2000)). Straightforward alterations in the formulations shown below will provide other formulations (e.g., more or less viscous formulations) suitable for a host of other dental and orthodontic applications. Unless otherwise indicated, all parts and percentages are on a weight basis and all water is deionized water.
The following abbreviations for starting materials were employed:
AA:ITA
Polymer A, made from a 4:1 mole ratio copolymer of acrylic
acid:itaconic acid, prepared according to Example 3 of U.S. Pat.
No. 5,130,347, Mw (avg) = 106,000; polydispersity ρ = 4.64.
AA:IA:IEM
Polymer B, made by reacting AA:ITA with sufficient 2-
isocyanatoethyl methacrylate to convert 16 mole percent of the acid
groups of the copolymer to pendent methacrylate groups, according
to the dry polymer preparation of Example 11 of U.S. Pat. No.
5,130,347.
BHT
Butylated hydroxytoluene.
EPS
Encapsulated potassium persulfate, prepared according to Example
9 of U.S. Pat. No. 5,154,762.
FAS I
An ascorbic acid-treated FAS glass powder like Glass A of
Example 1 of U.S. Pat. No. 5,154,762 (but having a surface area
of 2.8 m 2 /g) was silane-treated with a liquid treatment solution. The
treatment solution had been prepared by combining 4 parts A174 γ-
methacryloxypropyl trimethoxysilane (CK Witco Corp.) and 40
parts water, adding glacial acetic acid to obtain a pH of 3.01, and
stirring for 0.5 hours. The resultant clear treatment solution was
mixed with 100 parts of the glass powder to provide a slurry. The
slurry was stirred for 1.5 hours, poured into tray lined with
TEFLON ™ polytetrafluoroethylene (DuPont) and dried for 16
hours at 80° C. The resulting dried cake was crushed by sifting it
through a 60 micrometer sieve.
FAS II
An FAS glass like FAS I was prepared but sifted through a 74
micrometer sieve.
FAS III
The glass frit of Example 1 of U.S. Pat. No. 5,154,762 was
ground to a surface area of 84 m 2 /g and silane-treated with a liquid
treatment solution. The treatment solution had been prepared by
combining 32 parts A174 γ-methacryloxypropyl trimethoxysilane
(CK Witco Corp.), 224 parts water and 32 parts glacial acetic acid,
and stirring for 0.5 hours. The resultant clear treatment solution
was mixed with 400 parts of the glass powder to provide a slurry.
After 30 minutes of mixing the pH was adjusted to 6.7 by adding
ammonium hydroxide. The mixture was then poured into a glass
tray and dried for 17 hours at 80° C. The resulting dried cake was
crushed by sifting it through a 74 micrometer sieve.
FAS IV
FAS IV was like FAS I but without silane treatment.
FAS V
50/50 Blend of FAS II and IV.
GDMA
Glyceryl dimethacrylate.
HEMA
2-Hydroxyethyl methacrylate.
PS
Finely ground potassium persulfate.
STS
Sodium p-toluene sulfinate.
The following abbreviations for measurements were employed:
CS
Compressive strength, evaluated by first injecting the mixed cement
samples into a glass tube having a 4 mm inner diameter. The ends
of the sample were plugged with silicone plugs. The filled tubes
were subjected to 0.275 MPa pressure for 5 minutes. For light-
cured cement specimens, the samples were cured by radial exposure
to two XL3000 ™ dental curing lights (3M) while still under
pressure. For self-cured cement specimens, the samples were
instead placed in a chamber at 37° C. and ≧90% relative humidity
and allowed to stand for 1 hour. The cured samples were next
placed in 37° C. water for 1 day, and then cut to a length of 8 mm.
Compressive strength was determined according to ISO Standard
7489 using an INSTRON ™ universal tester (Instron Corp.)
operated at a crosshead speed of 1 mm/min.
DA
Dentin adhesion, measured according to the procedure described in
U.S. Pat. No. 5,154,762, but without using any pretreatment of
the dentin.
DTS
Diametral tensile strength, measured using the above-described CS
procedure but using samples cut to a length of 2 mm.
EA
Enamel adhesion, measured according to the procedure described in
U.S. Pat. No. 5,154,762.
FR
Fluoride release, was evaluated in vitro by mixing samples of the
cements and placing them in a 20 mm diameter × 1 mm high
cylindrical mold capped with two plastic sheets clamped under
moderate pressure using a C-clamp. The cements were allowed to
cure for 20 minutes, and then stored in a humidity chamber for one
hour. The samples were removed from the chamber and each
specimen immersed separately in a vial containing 25 ml of water in
a 37° C. oven for varying periods of time. At each measurement
interval, a specimen vial was removed from the oven and 10 ml of
the water was measured out from the specimen vial and combined
with 10 ml of TISAB II ™ Total Ionic Strength Adjustment Buffer
(Sigma Aldrich). The resulting mixture was stirred and measured
using a fluoride ion selective electrode to determine the cumulative
micrograms of fluoride leached per gram of the cement for the
applicable measurement period, using an average of three samples.
The vials were replenished with fresh deionized water and returned
to the oven until the next measurement period.
FS
Flexural strength, evaluated by placing the mixed cement samples
in a 2 mm × 2 mm × 25 mm mold made of TEFLON ™
polytetrafluoroethylene (DuPont). The filled mold was sandwiched
between two polyester sheets and clamped between the jaws of a C-
clamp. The assembly was placed in a chamber at 37° C. and ≧90%
relative humidity and allowed to stand for 10 minutes. The C-
clamp was removed and the mold was allowed to stand in the
chamber for an additional hour. The samples were next placed in
37° C. water for 1 day. The cured cement was then removed from
the mold, sanded to make the sample flat and then tested for flexural
strength using a three-point bend test carried out according to ISO
Standard 4049. The crosshead speed of the INSTRON testing
machine was 0.75 mm/min and the distance between the two lower
supports was about 20 mm.
RH
Relative humidity.
EXAMPLE 1
A liquid portion was formulated by mixing 12.5 parts AA:ITA, 12.5 parts AA:ITA:IEM, 5 parts HEMA and 20 parts water until the components dissolved. A powder portion was formulated by tumbling together 100 parts FAS I, 1.2 parts STS and 1 part PS. The powder portion and liquid portion were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure in a mold described in ISO Standard 9917, without use of a dental curing lamp. The set time was evaluated using a 400 g indenter. The cement had a set time of 2 minutes, 55 sec; CS of 162 MPa; DTS of 28 MPa; DA of 4.2 MPa and an EA of 6.2 MPa. These values represent excellent physical properties and performance.
EXAMPLE 2
Using the method of Example 1, a liquid portion was formulated by mixing 12.5 parts AA:ITA, 12.5 parts AA:ITA:IEM, 5 parts GDMA and 20 parts water until the components dissolved. The resulting liquid portion and the powder portion of Example 1 were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure. The cement had a set time of 3 minutes, 15 sec; CS of 145 MPa; DTS of 27 MPa; FS of 58 MPa; DA of 4.5 MPa and an EA of 8.0 MPa. These values represent excellent physical properties and performance.
EXAMPLE 3
Using the method of Example 1, a liquid portion was formulated by mixing 14.4 parts AA:ITA, 35.6 parts AA:ITA:IEM, 17.1 parts HEMA, 0.06 parts BHT and 32.9 parts water until the components dissolved. The resulting liquid portion and the powder portion of Example 1 were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure. The cement had a set time of 3 minutes, 35 sec; CS of 173 MPa; DTS of 32 MPa; FS of 60 MPa; DA of 5.1 MPa and an EA of 9.1 MPa. These values represent excellent physical properties and performance.
EXAMPLE 4
Using the method of Example 1, a powder portion was formulated by mixing 100 parts FAS III, 1.2 parts STS and 2 parts EPS. The resulting powder portion and the liquid portion of Example 3 were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure. The cement had a set time of 3 minutes, 10 sec; CS of 189 MPa; DTS of 33 MPa; FS of 62 MPa; DA of 4.11 MPa and an EA of 5.57 MPa. These values represent excellent physical properties and performance.
EXAMPLE 5
Using the method of Example 1, a powder portion was formulated by mixing 100 parts FAS IV, 1.2 parts STS and 2 parts EPS. The resulting powder portion and the liquid portion of Example 3 were hand-spatulated at a 2.5:1 powder/liquid ratio and allowed to self-cure. The cement had a set time of 3 minutes, 15 sec; CS of 210 MPa, DTS of 41 MPa, DA of 4.11 MPa, FS of 58 MPa, DA of 5.19 MPa and EA of 9.57 MPa. These values represent excellent physical properties and performance.
The powder portion was aged in an open container at 90% RH and 37° C. for two months, then mixed with the liquid portion to reevaluate the physical properties of the cement after a 2 month aging period. As shown below in Table 1, the aged powder gave very similar properties to the initial powder.
TABLE 1
Aging
Aging
Set Time,
CS,
DTS,
DA,
EA,
Interval
conditions
min:sec
MPa
MPa
MPa
MPa
Initial
Ambient
3:20
210
41
5.19
9.57
2 Weeks
37° C./90 RH %
3:25
196
37
5.53
7.01
1 Month
37° C./90 RH %
3:45
188
37
4.33
9.43
2 Months
37° C./90 RH %
4:00
198
37
4.56
9.48
Fluoride Release of the cement was evaluated and compared to two commercially available glass ionomer materials. The results are shown in FIG. 1, which shows the cumulative fluoride release over a 6 month time span for the cement of Example 5, VITREMER™ RMGI cement (3M ESPE) and FUJI IX™ conventional glass ionomer cement (G-C Dental Industrial Corp.) as curves 11 , 13 and 15 , respectively. As shown in FIG. 1, the cement of Example 5 provided higher fluoride release than the two commercial glass ionomer cements. In addition, unlike the RMGI cement, the cement of Example 5 did not require use of a curing light. Also, unlike both the commercial cements, the cement of Example 5 did not require use of a tooth pretreatment.
COMPARATIVE EXAMPLE 1
Using the method of Example 1, a liquid portion was formulated by mixing 50 parts AA:ITA, 45 parts water and 5 parts tartaric acid until the components dissolved. The resulting liquid portion and the non-silane treated precursor of FAS IV were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure. The resulting cement approximated a conventional glass ionomer, and had a set time of 3 minutes; CS of 173 MPa; DTS of 28 MPa and FS of 29 MPa. Thus although the CS and DTS values were relatively high, the FS value was not.
COMPARATIVE EXAMPLE 2
Following the manufacturer's directions, FUJI IX™ conventional glass ionomer cement was mixed and allowed to self-cure in a mold. The resulting cement had an FS of 31 MPa; a DA (without tooth pretreatment) of 2.4 MPa and an EA (also without tooth pretreatment) of 6.26 MPa. This represented a small increase in FS compared to Comparative Example 1 but was not as high as the FS values obtained for the cements of the invention reported above. In addition, the cements of the invention provided improved adhesion to untreated dentin and enamel.
COMPARATIVE EXAMPLE 3
Following the manufacturer's directions, VITREMER™ resin-modified glass ionomer cement (3M ESPE) was mixed and allowed to self-cure in a mold. The resulting cement had a DA (without tooth pretreatment) of zero MPa and an EA (also without tooth pretreatment) of 2.2 MPa. Again, the cements of the invention provided improved adhesion to untreated dentin and enamel.
EXAMPLES 6-14
Using the method of Example 1, a series of liquid portions was prepared by combining Polymer A (AA:ITA), Polymer B (AA:ITA:IEM), HEMA and water in the relative amounts shown below in Table 2. Each liquid also contained 0.06 parts BHT. The liquids had pH values between 3 and 4. A powder portion was formulated by mixing 100 parts FAS I, 1.2 parts STS and 1 part PS. The liquid portions and the powder portion were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure. The cements had set time, compressive strength, diametral tensile strength, dentin adhesion and enamel adhesion values as set out below in Table 2. Because these examples included endpoints for a designed experiment, some of the measured values were not as high as those obtained for the other cements of the invention reported above.
TABLE 2
Example
Set Time,
CS,
DTS,
DA,
EA,
No.
AA:ITA
AA:ITA:IEM
HEMA
Water
min:sec
MPa
MPa
MPa
MPa
6
35.6
14.4
2.94
47.1
2:25
132
21
2.94
3.96
7
14.4
35.6
2.94
47.1
2:15
129
23
1.64
3.82
8
35.6
14.4
17.1
32.9
3:30
157
27
1.96
5.64
9
14.4
35.6
17.1
32.9
3:35
173
32
2.42
7.27
10
25
25
0.01
50
2:00
118
19
1.07
2.31
11
25
25
20
30
4:10
155
24
2.86
7.57
12
40
10
10
40
3:00
133
22
2.86
4.04
13
10
40
10
40
2:30
160
29
2.38
7.11
14
25
25
10
40
2:35
156
26
2.38
5.25
The results in Table 2 show a range of liquid formulations and their effect on several physical properties of the cement.
EXAMPLE 15 AND COMPARATIVE EXAMPLES 4-7
Using the method of Example 1, a series of liquid portions was prepared by combining Polymer A (AA:ITA), Polymer B (AA:ITA:IEM), HEMA, water, tartaric acid and BHT in the relative amounts shown below in Table 3. A powder portion was formulated by mixing 100 parts FAS IV, 1.16 parts STS and 1.94 part EPS. The liquid portions and the powder portion were hand-spatulated at a 2.7:1 powder/liquid ratio and allowed to self-cure. The cements had set time, compressive strength, diametral tensile strength, flexural adhesion, dentin adhesion and fluoride release values as set out below in Table 3. The results in Table 3 show a synergistic increase in CS, DTS, FS and DA for a cement containing both Polymer A and Polymer B, together with very good fluoride release.
TABLE 3
Example
No. or
FR at
Comp.
Tartaric
Set Time,
CS,
DTS,
FS,
DA,
14 days,
Ex. No.
AA:ITA
AA:ITA:IEM
HEMA
Water
Acid
BHT
min:sec
MPa
MPa
MPa
MPa
μg/g
15
14.4
35.6
17.1
32.9
0
0.0625
3:50
201
39
66
4.97
803
Comp. 4
0
50
17.1
32.9
0
0.0625
3:20
197
36
55
1.11
621
Comp. 5
50
0
17.1
32.9
0
0.0625
3:40
112
22
26
0
1118
Comp. 6
50
0
0
50
0
0
3:50
137
16
24
0
320
Comp. 7
45
0
0
50
5
0
3:40
130
17
21
1.28
480
Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. Thus this invention should not be restricted to that which has been set forth herein only for illustrative purposes.
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Resin-modified glass ionomer cements contain a polymer having a plurality of acidic repeating units but being substantially free of polymerizable vinyl groups, a polymer having a plurality of acidic repeating units and a plurality of polymerizable vinyl groups, a fluoroaluminosilicate glass, a redox cure system that can initiate dark cure of the vinyl groups, and water. The cements can be used without requiring a preliminary tooth priming or conditioning step and without requiring a curing lamp. The cements offer ease of mixing, convenient viscosity, convenient cure, good flexural strength, good adhesion to dentin and enamel, and high fluoride release, even when cured in thick sections and in the dark.
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FIELD AND BACKGROUND OF THE INVENTION
The present invention relates, in general, to offshore technology and, in particular, to a new and useful method that makes cylindrical piling easier to drive. The method works particularly well for piling driven in sensitive clays. In addition to making the piling easier to drive, the installation operations required to install piling for an offshore platform are greatly facilitated. The method involves putting a plug in the pile at or near its bottom end and leaving this plug in place during the driving of the pile.
The use of piling in offshore platforms has evolved over many years and includes a wide variety of known operations. Generally, however, the pile is driven either through the legs of a jacket or template already in place on the sea floor or through sleeves attached to the jacket.
In any event, a derrick barge carrying lengths of pile as well as pile add-ons is generally secured adjacent the site where the driving operation is to occur. These pile add-ons extend the length of the pile until it reaches the seabed. This pile is then driven into the seabed with additional add-ons being supplied as needed until the desired depth is reached.
Occasionally, removable closure plates are installed in the pile to add buoyancy to selected sections of the pile. This buoyancy reduces the hook load on the derrick that must be provided to manipulate the pile and its add-ons as it is lowered to the seabed.
U.S. Pat. Nos. 4,696,603, 4,696,604, and 4,705,430 disclose various compliant tower or composite leg platform designs. These structures require piling that is much longer and heavier than that which has been installed to date. A single pile for a compliant tower may weigh 2,000 tons and have a length of over 2,000 feet. In contrast, a current single skirt pile might weigh only about 400 tons and have a length of about 550 feet. Thus, currently known problems regarding the manipulation and lowering of existing piles with add-ons are greatly exacerbated by the 4 or 5 fold increase in pile weight and length associated with such compliant towers.
U.S. Pat. No. 5,060,731 discloses a well conductor, as contrasted with a pile, that is plugged and then driven to a design penetration depth afterwhich the plug is drilled out as the drilling rig begins drilling the well. However, as can be appreciated, conductors are normally 22 to 30 inches in diameter whereas piling for offshore platform foundations is often in the 72 to 96 inch diameter range. Also, such well conductors are often only driven to a rather shallow range of about 200-300 feet as compared to the driven depth for anchoring purposes which involves considerably deeper penetrations.
It is, therefore, an object of this invention to make piling easier to drive regardless of its length, desired penetration depth, or diameter. A further object of this invention is to reduce or eliminate the large support structures on the platform that are normally required or associated with the driving of piles. Yet another object of this invention is to facilitate and expedite pile driving operations thereby reducing their costs. It is also an object of this invention to achieve all of the operational advantages of a sealed pile, such as its control and buoyancy advantages, without the disadvantage of having to remove any of the seals. Another object of this invention is to make piles easier to drive in sensitive clays. Driving may also be easier in other types of soils, but the effect will be less pronounced than in sensitive clays. Still another object of this invention is to make the pile easier to transport, handle at the site, assemble, and lower.
For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which the preferred embodiments of the invention are illustrated.
SUMMARY OF THE INVENTION
The invention comprises the use of a plug at or near the bottom or end of a pile during handling, assembly, and lowering of the pile to self support in the sea bottom, followed by the driving of the pile with the plug intact. General consensus in the industry is that the plug will make the driving of the pile more difficult since it presents more of a profile that must be moved through the soil. However, this was not found to be the case in highly sensitive clays, the driving of a plugged pile is considerably easier than the driving of an open pile. While plugs have been employed in the past to facilitate certain aspects of pile transportation, handling, assembly, and lowering, they were always removed prior to pile driving because of the belief that the plug would make the pile more difficult or impossible to drive. Previously, the advantages derived from using plugs did not compensate for the costs related to installing and removing the plugs.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of a pile driving template or jacket.
FIG. 2 is a sectional view taken along lines 2--2 of FIG. 1.
FIG. 3 is a side elevational view of a platform supported on skirt piles.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to FIGS. 1 and 2, piling 10 for offshore platform 12 is generally driven through the hollow tubular legs 14 of a pile driving template or jacket 16. Piling 10 and jacket legs 14 are generally both made from pipe with piling 10, of course, being sized slightly smaller than the inside diameter of leg 14.
After pile 10 has been driven to the design penetration depth, deck leg 18 is secured thereto above sea level 20 for the support of platform 12. Piling 10 installed in this manner is commonly referred to as main piling. Such piling 10 ranges from two to ten feet or more in diameter and can weigh from a few tons to several hundred tons. The total length of such piling 10 varies from about 200 to over 1,200 feet or more.
In the past, such piling has been open ended so as to displace as little soil below mudline 22 as possible. In other words, open-ended piles slice through mudline 22 as if a core of mudline 22 is being taken. Consequently, the driving force of the pile must not only overcome the soil resistance or soil shear along its outer perimeter, but this force must also overcome the resistance or shear of the soil now contained within the pile
In accordance with this invention, however, pile 10 is plugged at its end region 24. This plug may take the shape of a cone or it can be rounded or flush with end 24 of pile 10. It can also be of any other shape, the important feature being that pile 10 is now plugged rather than being open.
Driving a plugged pile 10 is contrary to current knowledge which holds that driving such a blunt object (remember that pile 10 is from 2 to 10 or so feet in diameter) is more difficult than driving an open pile which slices through mudline 22. This common belief is held because as plugged pile 10 advances, it presents a greater area subject to soil end bearing than would otherwise be seen by an open pile. Additionally, since the pile is plugged, the displaced soil must be moved to the outside of the pile whereas in an open pile, thee soil merely moves up within the pile without being forced or moved to the outside.
However, is was found that highly sensitive clays, such as those found below mudline 22 in the Gulf of Mexico, become remolded once they are disturbed. These clays were also found to temporarily lose much of their strength when they are so remolded thereby invalidating the presumption that a greater driving force is needed to drive a plugged pile. In fact, it was discovered that the actual driving force required to drive such a blunt pile 10 in such soils was actually reduced threefold or more!
Another factor in a lower driving force required to drive plugged pile 10 is the fact that in open piles, the soil plug inside the pile absorbs much of the driving energy of the hammer in internal damping. In contrast, plugged pile 10 has only water (or air) inside which obviously absorbs much less energy than the soil plug. This enables more of the driving force to be applied to advancing the pile.
The present invention can be used in operations involving pile handling and driving that have been employed over the years. One Advancement in pile driving was the introduction of battered skirt piling 36 as shown in FIG. 3. The present invention of plugging the ends of skirt piling 36 is also applicable in such cases. Normally, skirt piling 36 is driven through sleeves 38 secured to a lower region of legs 14. However, such skirt piles 36 do not extend the entire length of legs 14, instead they extend upward from mudline 22 a distance of generally only one bay of jacket 16. Also, like legs 14 of jacket 16, sleeves 38 oftentimes extend at an angle with respect to mudline 22. To install such skirt piling 36, however, a follower pile 42 is secured to the top of the skirt piling 36 that has had its end 40 plugged and driven to the desired depth in the normal fashion. Oftentimes, holding devices such as internal or external grippers are utilized to lift and lower skirt pile 36 rather than support lugs. In other cases, an underwater hammer can be utilized to drive skirt pile 36 without the need for a follower pile (or at least a reduced length follower pile).
Some examples of the improvements provided by this invention for both main piled and skirt piled jackets are as follows:
First, when main piles are assembled, they must be hung from the top of jacket leg 14 using support lugs or grippers or the like. The weight of main pile string 10 is then delivered through the jacket 16 to the mudmats at the mudline 22. If pile 10 is plugged, then its buoyancy greatly reduces the load that these items must carry, thereby making them lighter and more economical to construct and install.
Second, when main pile 10 is lowered, it must be lifted by a derrick. If pile 10 is plugged, then the derrick, the gripper, and the rigging required to make the lift can be of lower capacity. This will often mean that a lower capacity block, which will be smaller and faster, can be used for handling pile 10.
Third, often battered skirt piles 36 are assembled from sections working from the top of jacket 16. This skirt pile string 36 is then lowered to self support and driven utilizing a follower string or pile 42. Plugged piling offers the same advantages in this instance as it does for main piles. Also, if a removable closure plate 44 is installed near the top of plugged skirt pile 36, then the weight of the follower string or pile 42 will be utilized to push skirt pile 36 down against the resultant upward buoyant force. Thus, a simple gravity connection (compression only) between skirt pile 36 and the follower string 42 will function for both the lowering and driving operations of pile 36. After driving, the follower string 42 is simply lifted off skirt pile 36. In contrast, in an unplugged skirt pile, i.e. one not buoyant, the skirt pile must hang from the follower string during the lowering operation so that after the pile is driven, the tension connection between the skirt pile and the follower must also be released before the follower can be retrieved.
Fourth, should a one piece skirt pile, battered or vertical, be plugged and a closure plate installed near the top of the pile, then the pile will float and a number of operations will be facilitated. For instance, a wet tow of the pile is possible, or the piling may be loaded out on a transport barge and side launched at the site. The pile may be upended at the site using a combination of flooding and lifting with the derrick barge, or it might be upended without derrick assist by selectively flooding one or more bottom chambers formed by installing additional closure plates within the pile. Once upended the pile can be lowered using much lighter rigging than would be possible with an open ended pile. A smaller, faster block on the derrick or possibly even a winch can be used to lower the pile to self support in the sea floor, possibly without having to stop and change rigging because of limits on block travel.
Fifth, when a plugged pile iS driven with an underwater, slim-line hammer in the free riding mode, the problem of venting the water from the interior of the pile is eliminated. This permits a smaller annulus between the hammer and the pile and a smaller driving shoulder for the hammer anvil to strike.
Sixth, when support lugs for either an external or internal gripper are used to handle or hang a pile or follower string, these devices induce stresses in! the region of the pile or follower upon which they act. The stresses induced are proportional to the weight of the pile or follower string and can control the design of that region of the pile or follower string. The reduction of the effective weight of a plugged, buoyant pile eliminates this problem.
Seventh, all of the advantages already stated for a plugged pile are much more pronounced for the extended piles of a compliant tower because of their much greater weights and lengths. Furthermore, the plug and any closure plates installed do not have to be removed as they do in driving techniques utilizing conventional piles. Thus, any problems associated with the removal of the plug or these closure plates are eliminated.
While a specific embodiment or, the invention has been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.
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A pile is plugged at its lower end or tip region so as to make it easier to drive. Additionally, such a plugged pile facilitates the transportation and handling of the pile prior to its driving.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to a method of making a composite of metal particles and exfoliated silicate clay, and more particularly to a method of making a composite which is able to control the size of metal nanoparticles.
[0003] 2. Description of the Related Art
[0004] Silver nanoparticles are well known in antimicrobial activity, and can be used to kill more than 600 species of bacteria. Silver nanoparticles are important nanomaterials applied in many fields, such as biotechnology, medicine, biomedical material, chemistry, chemical engineering, nanocomposite, etc. In synthesis of silver nanoparticles, the silver particles are hard to disperse because of the effect under nanometer scale and the van der Waals force. Therefore, the important target in study of producing silver nanoparticles is to find methods to control their size, stability and dispersion.
[0005] The conventional methods of producing the silver nanoparticles are mainly classified into physical and chemical processes. The silver nanoparticles can be directly obtained through the physical process. However, specific equipment is needed in the physical process, such as decomposing a bulk phase material into nanoparticles by high power laser, or vaporizing metal and condensing the vapor to obtain nanoparticles. However, these two physical processes are very complex and need expensive equipments. Furthermore, in operation or the process of producing silver nanoparticles, the concentration of silver ions solution must be in a limited range, usually between several ppm and hundreds ppm. The silver particles will aggregate if the concentration of silver ions solution is too high.
[0006] Chemical process is to reduce silver ions into silver atoms in a specified solution. The silver atoms will aggregate after reduction reaction so that stabilizer will be added to stabilize the nanoparticles. The stabilizer will be on the surfaces of the nanoparticles to avoid aggregation. The actions of the stabilizer include:
[0007] 1) The stabilizer makes the nanoparticles have electric charges on their surface to form electric double layer, so that each nanoparticle carries the same electric charges. Therefore, the nanoparticles will disperse because of the Coulomb force. However, the nanoparticles will aggregate while the electric charges on the surfaces of nanoparticles being replaced by neutral elements. Furthermore, in a high concentration or high ionic strength solution, with the increase of dielectric strength, the electric double layer is compressed, which is bad for stabilizing the nanoparticles.
[0008] 2) The organic component of the stabilizer forms a protective layer on the nanoparticles to avoid aggregation. It is called “steric stabilization”. The common stabilizer includes water-soluble synthetic polymers (e.g. PVP, PVA, polymethylvinylether, PAA, etc.), dendrimer, sodium citrate, surfactant, ligand, and chelating agent, etc.
[0009] Conventional stabilizer is mostly organic polymer. The species and the mixture ratio of the polymers affect the sizes of the silver nanoparticles. However, the composite having the polymers and the silver nanoparticles will aggregate because of heat, and therefore the silver nanoparticles are getting bigger.
[0010] The earlier inventions of the present inventors provide exfoliated inorganic clay as the dispersing agent or stabilizer of metal particles to synthesize a composite of metal nanoparticles and exfoliated platelet-shaped clay. The exfoliated platelet-shaped clay is nano silicate platelet which is developed by the present inventors, and the methods of making such nano silicate platelet are taught in Taiwan patents 1280261, 1284138, 1270529, 577904, and 593480. As shown in FIG. 1 , sodium montmorillonite 1 enters the clay platelets through the polymer 2 to exfoliate the clay platelets, and then the nano silicate platelet 3 will be obtained after a series of extracting processes. The silicate platelet has many characteristics, including high aspect ratio (average 100×100×1 nm 3 ), high surface area (700-800 m 2 per gram), and high electric charge (ca. 20,000 ions per piece). An average weight of the silicate platelet is 4×10 16 pieces per gram. These characteristics make the silicate platelet to disperse the silver nanoparticles stably.
[0011] The composite of the metal nanoparticles and the exfoliated platelet-shaped clay made by aforesaid method is inorganic. It is different from the conventional organic-inorganic composite in which the silver nanoparticles are reduced and stabilized by the organic polymers. But it is still not easy to make high-dispersed silver nanoparticles, and hard to control the particle's size, and furthermore, the stability of the silver nanoparticles under thermal treatment still has to be improved, therefore the present inventors are working on the study of the composite of the metal nanoparticles and the platelet-shaped clay.
SUMMARY OF THE INVENTION
[0012] The primary objective of the present invention is to provide a method of making a composite of metal nanoparticles, which is able to control the size of metal particles.
[0013] The secondary objective of the present invention is to provide a method of making a composite of metal nanoparticles, in which the metal nanoparticles have high stability under thermal treatment and can be re-dissolved in the solution without aggregation.
[0014] According to the objective of the present invention, the present invention provides a method of making a composite of size-controllable metal nanoparticles, which includes the steps of a) preparing a solution of exfoliated silicate clay and a solution of metal ions; and b) mixing the solution of the exfoliated silicate clay with the solution of the metal ions to reduce the metal ions to metal nanoparticles and attach the metal nanoparticles to the exfoliated silicate clay.
[0015] The method further comprise the step of adjusting a weight ratio of the metal ion to the exfoliated silicate clay in the step a), whereby the size of the metal nanoparticles in the step b) is reducing while the weight ratio of the metal ion to the exfoliated silicate clay is increasing.
[0016] In an embodiment, the metal nanoparticles may be silver, copper, iron, or gold, and silver is preferable.
[0017] In an embodiment, the exfoliated silicate clay is made by an exfoliated platelet-shaped clay, and the clay is selected from the group consisting of bentonite, Li-based bentonite, montmorillonite, artificial mica, kaolinite, talc, attapulgite, vermiculite, and smectic hydroxide, and nanoscale silicate platelets of exfoliated montmorillonite is preferable.
[0018] In an embodiment, the solution of metal ion is selected from the group consisting of nitrate solution, chloride solution, and bromated solution of the selected metal ion. For example, if the metal ion is silver ion, then the preferred solution is selected among silver nitrate solution, silver chloride solution, and silver bromated solution.
[0019] In an embodiment, the composite is made into a film, and the film is reversible to be re-dissolved in the solution. The change of diameters of metal nanoparticles before and after re-dissolving is less than 7%.
[0020] In an embodiment, the weight ratio of the metal ion to the exfoliated silicate clay is in a range between 0.5/99.5 and 50/50.
[0021] Therefore, it provides a method of making composite of size-controllable metal nanoparticles, which has the ability to disperse and stabilize the metal nanoparticles, and it may control the diameter of the metal nanoparticles by adjusting the weight ratio of the metal ion to the exfoliated silicate clay.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a sketch diagram, showing fabrication of the nano silicate platelets and stable production of the silver nanoparticles;
[0023] FIG. 2 is a spectrogram of the solution of AgNP/NSP (7/93) which is reduced by ethanol;
[0024] FIG. 3 is a spectrogram of the solution of AgNP/MMT (7/93) which is reduced by ethanol;
[0025] FIG. 4 is a spectrogram of the solution of AgNP/NSP (7/93) which is reduced by methanol;
[0026] FIG. 5 is a spectrogram of the solution of AgNP/NSP (7/93) which is reduced by isopropanol;
[0027] FIG. 6( a ) to FIG. 6( d ) are pictures taken via TEM, showing the distribution of the particle's size of (a) AgNP/NSP reduced by ethanol; (b) AgNP/MMT reduced by ethanol; (c) AgNP/NSP reduced by methanol; and (d) AgNP/NSP reduced by isopropanol;
[0028] FIG. 7 are pictures taken via TEM, showing the size change because of the thermal treatment, in which (a) and (d) are Ag/SMA3000-M2070, (b) and (e) are Ag/MMT, and (c) and (f) are Ag/NSP; (a)-(c) show the particle's size before the thermal treatment, and (d)-(f) show the particle's size after accepting thermal treatment for 8 hours;
[0029] FIG. 8 is a spectrogram of (a) UV absorbance of AgNP/NSP solution; and (b) UV absorption of AgNP/MMT solution;
[0030] FIG. 9( a ) to FIG. 9( f ) are pictures taken via TEM, showing the mean diameter of AgNP/NSP in (a) 0.5/99.5 wt % (P3.6), (b) 1/99 wt % (P3.8), (c) 7/93 wt % (P5), (d) 15/85 wt % (P9), (e) 30/70 wt % (P17), and (f) 50/50 wt % (P35);
[0031] FIG. 10( a ) to FIG. 10( e ) are pictures taken via TEM, showing the mean diameter of AgNP in EtOH/H 2 O in different weight ratios (a) 1/1, (b) 3/1, (c) 5/1, (d) 10/1, and (e) 1/0;
[0032] FIG. 11 is a diagram of the mean diameter of AgNP with different contents of ethanol;
[0033] FIG. 12 is a spectrogram of the UV absorbance of AgNP in (a) solution, (b) film, and (c) re-solution;
[0034] FIG. 13 is a spectrogram of the AgNP in solution, film, and re-solution;
[0035] FIG. 14 are pictures taken via TEM, showing the diameter of AgNP in (a) solution, and (b) re-solution (Ag-NSP(7/93)/PVA=10/90);
[0036] FIG. 15 shows the antimicrobial effect of AgNP/clay (AgNP: 10 ppm) on E. coli;
[0037] FIG. 16 shows the antimicrobial effect of AgNP/NSP on Gram-negative bacteria and Gram-positive bacteria (a) E. coli (AgNP: 10 ppm), (b) Pseudomonas aeruginosa (AgNP: 20 ppm), (c) Staphylococcus aureus (AgNP: 30 ppm), and (d) Streptococcus pyogenes (AgNP: 10 ppm); wherein the control group is NSP;
[0038] FIG. 17 are FE-SEM pictures of E. coli cultured on AgNP/NSP;
[0039] FIG. 18 are FE-SEM pictures of Staphylococcus aureus cultured on AgNP/NSP; and
[0040] FIG. 19 shows the antimicrobial effect of AgNP/NSP, wherein AgNP having similar size but different weight ratio, on E. coli , and the control group is 0.1 wt % NSP.
DETAILED DESCRIPTION OF THE INVENTION
[0041] The materials and bacteria used in the present invention include:
[0042] 1. Nanoscale silicate platelets (NSP), which is made of exfoliated sodium montmorillonite, and the detail process can be found in Taiwan patents 1280261, 1284138, 1270529, 577904, and 593480.
[0043] 2. Sodium montmorillonite (Na+-MMT), which is smectic aluminium silicate clay, purchased from Nancor Co.
[0044] 3. Silver nitrate (AgNO 3 , Mw.=169.87 g/mol) purchased from J.T. Baker, Inc.
[0045] 4. Methanol (MeOH, 95%), which is a weak reducing agent to slowly reduce silver ion to silver nanoparticle in 30° C.-150° C.
[0046] 5. Ethanol (EtOH, 99.5%), which is a weak reducing agent to slowly reduce silver ion to silver nanoparticle in 30° C.-150° C.
[0047] 6. Isopropyl alcohol (C 3 H 8 O, 95%), which is a weak reducing agent to slowly reduce silver ion to silver nanoparticle in 30° C.-150° C.
[0048] 7. Sodium borohydride (NaBH 4 ), which is a strong reducing agent to rapidly reduce silver ion.
[0049] 8. SMA (SMA3000-M2070), referring to Macromolecules 2007, 40, 1579-1584 for detail.
[0050] 9. poly(vinyl alcohol) (PVA, Mw.=74800g/mo, hydrolysis=98.5−99.2 mol %) purchased from Chang Chun Petrochemical Co.
[0051] 10. Bacteria strains: Staphylococcus aureus 71 ; 431 ; 10781, Streptococcus pyogenes Rob 193-2, Pseudomonas aeruginosa , and E. coli provided by Dr. Su, Hong-Lin who is a professor of department of life sciences of National Chung Hsing University.
[0052] 11. Standard bacteria solution, which is made by adding overnight bacteria solution into fresh Luria-Bertani (LB) in a volume ratio of 1/100 for three hours, and choose the bacteria solution with OD600 in a range between 0.4 and 0.6.
[0053] The detailed description and technical contents of the present invention will be explained with reference to the accompanying drawings. However, the drawings are illustrative only but not used to limit the present invention.
[0054] We take the synthesis of silver nanoparticles (AgNP)/nanoscale silicate platelets (NSP) for example to explain the metal particles/exfoliated silicate clay of the preferred embodiment of the present invention. It is easy to understand that it may use different exfoliated platelet shaped clay as carrier, such as bentonite, Li-based bentonite, montmorillonite, artificial mica, kaolinite, talc, attapulgite, vermiculite and smectic hydroxide, etc.
[0055] The metal ion in the present embodiment may be silver ion, gold ion, copper ion, iron ion, and other suitable ions. The silver ion may be obtained from silver nitrate, silver bromide, silver chloride, silver bromated, silver chlorate, and any suitable solution.
[0056] In an embodiment of the present invention, the synthesis of silver nanoparticles (AgNP)/nanoscale silicate platelets (NSP) includes the following three parts:
[0057] 1) Reduce the silver ions by ethanol and stabilize the dispersed AgNP by the NSP;
[0058] 2) Adjust the weight ratio of the silver ions (Ag + ) to the NSP to control the size of the AgNP; and
[0059] 3) Adjust the weight ratio of ethanol to water to control the size of the AgNP.
EXAMPLE 1
Reduce A g + by Ethanol and Stabilize the Dispersed AgNP by the NSP.
[0060] The weight ratio of Ag + to NSP is 7/93. First, prepare the NSP solution (46.5 g, 2wt % in water) and the AgNO 3 solution (0.11 g, 1 wt %), and then pour the NSP solution(2 wt %) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. Next, stir the solution by a magnet for half an hour, and provide nitrogen to prevent generation of silver oxidant. A cooling device is provided to prevent evaporation of ethanol. Next, slowly drop the AgNO 3 solution into the solution, and keep stirring for half an hour until the color of the solution changing to milky white. A reduction-oxidation reaction will occur in the solution while the temperature rises to 80° C., and the color of the solution changes to yellowish-brown three hours later. An UV spectrometer is used here to monitor the growth of the silver nanoparticles (the characteristic absorbance wavelength is 408 nm). It tells that the reaction is completed when the absorbance strength keeps still. Next, filter out of the un-reacted ethanol by suction filtration (using No. 5 filter paper of whatman®, Cat. No. 1005 090), and scratch the residual material off the filter paper, and then dissolve the residual material in the water to form a re-solution (3 wt %). The color of the re-solution in 100 ppm is golden. FIG. 2 shows the UV absorbance spectrogram of the reduced silver ions, in which the characteristic absorbance peak of the nanoparticles is 408 nm, which proves the existence of the silver nanoparticles.
EXAMPLES 2-6
Adjust the Weight Ratio of the Silver Ions (Ag + ) to Nanoscale Silicate Platelets (NSP) to Control the Size of Silver Nanoparticle (AgNP)
[0061] In these examples we apply the same test as EXAMPLE 1 and control the weight ratios of the silver ions (Ag + ) to nanoscale silicate platelets (NSP). The weight ratios are shown in Table 1.
EXAMPLE 2
Weight Ratio of Ag + /NSP is 0.5/99.5
[0062] First, prepare the NSP solution (9.95 g, 10 wt % in water) and the AgNO 3 solution (0.79 g, 1 wt % in water), and then pour the NSP solution, water (39.76 g) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. The weight ratio of water to ethanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 3
Weight Ratio of Ag + /NSP is 1/99
[0063] First, prepare the NSP solution (9.9g, 10 wt % in water) and the AgNO 3 solution (1.57 g, 1 wt % in water), and then pour the NSP solution, water (39.04 g) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 4
Weight Ratio of Ag + /NSP is 15/85
[0064] First, prepare the NSP solution (8.5 g, 10 wt % in water) and the AgNO 3 solution (23.62 g, 1 wt % in water), and then pour the NSP solution, water (18.47 g) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 5
Weight Ratio of Ag + /NSP is 30/70
[0065] First, prepare the NSP solution (7.0 g, 10 wt % in water) and the AgNO 3 solution (23.62 g, 2 wt % in water), and then pour the NSP solution, water (20.05 g) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 6
Weight Ratio of Ag + /NSP is 50/50
[0066] First, prepare the NSP solution (5.0g, 10 wt % in water) and the AgNO 3 solution (39.37 g, 2 wt % in water), and then pour the NSP solution, water (6.42 g) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLES 7-10
Adjust a Weight Ratio of Deionized (DI) Water to Ethanol to Control the Size of Silver Nanoparticle (AgNP):
[0067] A constant weight ratio of Ag + /NSP is 1/99, and the weight ratios of DI water/ethanol are shown in the Table 1.
EXAMPLE 7
Weight Ratio of DI Water/Ethanol=3/1
[0068] A weight ratio of Ag + /NSP is 1/99: First, prepare NSP solution (9.9 g, 10 wt % in water) and the AgNO 3 solution (1.57 g, 1 wt % in water), and then pour the NSP solution, water (63.79 g) and ethanol (24.75 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 3/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 8
Weight Ratio of DI Water/Ethanol is 5/1
[0069] A weight ratio of Ag + /NSP is 1/99: First, prepare the NSP solution (9.9 g, 10 wt % in water) and the AgNO 3 solution (1.57 g, 1 wt % in water), and then pour the NSP solution, water (72.04 g) and ethanol (16.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 5/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 9
Weight Ratio DI Water/Ethanol is 10/1
[0070] A weight ratio of Ag + /NSP is 1/99: First, prepare the NSP solution (9.9 g, 10 wt % in water) and the AgNO 3 solution (1.57 g, 1 wt % in water), and then pour the NSP solution, water (79.54 g) and ethanol (9 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 10/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
EXAMPLE 10
Weight Ratio of DI Water/Ethanol is 1/0
[0071] A weight ratio of Ag + /NSP is 1/99: First, prepare the NSP solution (9.9 g, 10 wt % in water) and the AgNO 3 solution (1.57 g, 1 wt % in water), and then pour the NSP solution and water (88.54 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 1/0. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1.
[0072] The preferred compared examples of the synthesis of AgNP/NSP include the following three parts:
[0073] 1) Reduce silver ions (Ag + ) by ethanol, and stabilize the dispersed AgNP by montmorillonite (MMT);
[0074] 2) Reduce silver ions (Ag + ) by different solutions, which are reducing agents also, and stabilize the dispersed AgNP by nanoscale silicate platelets (NSP); and
[0075] 3) Reduce silver ions (Ag + ) by NaBH 4 and stabilize the dispersed AgNP by polymer.
Compared Example 1
Reduce Ag + by Ethanol and Stabilize the Dispersed AgNP by MMT
[0076] A weight ratio of Ag + /MMT is 7/93: First, swell MMT powder with DI water to obtain a MMT solution (18.6 g, 5 wt % in water), and prepare AgNO 3 solution (11.02 g, 1 wt % in water), and then pour the MMT solution, water (20.92 g) and ethanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to ethanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour. The following steps are the same as EXAMPLE 1. FIG. 3 shows a UV spectrogram of the solution, in which the characteristic absorbance peak of AgNP is 413 nm after three hours. It is an evidence of the existence of AgNP.
Compared examples 2-3
Reduce Silver Ions (A g +) by Different Solutions, Which are Reducing Agent Also, and Stabilize the Dispersed AgNP by Nanoscale Silicate Platelets (NSP)
[0077] Methanol (MeOH) and isopropyl alcohol are selected to be a solvent to reduce Ag + .
Compared Example 2
Methanol Solvent
[0078] A weight ratio of Ag + /NSP is 7/93: First, prepare NSP solution (9.3 g, 10 wt % in water) and AgNO 3 solution (11.02 g, 1 wt % in water), and then pour the MMT solution, water (30.22 g) and methanol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to methanol in the solution is 1/1. Next, stir the solution with a magnet for half an hour, and provide nitrogen to prevent generation of silver oxidant. A cooling device is provided to prevent evaporation of methanol. Next, slowly drop the AgNO 3 solution into the solution, and keep stirring for half an hour until the color of the solution changing to milky white. A reduction-oxidation reaction is occurred in the solution while the temperature rises to 60° C., and the color of the solution will change to deep yellowish-brown three hours later. An UV spectrometer is used here to monitor the growth of the silver nanoparticles (the characteristic absorbance wavelength is 420 nm). It tells that the reaction is completed when the absorbance strength keeps still. Next, filter out of the un-reacted methanol by suction filtration (using No. 5 filter paper of whatman®, Cat. No. 1005 090), and scratch the residual material off the filter paper, and dissolve the residual material in the water to form a re-solution (3 wt %). The color of the re-solution in 100 ppm is golden. FIG. 4 shows the UV absorbance spectrogram of the reduced silver ions, in which the characteristic absorbance peak of the nanoparticles is 420 nm after accepting twelve hours of reaction, which proves the existence of the AgNP.
Compared Example 3
Isopropyl Alcohol Solvent
[0079] A weight ratio of Ag + /NSP is 7/93: First, prepare NSP solution (9.3 g, 10 wt % in water) and AgNO 3 solution (11.02 g, 1 wt % in water), and then pour the NSP solution, water (30.22 g) and isopropyl alcohol (49.5 g) into a 250 mL three-neck round-bottom flask to obtain a 1 wt % solution. A weight ratio of water to isopropyl alcohol in the solution is 1/1. Next, stir the solution with a magnet for half an hour, and provide nitrogen to prevent generation of silver oxidant. A cooling device is provided to prevent evaporation of isopropyl alcohol. Next, slowly drop the AgNO 3 solution into the solution, and keep stirring for half an hour until the color of the solution changing to milky white. A reduction-oxidation reaction is occurred in the solution while the temperature rises to 80° C., and the color of the solution changes to deep yellowish-brown two hours later. An UV spectrometer is used here to monitor the growth of the silver nanoparticles (the characteristic absorbance wavelength is 420 nm). It tells that the reaction is completed when the absorbance strength keeps still. Next, filter out of the un-reacted isopropyl alcohol by suction filtration (using No. 5 filter paper of whatman®, Cat. No. 1005 090), and scratch the residual material off the filter paper, and dissolve the residual material in the water to form a re-solution (3 wt %). The color of the re-solution in 100 ppm is golden. FIG. 5 shows the UV absorbance spectrogram of the reduced silver ions, in which the characteristic absorbance peak of the nanoparticles is 420 nm after accepting eight hours of reaction, which proves the existence of the AgNP.
Compared example 4
Reduce Silver Ions (A g +) by NaBH 4 and Stabilize the Dispersed AgNP by Polymer
[0080] NSP is replaced by polymeric dispersant (SMA) to disperse AgNP.
Compared Example 4
Polymeric Dispersant (SMA)
[0081] A weight ratio of Ag + /SMA is 7/93: First, respectively dissolve SMA3000-M2070 (0.93 g) and AgNO 3 (0.11 g) in DI water (25 g), and then pour the SMA solution and the AgNO 3 solution into a 250 mL three-neck round-bottom flask, and then stir the solution with a magnet for half an hour and provide nitrogen to prevent generation of silver oxidant. Next, dissolve 0.03 g NaBH 4 in DI water (50 g) to obtain a NaBH 4 solution. Drop the NaBH 4 solution slowly into the solution of SMA and AgNO 3 to obtain a 1 wt % solution. A reduction-oxidation reaction is occurred in the solution, and the color of the solution changes to deep yellowish-brown three hours later. An UV spectrometer is used here to monitor the growth of the silver nanoparticles (the characteristic absorbance wavelength is 390 nm). It tells that the reaction is completed when the absorbance strength keeps still (about 3 or 4 hours), and a 1 wt % AgNP/SMA solution is obtained. The color of the solution in 100 ppm is golden.
[0000]
TABLE 1
Color of AgNP/NSP solution and UV-visible spectrometer
UV
DI water/
Reducing
wavelength
Ag + /dispersant a
reducing agent
agent
Color
(nm)
Ag + /NSP
EXP. 1
7/93
1/1
ethanol
yellowish-brown
408
EXP. 2
0.5/99.5
light brown
408
EXP. 3
1/99
brown
408
EXP. 4
15/85
deep
409
yellowish-brown
EXP. 5
30/70
deep
413
yellowish-brown
EXP. 6
50/50
deep
416
yellowish-brown
EXP. 7
1/99
3/1
brown
406
EXP. 8
1/99
5/1
brown
412
EXP. 9
1/99
10/1
brown
413
EXP. 10
1/99
1/0
brown
414
Ag + /MMT
CEXP. 1
7/93
1/1
ethanol
yellowish-brown
413
Ag + /NSP
CEXP. 2
7/93
1/1
methanol
yellowish-brown
420
CEXP. 3
7/93
1/1
isopropyl
yellowish-brown
420
alcohol
Ag + /polymer
solvent
Ag + /SMA
CEXP. 4
7/93
DI water
sodium
deep brown
413
borohydride
a AgNO 3 is added into silicate platelet solution (NSP: nanoscale silicate platelets; MMT: montmorillonite) or polymer solution (SMA: SMA3000-M2070); weight ratios of Ag + /NSP are 0.5/99.5, 1/99, 7/93, 15/85, 30/70, and 50/50.
[0082] The above examples disclose the materials and the methods of the present invention. Hereunder we will discuss the thermal stabilization of AgNP. The test of the thermal stabilization includes the following three parts:
[0083] 1) Exposure Under the UV Spectrometer:
[0084] The sample (0.05 wt %) is put under a UV lamp (UVGL-58 Handheld UV lamp, 254/365 nm, 6-Watt, 115 V - 60 Hz, 0.12 Amps) for four hours, and then check the redshift of the absorbance peak by a UV-visible spectrometer (Hitachi U-4100).
[0085] 2) Thermal treatment:
[0086] The sample (1 wt %) is put in 80° C. oil for eight hours, and then check the redshift of the absorbance peak with a UV-visible spectrometer (Hitachi U-4100) and observe the aggregation of particles with a transmission electron microscopy (TEM) (JOEL JEM-1230 electron microscope operating at 100 kV and with a Gatan DualVision CCD Camera).
[0087] 3) Stability (Reversibility) of the Film:
[0088] a) Pure Inorganic Film-Ag/NSP and Ag/MMT Film:
[0089] The sample (1 wt %) is dropped on a microscope slide, and then cured in a 60° C. oven. The film on the microscope slide is tested for its absorbance by a UV spectrometer, and then dissolved with DI water. Next, a UV-visible spectrometer (Hitachi U-4100) is used to check the change of the absorbance peak.
[0090] b) Inorganic/Organic Film-Ag/NSP/PVA Film
[0091] The sample (1 wt %) is mixed with 1 wt % PVA, and then dropped evenly on a Petri dish and baked in a 60° C. oven to obtain a film. The film is tested by the UV spectrometer for its absorbance. Next, dissolve the film by DI water, and use a UV-visible spectrometer (Hitachi U-4100) to check the change of the absorbance peak.
[0092] Test 1 and test 2 are applied in EXAMPLE 1, compared example 1, and comparison example 4; test 3-a is applied in EXAMPLE 1 and compared example 1; and test 3-b is applied in EXAMPLE 1, EXAMPLE 3, EXAMPLE 4, EXAMPLE 5, and EXAMPLE 6.
[0093] The test of the antimicrobial performance of the silver nanoparticles of the present invention is hereunder:
[0094] AgNP/inorganic clay solutions with various concentrations are made in 10 ml Lysogeny broths, and then 100λ standard bacteria solution 1×10 5 CFU/ml is added. The bacteria is cultured with 37° C. for 3 hours and 24 hours, and then the solution is diluted to suitable concentration. Next, 50λ diluted solution is coated on 10 ml Lysogeny broth by a sterile glass ball. After 24 hours (temperature is 37° C.), the bacterial count is obtained.
[0095] There are three different samples:
[0096] 1) Comparison of antimicrobial performance of AgNP with different stabilizers: AgNP/NSP vs. AgNP/MMT.
[0097] 2) Comparison of antimicrobial performance under different particle sizes: Four bacteria strains are under comparison, including E. coli, Pseudomonas aeruginosa, Staphylococcus aureus , and Streptococcus pyogenes Rob. And five AgNP/NSP samples are selected with a ratio from 1/99 to 50/50.
[0098] 3) Comparison of antimicrobial performance under different concentrations: Ratios of AgNP/NSP are 0.5/99.5 vs. 1/99.
[0099] The first sample is applied in example 1 and compared example 1; the second sample is applied in EXAMPLE 1, EXAMPLE 3, EXAMPLE 4, and EXAMPLE 5; and the third sample is applied in EXAMPLE 2 and EXAMPLE 3.
[0100] The result and analysis of the experiments are:
[0101] 1) Selection of the Reducing Agent and the Stabilizer:
[0102] According to the TEM analysis of example 1 and compared examples 1-3, the distribution of particle sizes of AgNP which is reduced by ethanol ( FIG. 6( a )) is more uniform than the AgNP reduced by methanol ( FIG. 6( c )) and isopropyl alcohol ( FIG. 6( d )). The dispersion of the AgNP by NSP ( FIG. 6( a )) is better than by MMT ( FIG. 6( b )). There are fewer AgNP on the MMT so that AgNP aggregate around MMT. Therefore, methanol and NSP are the preferred stabilizer and reducing agent for AgNP.
[0103] 2) Stabilization of Dispersion of the AgNP by NSP:
[0104] Using NSP to stabilize the dispersion of the AgNP could obtain high stabilization. The particles will not aggregate under UV light and thermal treatment (as EXAMPLE 1). In comparison with EXAMPLE 4, SMA can't provide satisfied result. The aggregation of the AgNP may be observed by red shift of the peak under
[0105] UV-visible spectrometer, as shown in Table 2. FIG. 7 shows the same result.
[0000]
TABLE 2
absorbance peak's change of the AgNP after exposure under UV
light and thermal treatment
Stabilization of AgNP
Wavelength a
dispersing
(nm)
agent b
MMT
NSP
UV light
254
2
0
0
365
2
0
0
Thermal
80° C.
14
0
0
treatment
a Δλ max is the maximum change of the wavelength after UV light exposure or thermal treatment;
b SMA3000-M2070
[0106] 3) The Reversibility of the AgNP after Film-Forming Process:
[0107] Clay stabilizer is better than SMA, and NSP is even better than normal clay (e.g. MMT). According to EXAMPLE 1 and comparison example 1, during the stabilization test, when AgNP/NSP is re-dissolved in water after film-forming process, it will find that the characteristic absorbance peak of AgNP/NSP returns to the state in the original solution. It indicates the reversibility of the AgNP. However, the reversibility is not found in AgNP/MMT. FIG. 8 shows the result of the UV-visible spectrometer, and the reversibility can be determined through the position of the absorbance peak.
[0108] 4) Control of the Size of the AgNP:
[0109] By using the ion attracting force on the surfaces of NSP to disperse the ball-like AgNP which may steadily keep the AgNP on the NSP, different mano-scale silver particles solutions may be obtained through the reactions with different weight ratios of Ag + /NSP (as the EXAMPLE 1-6 in Table 1), and the diameters of the silver particles is in a range between 3.6nm and 35nm ( FIG. 9( a ) to FIG. 9( f )). The reactions under different weight ratios of DI water/ethanol (the EXAMPLE 1, 7-10 in Table 1) may control the diameters of the AgNP. The smallest diameter may be obtained while the ratio of DI water/ethanol is 3/1 (EXAMPLE 7), and the mean diameter is about 3.3nm ( FIG. 10( a ) to FIG. 10( e ) and FIG. 11) . Table 3 shows the diameter distribution of the AgNP.
[0000]
TABLE 3
Diameter of AgNP/dispersing agent and the wavelength obtained
by UV-visible spectrometer
Weight
Weight
ratio of
ratio of
AgNP/
DI water/
UV
Diameter
dispersing
reducing
Reducing
wavelength
of TEM
agent a
agent
agent
(nm)
(nm)
Ag + /NSP
EXP 1
7/93
1/1
Ethanol
408
5.0
EXP 2
0.5/99.5
408
3.6
EXP 3
1/99
408
3.8
EXP 4
15/85
409
9.3
EXP 5
30/70
413
17.0
EXP 6
50/50
416
35.0
EXP 7
1/99
3/1
406
3.3
EXP 8
1/99
5/1
412
6.3
EXP 9
1/99
10/1
413
6.9
EXP 10
1/99
1/0
414
4.6
Ag + /MMT
CEXP 1
7/93
1/1
Ethanol
413
5.1
Ag + /NSP
CEXP 2
7/93
1/1
Methanol
420
6.3
CEXP 3
7/93
1/1
Isopropyl
420
6.6
alcohol
Ag + /SMA
solvent
CEXP 4
7/93
DI water
Sodium
413
6.9
borohydride
[0110] 5) The Reversibility of the AgNP with Different Diameters:
[0111] Next, we further tested the reversibility of the AgNP with different diameters and found that the stability of the AgNP is best while the weight ratio of Ag + /NSP is in a range between 1/99 and 15/85 (EXAMPLE 1, 3, 4). During the stability test, we found that the characteristic absorbance peak of AgNP/NSP returns to the state in the original solution after re-dissolving the film into water. It is the evidence of the reversibility of the AgNP. The reversibility still works even the AgNPs aggregate while forming the film. The reversibility is poorer while the weight ratio of Ag + /NSP is in a range between 30/70 and 50/50 (EXAMPLE 5 and 6), however, it is still better than the AgNP/MMT (comparison example 1). FIG. 12 shows the test result of the UV-visible spectrometer, we can check the reversibility by the position of the absorbance peak. FIG. 13 and FIG. 14 show the UV-visible spectrogram and the test result via the TEM, which shows the size of the AgNP is reversible after the film-forming process, and the particle's size of the AgNP has only slight change before film-forming process and after re-dissolving.
[0112] 6) The Inhibitory and Bactericidal Ability of the AgNP/Clay:
[0113] The AgNP/NSP of the present invention has a superior inhibitory ability. FIG. 15 shows the result of the inhibitory test of the AgNP of the comparison example 1, and we found that the AgNP/NSP of EXAMPLE 1 has a superior inhibitory ability. 10 ppm Ag + may kill all the E. coli in three hours of contact. The AgNP/MMT of the comparison example 1 (l0ppm A g +) will lose the inhibitory ability after six hours of contact.
[0114] We test the inhibitory ability of the AgNP of EXAMPLE 1, 3-6 with the minimum bactericidal concentration (MBC) of AgNP/NSP (10 ppm). The result shows that the bactericidal ability on the E. coli is better with smaller particles, and the result is the same for the P. aeruginosa, S. aureus, S. pyogenes , and Gram-negative/positive bacteria, as shown in FIG. 16 and Table 4. Therefore, the bactericidal ability is affected by the weight ratio of the AgNP/NSP. It proves that the main fact that affects the bactericidal ability is the particle's size. FIG. 17 and FIG. 18 show the change of strains of E. coli and S. aureus in contact with the AgNP/NSP via the SEM.
[0000]
TABLE 4
the minimum inhibitory concentration (MIC a ) and the minimum
bactericidal concentration (MBC b ) of the AgNP/NSP
bacteria
P 35
P 17
P 19
P 5
P 3.8
MIC (ug/mL)
E. coli
14.9
14.4
19.0
3.1
1.7
P. aeruginosa
>40
>40
40.0
26.3
17.2
S. aureus
>30
27.5
30.7
12.7
12.4
S. pyogenes
16.0
13.3
14.3
4.7
4.1
MBC (ug/mL)
E. coli
18.2
19.4
25.4
7.2
4.9
P. aeruginosa
>50
>50
50.0
30.1
21.5
S. aureus
>30
29.1
32.0
14.9
14.7
S. pyogenes
19.2
16.1
20.5
6.6
4.9
a the concentration of no visible bacteria colonies growth (after 24 hours, observation with naked eyes)
b the concentration of 99.9% bacteria colonies being killed (24 hours after no bacteria colonies growth being found)
[0115] A further bactericidal test is undertaken for comparing the bactericidal ability of AgNP with the same size but in different weight ratios with the NSP (AgNP/NSP is 1/99 and 0.5/99.5 as in EXAMPLE 2 and 3). The result shows that the bactericidal ability of the AgNP/NSP in 0.5/99.5 is better than the AgNP/NSP in 1/99, as shown in FIG. 19 . It also proves that the higher ratio of the NSP is, the better bactericidal ability comes. Due to the large surface area and high surface charges of the NSP, the NSP is attached to the bacteria easily, and therefore more AgNP has contact with the bacteria. In other words, the bactericidal ability of the present invention may be controlled by the weight ratio of the AgNP/NSP.
[0116] The description above is a few preferred embodiments of the present invention, and the equivalence of the present invention is still in the scope of claim construction of the present invention.
|
A method of synthesizing size-controllable metal nanoparticles includes the following steps: a) Preparing an exfoliated silicate clay solution and a metal ion solution; and b) Mixing the exfoliated silicate clay solution with the metal ion solution, and the metal ions are reduced to the metal nanoparticles, which are attached to the exfoliated silicate clays. Additionally, in step A, adjust the weight ratio of the silicate clays to the metal ions to control the size of the reduced metal particles. And with larger weight ratio of the silicate clays to the metal ions, the size of the reduced metal particles becomes smaller.
| 8
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FIELD OF THE INVENTION
[0001] This invention relates to certain novel carboximide derivatives which selectively inhibit binding to the α 1A adrenergic receptor, a receptor which has been shown to be important in the treatment of benign prostatic hyperplasia. The compounds of the present invention are potentially useful in the treatment of benign prostatic hyperplasia. This invention also relates to methods for synthesizing the novel compounds, pharmaceutical compositions containing the compounds, and method of treating benign prostatic hyperplasia using the compounds.
BACKGROUND OF THE INVENTION
[0002] Benign prostatic hyperplasia (BPH), a nonmalignant enlargement of the prostate, is the most common benign tumor in men. Approximately 50% of all men older than 65 years have some degree of BPH and a third of these men have clinical symptoms consistent with bladder outlet obstruction (Hieble and Caine, Fed. Proc., 1986; 45:2601). Worldwide benign and malignant diseases of the prostate are responsible for more surgery than diseases of any other organ in men over the age of fifty.
[0003] It is generally accepted that there are two components of BPH, a static and a dynamic component. The static component is due to enlargement of the prostate gland, which may result in compression of the urethra and obstruction to the flow of urine from the bladder. The dynamic component is due to increased smooth muscle tone of the bladder neck and the prostate itself (which interferes with emptying of the bladder) and is regulated by alpha 1 adrenergic receptors (α 1 -ARs). The medical treatments available for BPH address these components to varying degrees, and the therapeutic choices are expanding.
[0004] Surgical treatment options address the static component of BPH and include transurethral resection of the prostate (TURP), open prostatectomy, balloon dilatation, hyperthermia, stents and laser ablation. Although, TURP is the gold standard treatment for patients with BPH, approximately 20-25% of patients do not have a satisfactory long—term outcome (Lepor and Rigaud, J. Urol., 1990; 143:533). Postoperative urinary tract infection (5-10%), some degree of urinary incontinence (2-4%), as also reoperation (15-20%) (Wennberg et al., JAMA, 1987; 257:933) are some of the other risk factors involved.
[0005] Apart from surgical approaches, there are some drug therapies which address the static component of this condition. Finasteride (Proscar, Merck), is one such therapy which is indicated for the treatment of symptomatic BPH. This drug is a competitive inhibitor of the enzyme 5α-reductase which is responsible for the conversion of testosterone to dihydrotestosterone in the prostate gland (Gormley et al., N. Engl. J. Med., 1992; 327:1185). Dihydrotestosterone appears to be the major mitogen for prostate growth, and agents which inhibit 5-α-reductase reduce the size of the prostate and improve urine flow through the prostatic urethra. Although finasteride is a potent 5α-reductase inhibitor and causes a marked decrease in serum and tissue concentration of dihydrotestosterone, it is only moderately effective in treating symptomatic BPH (Oesterling, N. Engl. J. Med., 1995; 332:99). The effects of finasteride take 6-12 months to become evident and for many men the clinical improvement is minimal.
[0006] Due to the limited effectiveness of 5α-reductase inhibitors in terms of immediate symptomatic and urodynamic relief, other pharmacological approaches have been assessed in the clinical setting.
[0007] The dynamic component of BPH has been addressed by the use of adrenergic receptor blocking agents (α 1 -AR blockers) which act by decreasing the smooth muscle tone within the prostate gland itself. α 1 -adrenergic receptor antagonists appear to be much more effective and provide immediate subjective symptomatic improvements and are, therefore, the preferred modalities of treatment in the control of benign prostate hypertrophy. α 1 -Adrenoceptors are also present in blood vessels and play an important role in the regulation of blood pressure. Thus, α 1 -adrenoceptor antagonists are of particular importance as they were originally developed as antihypertensive agents and are likely also to have a beneficial affect on lipid dysfunction and insulin resistance, which are commonly associated with essential hypertension.
[0008] The use of α 1 -AR antagonists in the treatment of BPH is related to their ability to decrease the tone of prostatic smooth muscle, leading to relief of the obstructive symptoms. Adrenergic receptors found throughout the body play a dominant role in the control of blood pressure, nasal congestion, prostate function and other processes (Harrison et al., Trends Pharmacol. Sci., 1991; 12:62). There are a number of cloned α 1 -AR receptor subtypes: α 1A -AR, α 1B -AR and α 1D -AR (Bruno et al., Biochem. Biophys. Res. Commun., 1991; 179:1485; Forray et al., Mol. Pharmacol., 1994; 45:703; Hirasawa et al., Biochem. Biophys. Res. Commun., 1993; 195:902; Ramarao et al., J. Biol. Chem., 1992; 267:21936; Schwinn et al., JPET, 1995; 272:134; Weinberg et al., Biochem. Biophys. Res. Commun., 1994; 201:1296). A number of laboratories have characterized the α 1 -ARS in human prostate by function, radioligand binding, and molecular biological techniques (Forray et al., Mol. Pharmacol. 1994; 45:703; Hatano et al., Br. J. Pharmacol, 1994; 113:723; Marshall et al., Br. J. Pharmacol. 1992; 112:59; Marshall et al., Br. J. Pharmacol., 1995; 115:781; Yamada et al., Life Sci., 1994; 54:1845). These studies provide evidence in support of the concept that the α 1A -AR subtype comprises the majority of α 1 -ARS in human prostatic smooth muscle and mediates contraction in this tissue. These findings suggest that the development of a subtype-selective α 1A -AR antagonists might result in a therapeutically effective agent with reduced side effects for the treatment of BPH.
[0009] A variety of α 1 -AR blockers (terazosin, prazosin, and doxazosin) have been investigated for the treatment of symptomatic bladder outlet obstruction due to BPH, with terazosin (Hytrin, Abbott) being the most extensively studied. Although the α 1 -AR blockers are well tolerated, approximately 10-15% of patients develop a clinically adverse event. The undesirable effects of all members of this class are similar, with postural hypotension being the most commonly experienced side effect.
[0010] The α 1 -AR blocking agents have a more rapid onset of action. However, their therapeutic effect, as measured by improvement in the symptom score and the peak urinary flow rate, is moderate. (Oesterling, N. Engl. J. Med., 1995; 332:99). The vascular side effects (e.g., postural hypertension, dizziness, headaches, etc.) associated with these drugs is due to lack of selectivity of action between prostatic and vascular α 1 -adrenoceptors. Clearly, α 1 -adrenoceptor antagonists which have inherently greater selectivity for prostatic α 1 -adrenoceptors offer the potential of increased urodynamic benefits. This underscores the importance of the discovery of prostate-selective α 1 -adrenoceptor antagonists which will confer urodynamic improvement without the side effects associated with existing drugs.
[0011] There are many description in the literature about the pharmacological activities associated with α,ω-dicarboximide derivatives. Eur. J. Med. Chem. Chemica Therapeutica; 1977; 12(2):173, J. Indian. Chem. Soc., 1978; LV:819; J. Indian Chem. Soc., 1979; LVI:1002 discuss the synthesis of these derivatives with CNS and antihypertensive activity. Other references like U.S. Pat. Nos. 4,524,206; 4,598,078; 4,567,180; 4,479,954; 5,183,819; 4,748,240; 4,892,943; 4,797,488; 4,804,751; 4,824,999; 4,957,913; 5,420,278; 5,330,762; 4,543,355 and PCT application Nos. WO 98/37893; WO 93/21179, also describe CNS and antihypertensive activity of these compounds. There is no mention of adrenoceptor blocking activity of these compounds and thus their usefulness in the treatment of BPH did not arise.
[0012] J. Med. Chem., 1983; 26:203 reports dopamine and α 1 -adrenergic activity of some Buspirone analogues. EP 078800 discusses α 1 -adrenergic receptor antagonistic activity of pyrimidinedione, pyrimidinetrione and triazinedione derivatives. These compounds, however, had low α 1 -adrenergic blocking activity as compared to known α 1 -antagonists.
[0013] The earlier synthesis of various 1-(4-arylpiperazin-1-yl)-3-(2-oxo-pyrrolidin-1-yl/piperidin-1-yl)alkanes and their usefulness as hypotensive and antischemic agents is disclosed in Indian Patent applications 496/DEU95, 500/DEU95 and 96/DEU96. These compounds had low α 1 -adrenergic blocking activity (pKi˜6 as compared to >8 of the known α 1 -antagonists such as prazosin), and practically no adrenoceptor sub-class selectivity for α 1A vs. α 1B or α 1D adrenoceptors. Further work showed that structural modification of these compounds from lactam to dioxo compounds, i.e., from 2-oxopyrrolidin to 2,5-dioxopyrrolidin and 2,6-dioxopiperidine, enhances the adrenoceptor blocking activity, and also greatly increases the selectivity for α 1A in comparison to α 1B -adrenoceptor blocking activity, an essential requirement for compounds to be good candidates for treatment of benign prostatic hyperplasia (BPH) disclosed in our U.S. Pat. Nos. 6,083,950 and 6,090,809 which are incorporated herein by reference.
OBJECTS OF THE INVENTION
[0014] Recently, it has been demonstrated that the prostate tissue of higher species like man and dog has a predominant concentration of α 1A -adrenoceptor subtype. This makes it possible to develop agents with selective action against these pathological urodynamic states. The present invention is directed to the development of novel α 1 -adrenoceptors and which would thus offer a viable selective relief for prostate hypertrophy as well as essential hypertension, without the side effects associated with known α 1A -AR antagonists.
[0015] The objective of the present invention is to provide novel carboximide derivatives that exhibit significantly greater α 1A -adrenergic blocking potency than available with known compounds in order to provide specific treatment for benign prostatic hyperplasia.
[0016] It is also an object of the invention to provide a process for synthesis of the novel compounds.
[0017] It is a further object of the invention to provide compositions containing the novel compounds which are useful in the treatment of benign prostatic hyperplasia.
SUMMARY OF THE INVENTION
[0018] The above mentioned objectives are achieved by novel carboximide derivatives represented by Formula I below:
[0019] wherein X is selected from the group consisting of
[0020] where the points of attachment are depicted by hashed bonds, and
[0021] where one point of attachment is bonded to the carbonyl adjacent to the nitrogen and the second point of attachment is bonded to the other carbonyl;
[0000] W is O, S, SO or SO 2
[0022] A is —(CH 2 )m—,
[0023] where m is one of the integers 2, 3 or 4;
[0024] R 11 is independently selected from H, F, Cl, Br, I, OH, straight or branched lower (C 1-6 ) alkyl, lower (C 1-6 ) alkoxy, lower (C 1-6 ) perhaloalkyl and lower (C 1-6 ) perhaloalkoxy;
[0025] Y is selected from the group consisting of
[0026] R 1 and R 2 are independently selected from H, OH, CN, NO 2 , Cl, F, Br, I, OR 3 , COR 3 , OCOR 3 , COOR 3 , NH 2 , N(R 4 , R 15 ), lower (C 1-4 )alkyl, lower (C 1-4 )alkoxy, lower (C 1-4 )alkylthio, lower (C 1-4 ) perhaloalkyl, lower (C 1-4 ) perhaloalkoxy, lower (C 1-4 ) alkoxy substituted with one or more of F, Cl, Br, I, OH, or OR 3 , optionally substituted group selected from aryl, aryloxyaralkyl, heterocyclyl or heteroaryl and said substituents being H, F, Cl, Br, I, OH, OR 3 , lower (C 1-4 )alkyl, lower (C 1-4 )alkyl substitued with one or more of F, Cl, Br, I, OH or OR 3 , wherein R 3 is selected from the group consisting of H, straight or branched C 1 -C 6 alkyl and perhaloalkyl; R 4 and R 5 are independently selected from the group consisting of H, CHO, substituted or unsubstituted lower (C 1-4 )alkyl, lower (C 1-4 )alkoxy, COR 3 , COOR 3 , CH 2 CH(OR 3 ) 2 , CH 2 COOR 3 , CH 2 CHO and (CH 2 ) 2 OR 3 where R 3 is the same as defined above; R 6 , R 7 , R 8 , R 9 and R 10 are independently selected from H, OH, CN, NO 2 , Cl, F, Br, I, straight or branched lower (C 1-4 )alkyl optionally substituted with one or more halogens, lower (C 1-4 )alkoxy optionally substituted with one or more halogens, (C 3-6 )cycloalkoxy, NH 2 , N-lower (C 1-4 )alkylamino, N,N-di-lower (C 1 -C 4 )alkylamino, N-lower (C 1 -C 4 ) alkyl amino carbonyl, hydroxy substituted with aromatic or non-aromatic five or six membered ring, phenyl and phenyl substituted by Cl, F, Br, I, NO 2 , NH 2 , (C 1-4 )alkyl or (C 1-4 )alkoxy, (C 1-4 ) perhaloalkyl, (C 1-4 ) perhaloalkoxy wherein a broken line (----) is a single bond or no bond.
[0027] The present invention also provides pharmaceutical compositions for the treatment of benign prostatic hyperplasia. These compositions comprise an effective amount of at least one of the above compounds of Formula I and/or an effective amount of at least one physiologically acceptable acid addition salt thereof, with a pharmaceutically acceptable carrier and optionally included excipients.
[0028] An illustrative list of particular compounds of the invention is given below:
1-Carboxycyclohex-4-ene-2-[N-{3-(2-ethoxyphenyl)piperazin-1-yl}propyl]carboxamide, (Compound No. 1) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-isopropoxyphenyl)piperazin-1-yl}propyl]carboxamide, (Compound No. 2) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-methoxyphenyl)piperazin-1-yl}-2-hydroxypropyl]carboxamide, (Compound No. 3) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-hydroxyphenyl)piperazin-1-yl}-2-hydroxypropyl]carboxamide, (Compound No. 4) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-isopropoxyphenyl)piperazin-1-yl}-2-hydroxypropyl]carboxamide, (Compound No. 5) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-ethoxyphenyl)piperazin-1yl}-2-hydroxyphenyl]carboxamide, (Compound No. 6) 5-[N-{3-(2-hydroxyphenyl)piperazin-1-yl}]-1-aminopropyl-5-oxo-pentan-1-oic acid, (Compound No. 7) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-hydroxyphenyl)piperazin-1-yl}propyl]carboxamide, (Compound No. 8) 5-[N-{3-(2-Isopropoxyphenyl)piperazin-1-yl}-1-aminopropyl]-5-oxo-pentan-1-oic acid, (Compound No. 9) Methyl-5-[N-{3-(2-methoxyphenyl)piperazin-1-yl}-1-aminopropyl]-5-oxo-pentanoate hydrochloride, (Compound No. 10) 1-Carboxymethylcyclohex-4-ene-2-[N-{3-(2-isopropoxyphenyl)piperazin-1-yl}-propyl]carboxamide hydrochloride, (Compound No. 11) 5-[N-{3-(2-Methoxyphenyl)piperazin-1-yl}]-2-hydroxypropylamino-5-oxo-pentan-1-oic acid, (Compound No. 12)
[0041] Pharmaceutically acceptable, non-toxic acid addition salts of the compounds of the present invention having the utility of the free bases of Formula I, may be formed with inorganic or organic acids, by methods well known in the art and may be used in place of the free bases. Representative examples of suitable acids for formation of such acid addition salts are malic, fumaric, benzoic, ascorbic, pamoic, succinic, bismethylene salicylic, methanesulfonic, ethane disulfonic, acetic, propionic, tartaric, salicylic, citric, gluconic, aspartic, stearic, palmitic, itaconic, glycolic, p-aminobenzoic, glutamic, benzenesulfamic, phosphoric, hydrobromic, sulfuric, cyclohexylsulfamic, hydrochloric, and nitric acids.
[0042] The present invention also includes within its scope prodrugs of the compounds of Formula I. In general, such prodrugs will be functional derivatives of these compounds which readily get converted in vivo into the defined compounds. Conventional procedures for the selection and preparation of suitable prodrugs are known.
[0043] The invention also includes the enantiomers, diastereomers, N-oxides, polymorphs, pharmaceutically acceptable salts and pharmaceutically acceptable solvates of these compounds, as well as metabolites having the same type of activity. The invention further includes pharmaceutical compositions comprising the molecules of Formula I, or prodrugs, metabolites, enantiomers, diastereomers, N-oxides, polymorphs, solvates or pharmaceutically acceptable salts thereof, in combination with a pharmaceutically acceptable carrier and optionally included excipients.
[0044] In yet another aspect, the invention is directed to methods for selectively blocking α 1A receptors by delivering in the environment of said receptors, e.g., to the extracellular medium (or by administering to a mammal possessing said receptors), an effective amount of the compounds of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0045] In order to achieve the above mentioned objects and in accordance with the purpose of the invention as embodied and broadly described herein, there is provided a process for the synthesis of compounds of Formula I, as shown in Scheme I
[0046] wherein X is selected from the group consisting of
[0047] where the points of attachment are depicted by hashed bonds, and
[0048] where one point of attachment is bonded to the carbonyl adjacent to the nitrogen and the second point of attachment is bonded to the other carbonyl;
[0000] W is O, S, SO or SO 2
[0049] A is —(CH 2 )m—,
[0050] where m is one of the integers 2, 3 or 4;
[0051] R 11 is independently selected from H, F, Cl, Br, I, OH, straight or branched lower (C 1-6 ) alkyl, lower (C 1-6 ) alkoxy, lower (C 1-6 ) perhaloalkyl and lower (C 1-6 ) perhaloalkoxy;
[0052] Y is selected from the group consisting of
[0053] R 1 and R 2 are independently selected from H, OH, CN, NO 2 , Cl, F, Br, I, OR 3 , COR 3 , OCOR 3 , COOR 3 , NH 2 , N(R 4 , R 5 ), lower (C 1-4 )alkyl, lower (C 1-4 )alkoxy, lower (C 1-4 )alkylthio, lower (C 1-4 ) perhaloalkyl, lower (C 1-4 ) perhaloalkoxy, lower (C 1-4 ) alkoxy substituted with one or more of F, Cl, Br, I, OH, or OR 3 , optionally substituted group selected from aryl, aryloxyaralkyl, heterocyclyl or heteroaryl and said substituents being H, F, Cl, Br, I, OH, OR 3 , lower (C 1-4 )alkyl, lower (C 1-4 )alkyl substitued with one or more of F, Cl, Br, I, OH or OR 3 , wherein R 3 is selected from the group consisting of H, straight or branched C 1 -C 6 alkyl and perhaloalkyl; R 4 and R 5 are independently selected from the group consisting of H, CHO, substituted or unsubstituted lower (C 1-4 )alkyl, lower (C 1-4 )alkoxy, COR 3 , COOR 3 , CH 2 CH(OR 3 ) 2 , CH 2 COOR 3 , CH 2 CHO and (CH 2 ) 2 OR 3 where R 3 is the same as defined above; R 6 , R 7 , R 8 , R 9 and R 10 are independently selected from H, OH, CN, NO 2 , Cl, F, Br, I, straight or branched lower (C 1-4 )alkyl optionally substituted with one or more halogens, lower (C 1-4 )alkoxy optionally substituted with one or more halogens, (C 3-6 )cycloalkoxy, NH 2 , N-lower (C 1-4 )alkylamino, N,N-di-lower (C 1 -C 4 )alkylamino, N-lower (C 1 -C 4 ) alkyl amino carbonyl, hydroxy substituted with aromatic or non-aromatic five or six membered ring, phenyl and phenyl substituted by Cl, F, Br, I, NO 2 , NH 2 , (C 1-4 )alkyl or (C 1-4 )alkoxy, (C 1-4 ) perhaloalkyl, (C 1-4 ) perhaloalkoxy wherein a broken line (----) is a single bond or no bond.
[0054] The starting materials of Scheme I may be suitably adapted to produce the more specific compounds of Formula I.
SCHEME I
[0055] Scheme I shows the synthesis of the compounds of Formula I wherein X, Y, A, R 6 , R 7 , R 8 , R 9 and R 10 are as defined above. The preparation comprises reacting α,ω-dicarboximides of Formula II with a suitable strong base, at a temperature ranging from 20-100° C. for a period varying between one to several hours to produce the corresponding compounds of Formula I. The suitable base is selected from the group consisting of sodium hydroxide and potassium hydroxide. More specifically, the hydrolysis of compound of Formula II is carried out in a solution of the base made in a polar solvent selected from the group consisting of water, methanol and ethanol. The preferable temperature conditions for the reaction are 90-100° C. The starting compound of Formula II can be prepared by the process as disclosed in our internal application number RLL-236WO filed concurrently herewith.
[0056] The invention is explained in detail in the example given below which is provided by way of illustration only and therefore should not be construed to limit the scope of the present invention.
EXAMPLE
Preparation of 1-carboxy cyclohex-4-ene-2-[N-{3-(2-ethoxyphenyl)piperazin-1-yl}propyl]carboxamide (Compound No. 1).
[0057] 2-[3-{4-(2-Ethoxyphenyl)piperazin-1-yl}propyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione hydrochloride (0.5 g, 1.15 mmol) was dissolved in aqueous sodium hydroxide solution (11.5 ml, 0.2N) and heated to reflux for about 2 hours. After the reaction was over, the pH of the reaction was adjusted to about 7 using glacial acetic acid and extracted with chloroform (2×15 ml). The solvent was concentrated under reduced pressure and the crude product was crystallized from chloroform and diethylether to afford the title product 0.13 g (25%), m.pt. 128-131° C.
[0000] MS m/z: 430.5 (MH + )
[0058] IR (KBr cm −1 ): 1645.8 (C=0)
[0059] 1 H NMR (300 MHz, TFA) δ:1.72-1.74 (3H,d), 2.59 (2H, br s), 2.80 (3H, br s), 2.93-2.99 (1H, d), 3.53 (1H, br s), 3.69 (1H, br s), 3.86-3.98 (m, 4H), 4.47-4.50 (6H, m), 4.75-4.79 (2H, m), 5.11-5.19 (1H, m), 6.00-6.13 (2H, br d), 7.39-7.49 (2H, m), 7.82-7.88 (2H, m)
[0060] The following compounds were prepared similarly:
1-Carboxy cyclohex-4-ene-2-[N-{3-(2-isopropoxyphenyl)piperazin-1-yl}propyl]carboxamide; m.p. 186-188° C., (Compound NO. 2) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-methoxyphenyl)piperazin-1-yl}-2-hydroxypropyl]carboxamide; m.p. 140-143° C., (Compound No. 3) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-hydroxyphenyl)piperazin-1-yl}-2-hydroxypropyl]carboxamide; m.p. 124-127° C., (Compound No. 4) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-isopropoxyphenyl)piperazin-1-yl}-2-hydroxy propyl]carboxamide; m.p. 159-162° C., (Compound No. 5) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-ethoxyphenyl)piperazin-1yl}-2-hydroxyphenyl]carboxamide; m.p. 118-121° C., (Compound No. 6) 5-[N-{3-(2-hydroxyphenyl)piperazin-1-yl}]-1-aminopropyl-5-oxo-pentan-1-oic acid; m.p. 200-202° C., (Compound No. 7) 1-Carboxy cyclohex-4-ene-2-[N-{3-(2-hydroxyphenyl)piperazin-1-yl}propyl]carboxamide; m.p. 165-170° C., (Compound No. 8) 5-[N-{3-(2-Isopropoxyphenyl)piperazin-1-yl}-1-aminopropyl]-5-oxo-pentan-1-oic acid; m.p. 121-125° C., (Compound No. 9) Methyl-5-[N-{3-(2-methoxyphenyl)piperazin-1-yl}-1-aminopropyl]-5-oxo-pentanoate hydrochloride; m.p. 191-194° C., (Compound No. 10) 1-Carboxymethylcyclohex-4-ene-2-[N-{3-(2-isopropoxyphenyl)piperazin-1-yl}-propyl]carboxamide hydrochloride, (Compound No. 11) 5-[N-{3-(2-Methoxyphenyl)piperazin-1-yl}]-2-hydroxypropylamino-5-oxo-pentan-1-oic acid; m.p. 140-144° C., (Compound No. 12
Pharmacological Testing Results
[0000] Receptor Binding Assays
[0072] Receptor binding assays were performed using native α-adrenoceptors. The affinity of different compounds for α 1A and α 1B adrenoceptor subtypes was evaluated by studying their ability to displace specific [ 3 H] prazosin binding from the membranes of rat submaxillary and liver respectively (Michel et al, Br J. Pharmacol.; 1989; 98:883). The binding assays were performed according to U'Prichard et al. (Eur J Pharmacol., 1978; 50:87) with minor modifications.
[0073] Submaxillary glands were isolated immediately after sacrifice. The liver was perfused with buffer (Tris HCl 50 mM, NaCl 100 mM, 10 mM EDTA pH 7.4). The tissues were homogenised in 10 volumes of buffer (Tris HCl 50 mM, NaCl 100 mM, 10 mM EDTA pH 7.4). The homogenate was filtered through two layers of wet gauge and filtrate was centrifuged at 500 g for 10 min. The supernatant was subsequently centrifuged at 40,000 g for 45 min. The pellet thus obtained was resuspended in the same volume of assay buffer (Tris HCl 50 mM, 5 mM EDTA pH 7.4) and were stored at −70° C. until the time of assay.
[0074] The membrane homogenates (150-250 μg protein) were incubated in 250 μl of assay buffer (Tris HCl 50 mM, EDTA 5 mM, pH 7.4) at 24-25° C. for 1 hour. Non specific binding was determined in the presence of 300 nM prazosin. The incubation was terminated by vacuum filtration over GF/B fibre filters. The filters were then washed with ice cold 50 mM Tris HCl buffer (pH 7.4). The filtermats were dried and bound radioacivity retained on filters was counted. The IC 50 and Kd were estimated by using the non linear curve fitting program using G Pad Prism software. The value of inhibition constant Ki was calculated from competitive binding studies by using Cheng & Prusoff equation (Cheng & Prusoff, Biochem Pharmacol, 1973,22: 3099), Ki=IC 50 /(1+L/Kd) where L is the concentration of [ 3 H] prazosin used in the particular experiment (Table I).
[0000] In Vitro Functional Studies
[0075] In order to study selectivity of action of these compounds towards different α-adrenoceptor subtypes, the ability of these compounds to antagonise aorta (α 1D ), prostate (α 1A ) and spleen (α 1B ) was studied. Aorta, prostrate and spleen tissues were isolated from urethane anaesthetized (1.5 g/kg) male wister rats. Isolated tissues were mounted in organ bath containing Krebs Henseleit buffer of the following composition (mM): NaCl 118; KCl 4.7; CaCl 2 2.5; MgSO 4 7H 2 O 1.2; NaHCO 3 25; KH 2 PO 4 1.2; glucose 11.5. Buffer was maintained at 37° C. and aereated with a mixture of 95% O 2 and 5% CO 2 . A resting tension of 2 g (aorta) or 1 g (spleen and prostate) was applied to tissues. Contractile response was monitored using a force displacement transducer and recorded on chart recorders. Tissues were allowed to equilibrate for 2 hours. At the end of equilibration period, concentration response curves to norepinephrine (aorta) and phenylepinephrine (spleen and prostate) were obtained in the absence and presence of tested compound (at concentration of 0.1, 1 and 10 μM). Antagonist affinity was calculated and expressed as pK B values in Table II.
[0000] In Vivo Uroselectivity Study
[0076] In order to assess the uroselectivity in vivo, the effects of these compounds were studied on mean arterial pressure (MAP) and intraurethral pressure (IUP) in conscious beagle dogs as per the method of Brune et. al. (Pharmacol., 1996, 53:356). Briefly, male dogs were instrumented for chronic continuous measurement of arterial blood pressure by implanting a telemetry transmitter (TL11 M2-D70-PCT, Data Sci. International, St. Paul, Minn. USA) into the femoral artery, two weeks prior to the study. During the recovery period, the animal was acclimatized to stay in the sling restraint. On the day of testing, overnight fasted animal was placed in the sling restraint. A Swan-Ganz. Balloon tipped catheter was introduced into the urethra at the level of prostate and the balloon was inflated (Brune. et. al. 1996). After recording the base line readings, effect of 16 μg/kg, phenylephrine (i.v.) on MAP and IUP was recorded. The response of phenylephrine to MAP and IUP were recorded at 0.5, 1, 2, 3, 4, 6, 9 and 24 hours after the oral administration of vehicle or the test drug. The changes in MAP were recorded on line using Dataquest Software (Data Sci. International. St. Paul, Minn. USA). The change in phenylephrine response on MAP and IUP administration after the test drug administration was calculated as percent change of that of control values. Area under curve was calculated and the ratio of the values for MAP and IUP was used for calculating the uroselectivity.
TABLE1 Radioligand Binding Studies: Affinity of compounds for Alpha-1 Adrenoceptor Subtypes α 1A α 1B S No Compound No. (Rat Submaxillary) (Rat Liver) α 1B /α 1A 1 1 20 >1000 >50 2 2 19 >1000 >53 3 3 >1000 >1000 4 4 1892 9743 5 5 5 21 1759 84 6 6 398 1239 3 7 7 12640 12970 1 8 8 593 5082 9 9 9 777 2097 3 10 10 139 >1000 >7 11 11 3.15 99 31 12 12 >1000 >10000 1
[0077]
TABLE II
In Vitro Functional Assays
α-Adrenoceptor Subtype
Compound
(pK B )
Selectivity
S. No.
No.
α 1A
α 1B
α 1D
α 1B /α 1A
α 1D /α 1A
1
1
8.22
8.16
7.24
1.15
9.5
[0078] While the present invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the present invention.
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Novel carboximide derivatives, which selectively inhibit binding to the α 1A adrenergic receptor, a receptor which has been shown to be important in the treatment of benign prostatic hyperplasia. The compounds of the present invention are potentially useful in the treatment of benign prostatic hyperplasia.
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TECHNICAL FIELD OF THE INVENTION
The present invention relates to novel improved devices which can be used to transport the eggs of aquatic creatures and then incubate and grow out the eggs.
One important application of the present invention is in salmonid rearing. The principles of the present invention will, in large part, be developed herein with reference to that application for the sake of brevity and clarity. In that respect, generic terms will be used when possible. Where no generic term exists, the term salmonids will be used with the understanding that the equivalent term for other aquatic creatures is meant to be included. It is to be understood, therefore, that this discussion of salmon farming is not intended to limit the scope of the invention as defined by the appended claims.
BACKGROUND OF THE INVENTION
Salmon farming begins in freshwater. Farmers strip ready-to spawn broodstock salmon of eggs and sperm. Prior to fertilization, the eggs are referred to as "green eggs". Once fertilized, the eggs are stored in trays, boxes or baskets fitted with mesh and are constantly flushed with water as they develop. The advanced fertilized eggs when developed to the point where the eyes of the embryo are apparent are referred to as "eyed eggs". The time from fertilization to hatching takes roughly 40 days, at 10° C. although the process varies with each species and is particularly sensitive to water temperature. When the eggs hatch, the resulting fry are referred to as alevin or sac fry. In this stage, the sac fry are still attached to, and obtain nourishment from, the yolk sac. The sac fry tend to hug the bottom of the container in which they are kept.
After the nutrients in the yolk sac are depleted, the fry swim to the surface and begin feeding. At this point, the fry are referred to as "starter fed" or "swim up" fry. When the fry, or fingerlings, reach the feeding stage, they are moved to troughs, or tanks.
Rearing fry to the next, smolt stage, at which time the fish are capable of adapting to a marine environment, takes from zero to 15 months depending on the species. Smoltification changes a fish's body shape and physical coloration. Once salmon reach this stage, the two-to-three-ounce fish are released into the ocean or transported to saltwater netpens anchored close to shore to begin the grow-out phase.
During the grow-out phase, the salmon are given a commercial diet for from nine months (for coho) to two years (for Atlantic salmon). The fish are typically fed 2 percent of their body weight per day; between one and a half and two pounds of feed produce one pound of salmon. It is common for fertilized fish eggs to be harvested at one location, transported to a second location, and hatched at that location.
At the eyed stage the salmonid embryo can be transported over long distances. During transportation and incubation, nevertheless the eggs of most aquatic creatures must be kept within a given temperature range. For example, the eyed eggs of salmonids should be kept between 35° and 45° Fahrenheit while the eggs are being transported. Heretofore, separate pieces of equipment have been employed to transport and incubate the fertilized eggs and then grow out the fry. One heretofore proposed transport device is disclosed in U.S. Pat. No. 3,194,211 issued Jul. 13, 1965 to Stanek for TRANSPORT AND COOLING CONTAINER FOR LIVING FISH ROE AND/OR FRY; and other transport containers are discussed in that patent. U.S. Pat. No. 3,024,764 issued Mar. 13, 1962 to Brittain et al for FISH EGGS INCUBATORS; U.S. Pat. No. 4,014,293 issued Mar. 29, 1977 to Salter for FISH EGG INCUBATOR; U.S. Pat. No. 4,094,270 issued Jun. 13, 1978 to WHITLOCK for FISH EGG INCUBATORS; U.S. Pat. No. 4,180,012 issued Dec. 25, 1979 to Zenger, Sr. for FISH EGG INCUBATOR WITH FRY RELEASE MEANS; and U.S. Pat. No. 4,182,269 issued Jan. 8, 1980 to Young, II for INCUBATOR FOR SALMON ID EGGS AND ALEVIN disclose heretofore proposed incubators.
Also, it is often desirable to plant fish in spawning streams to supplement natural spawning runs. Currently, in planting fish in spawning streams, eggs are also fertilized at one location, transported in an appropriate container to the stream, and placed in a separate incubator at the stream where they are hatched. After the fry reach the feeding stage, they are released into the stream.
This need for two separate pieces of equipment, one for transporting and another for incubating eggs and then growing out the fry hatched therefrom increases significantly the cost of raising fish to the fry or fingerling stage. Also, heretofore proposed fish egg transporting devices and incubators tend to have such disadvantages as complexity, high cost, low structural integrety and survival rates as well as the quality of the fry are often marginal.
Currently, transportation of fish fry is accomplished by placing the fry in water in a closed container. Air is left in the closed container to allow oxygenation of the fish during transportation. The fry are then transported to another location. The problem with this method is that the number of fish that may be transported per container is undesirably limited because the closed container can be filled to only one-third of its capacity with water.
SUMMARY OF THE INVENTION
I have now invented and disclosed herein certain novel devices which are designed to supplant the heretofore available and proposed fish egg incubators and transport containers for extended transport periods and reuse.
These novel devices are so designed that they can be employed to both: (1) transport eggs from one location to another, and (2) then incubate the eggs and grow out the fry at their remote location destination. This substantially reduces the cost of the equipment needed for these separate functions. Also, the cost of transferring the eggs from one piece of equipment to another is eliminated as is the damage that handling inevitably causes.
Generally, the novel transportation and incubation devices of the present invention comprise: (a) an insulated container; (b) a spacing structure in the insulated container; (c) egg containers stacked within the insulated container on the spacing structure; (d) ice trays within the insulated container on top of the egg trays; and (e) a water inlet which allows water to be introduced into the point below the lower- most egg tray and also allows the container to be drained.
Assembled as above-described, the transportation and incubation container of the present invention allows cool water formed by the melting of the ice trays to flow through the eggs. This cool water prevents excessive dehydration of the eggs and keeps the temperature of the eggs within an acceptable range.
During incubation, water is continually or intermittently introduced and circulated through the water inlet and out of the open top of the insulated container or drained back through the in take with a delay period before the incubator is filled with water again. When the eyed eggs hatch into alevin, they swim against the water flow to the bottom of the insulated container through specially designed perforations or holes in the bottoms of the egg trays.
The egg container may be a flat, open tray with a lid or cylindrical tube having both ends closed by caps.
An important feature of the closed-style egg containing tubes means is that it may be removed from the insulated, outer container and placed in a spawning stream to allow natural incubation of the eggs contained therein. In this situation, the egg containing tube is preferably made from biodegradable material.
In yet another embodiment, a water recirculating, filtering, cooling, and aerating system is housed in a sealed, airtight compartment within the insulated outer container means. Such an arrangement allows developing fry to be transported in much greater density than has heretofore been possible.
OBJECTS OF THE INVENTION
From the foregoing, it is clear that one primary and important object of the present invention is to provide a single device for both transporting and incubating eggs of aquatic creatures and then growing out the fry that develop therefrom.
Other important, but more specific, objects of the present invention are to provide a transportation, incubation, and grow-out container that:
is inexpensively manufactured from readily available components;
reduces the cost associated with incubating and rearing fry;
allows fish to be planted in spawning streams without the heretofore existing requirement of a separate incubation and grow-out facility at the headwaters of the spawning stream;
enables transportation of fry in much greater density then has heretofore been possible.
Other important objects and features and additional advantages of the invention will be apparent to the reader from the foregoing and the appended claims and as the ensuing detailed description and discussion proceeds in conjunction with the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a first embodiment of the present invention with the cover open and the ice trays employed in that device removed;
FIG. 2 is a perspective, cut-away view of the first embodiment of the present invention with the cover closed and latched;
FIG. 3 is a perspective, exploded view of the spacing structure and egg containers means of the first embodiment;
FIG. 4 is a perspective view of the second embodiment of the present invention with the cover open;
FIG. 5 is a perspective, cut away view of a second embodiment of the present invention with the cover closed and latched;
FIG. 6A is a side view of the egg container of the second embodiment with its cap removed;
FIG. 6B is a side view of the egg container of the second embodiment in a horizontal position and with its end cap in place;
FIG. 6C is an end, cut away view of the egg container of the second embodiment taken along arrows 6C in FIG. 6B;
FIG. 7 is a perspective, detail view of the egg container and spacing structure of the second embodiment;
FIG. 8A is a side, schematic view of the second embodiment of the present as used in its transportation mode;
FIG. 8B is a side, schematic view of the second embodiment as used in its incubation mode;
FIG. 8C is a side, schematic view of the second embodiment as used in its grow-out mode; and
FIG. 9 is a side, schematic view of a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawing, FIG. 1 depicts a transportation, incubation, and grow-out container 10 constructed in accord with the principles of the present invention. Container 10 comprises: (a) an insulated shell 12 (FIGS. 1 and 2); (b) spacer 14 (FIG. 3); (c) egg trays 16 (FIG. 3); (d) ice trays 18 (FIG. 2); and (e) water inlet 20 (FIGS. 1 and 4).
When container 10 is used for transportation, eyed eggs are stored in trays 16, and ice is held by the trays 18 above the egg trays 16. This allows cool water to flow over the eggs as the ice melts. The eggs are thus kept cool and moist. Water accumulates at the bottom of box 12, but does not drown the eggs because the egg trays are supported above the water by spacer -4.
During incubation, water is either continually or intermittently introduced into the container through the inlet 20 and allowed to flow out the top or drained through the inlet. When the eyed eggs hatch into sac fry, the sac fry swim to the bottom of the container 10 through perforations or holes in the egg containers 16.
A grow-out phase then begins. For this any ice trays and egg containers are typically removed. When the sac fry develop into starter fed or swim up fry, feed may be introduced into the insulated container 10 to allow the fry to develop even further. When the fry reach a maximum size determined by the volume of water in the insulated container 10, they may be introduced into a stream or into starting tanks.
Referring still to the drawing, the container shell or box 12 has a front side 22, a back side 24, a left side 26, a right side 28, and a bottom 30. The top of the box 12 is open, but may be selectively covered by a cover 32. The cover 32 is rotatably attached to the back wall 24 by hinges 34 (FIG. 1). A latch 36 is employed to lock the cover 32 in a closed position (shown in FIG. 2).
As mentioned above, the container shell or box 12 has an insulating layer sandwiched between inner and outer wall layers. The inner layer is preferably fabricated of a high density, food grade polyethylene or other polymer so that the container 10 can be readily disinfected and reused. A polyurethane or other efficient insulation is preferably employed so that the eggs in the insulated container can be kept cool without an unacceptably bulky container. The outer layer of the insulated container is fabricated of a high density polyethylene or other material which will input a high degree of structural integrity to the container. This makes the container capable of withstanding rough handling and allows it to be reused many times.
A raised portion 38 is formed on the inner surface of cover 32. This raised portion 38 is dimensioned to fit snugly within the opening in the top of box 12 when cover 32 is closed. The raised portion 38 allows cover 32 to contact box 12 over a greater surface area when closed to provide a superior insulating seal.
A handle is also provided on box 12 to facilitate the carrying thereof.
The sides 22, 24, 26, and 28 and bottom 30 of box 12 and cover 32 ar designed to keep the interior of box 12 cool when cover 32 is closed. To this end, the sides, bottom, and cover have thin interior and exterior walls with a layer of insulation therebetween. Accordingly, when cover 32 is closed and latched, box 12 substantially inhibits the flow of heat from the exterior to the interior thereof.
Water inlet 20 is placed on box 12 at the lower portion of right side 28. The height and configuration of spacer 14 (FIG. 3) determines the placement of the inlet 20. In general, the spacer 14 must support the lowermost egg tray 16a a fixed distance above the bottom 30 of box 12. The height of spacer 14, indicated by reference character "h" in FIG. 3, is the separation distance between egg tray 16a and container bottom 30.
As mentioned above, as the ice in trays 18 melts, water accumulates at the bottom of box 12. This height "h" of the spacer 14 should be sufficient to keep egg containing tray 16a above the water level after all of the ice is melted. Of course, the displacement of spacer 14 itself must be taken into account.
Once the height "h" of spacer 14 has been determined, the exact placement of inlet 20 can be determined. Specifically, the inlet 20 is preferably placed on any of the walls of box 12 such that water introduced through the inlet 20 enters the box 12 at a height less than the distance "h" from the bottom 30 of the box 12.
Spacer 14 has a generally rectangular configuration. When the spacer 14 is placed in the box 12, its outer faces are adjacent the insides of the walls of the box 12. Accordingly, a gap 40 is formed in the spacer 14; this gap coincides with the point at which the inlet 20 introduces water into the box 12. Water therefore flows unhindered into the interior 42 of the spacer 14 underneath the egg tray 16a.
Egg trays 16a-h are arranged in groups on levels 44a-d comprised of two trays 16 each (Hereinafter, when a specific tray 16 is being discussed with reference to the drawing, a letter suffix will be used as necessary to distinguish among the trays). When two egg trays 16 are arranged in a level 44, the overall shape of the level 44 is rectangular. This rectangular shape substantially conforms to the shape of the interior of the box 12.
Each tray 16 is a five-sided flat box having an open top. Dividers 46 within each tray 16 divide the interior space 48 thereof into four sections 50 of approximately equal size. Holes 52 are formed in the bottom side 54 of each box 16. These holes 52 allow water to pass vertically through the trays 16, but still allow the trays 16 to hold eggs. The dividers 46 substantially inhibit movement of eggs in the egg trays 16, thus may be omitted depending upon the circumstances of use.
Also, formed on the bottom side 54 of each tray 16 is a projecting surface 56. The discontinuity between this surface 56 and the remaining surface of bottom 54 creates a beveled corner 58 traversing the periphery of the bottom 54. This beveled corner is designed to engage the top edge 60 of a like configured tray 16. Accordingly, when one tray 16 is stacked upon another tray 16, the beveled corners 58 and edges 60 interact to prevent front and back and left and right movement of the trays 16 with respect to each other. The egg trays 16a-h thus form a stable column or matrix of trays when stacked on top of one another inside of box 12. Initially, the interior of the box 12 is cleaned and disinfected to prevent contamination of the eggs contained therein during transportation. The spacer 14, egg trays 16a-h, and ice trays 18a and b are similarly cleaned and disinfected. The spacer 14 is then placed on the bottom 30 of the box 12 with gap 40 adjacent inlet 20. The first layer 44a of egg trays 16 is then placed in box 12 on top of spacer 14. Eggs (not shown in FIG. 1-5) may then be placed in the egg trays 16a and b of the first level 44a. Alternatively, the eggs may be placed in the egg trays 16a and b before these egg trays are loaded into container 10.
A wicking material (not shown in FIGS. 1-5) may be placed between each layer 44 of egg trays 16. The wicking material 66 may be made of cheesecloth or a similar porous material. The function of the wicking material is to ensure that water will be dispersed evenly over the eggs contained in the egg trays 16 as it flows downwardly through the several layers 44 of trays 16. This process of stacking egg trays separated by wicking material may be repeated until all of the trays 16 are loaded arranged in layers 44a-d.
At this point, ice trays 18a and b are placed in the box 12 on top of egg trays 16a-h. Ice 68 is then put in the ice trays 18a and b, and the cover 32 of the box 12 is closed and locked by latch 36.
It should also be noted that a valve 70 is employed to close inlet 20 during transportation to prevent water 72 which accumulates at the bottom of box 12 from leaking out of the box 12 through inlet 20.
A second embodiment of the present invention is illustrated in FIGS. 4-8. Elements of the second embodiment that are the same as those in the first embodiment will be given the same reference characters and will not be discussed in further detail.
In this second embodiment, the eggs are loaded into egg tubes, 78 having perforations or holes 52 formed therein (FIGS. 4 and 6).
Also the second embodiment employs spacers 74 which run only along the inside surfaces of the front side 22 and back side 24 of the box 12. The spacers 74 function in basically the same manner as spacer 14.
In this embodiment of the invention, a thin open cell foam pad 76 placed on each row of egg tubes. Ice is spread over each pad 76. This ice is kept away from the eggs by of foam pad 76, but water can drip through the open cells of the foam pad 76. Foam pad 76 is thus very similar in function to the wicking material 66 of the first embodiment.
The egg tubes 78 have a hollow, cylindrical container 80 and caps 82 (FIG. 6). Cylindrical container 80 is sealed at both end 84 and end 86. Cap 82 allows the open end 86 to be closed to prevent the eggs 64 from flowing out that end when the egg tube 78 is horizontal.
In use, eggs are introduced into the tube with the tube in a vertical position (FIG. 6). Cap 56 is then installed.
A known, verifiable amount of eggs is contained within each egg tube 78. Accordingly, once the end cap 82 is sealed on the end 86 of the tube 80, a known quantity of eggs will be delivered.
The perforations or holes 52 in tubes 78 (and egg trays 18) are rectangular. The width of the holes is slightly smaller than the diameter of the eggs to be transported. Therefore, the eggs cannot pass through the holes, and the eggs are effectively held within the egg trays 18 and tubes 78. The diameter of the eggs vary according to the specific aquatic creature. The width of the holes 52 is thus determined by the specific egg type that is being transported.
Once hatched, the sac fry can swim through the holes 52. This is because the fry are curled in the egg. When the fry hatch, they uncurl and have a smaller cross-section-section than the eggs from which they hatch. The uncurled sac fry easily pass through the rectangular openings 52.
The egg tubes 78 may be made of a variety of materials, depending on the use to which the egg tubes 78 is put. In the normal transportation and incubation modes described above, the tubes may be made, for example, of plastic, cardboard, glass, metal or the like. In this situation, the egg tubes 78 are used in an almost identical fashion as the egg trays 16. One difference between the two embodiments is the exact procedure for stacking the egg tubes 78 within the box 12. More specifically, the egg tubes 78 will not interlock when stacked. However, as they are effectively sealed against the possibility of eggs escaping therefrom, the egg tubes 78 may be placed in the box 12 in any arrangement. FIG. 8 depicts the egg tubes being laid horizontally in evenly spaced rows and columns.
Another difference alluded to above, is that ice trays are generally not needed in the second embodiment of the invention. Instead, the ice is simply layered between the rows of containers and spread on the uppermost layer.
Wicking material as optionally provided in the first embodiment may be used with equal or greater effectiveness in the second embodiment. Since the egg tubes 78 do not have an open surface into which water may easily flow, the wicking material will insure that cold water dripping from the ice tray 18 flows into the perforations 52 formed through the egg tubes 78. Thus, water flows into the egg tubes 78 and does not simply flow around the sides thereof.
In certain situations, the egg tubes 78 may be made so that wicking material lines the surface of each hole 52. Such an arrangement of wicking material further improves the flow of water into and through the egg tubes 78.
The second embodiment is prepared for transportation as follows. Spacers 74 are placed in the box 12 along the inside of the front wall 22 and the back wall 24. Tubes 78 are stacked in the box 12 in three rows and eight columns (FIG. 9A). Foam pads 76 are placed between each row and on top of the uppermost row, and ice 68 is over each foam pad 76. Cover 32 is closed and latched shut with latch 36.
During transportation, the ice 68 slowly melts. As the cool water resulting from melting of ice 68 drips through the open cells of foam pad 74, it drips on the eggs in egg tubes 72, continues flowing through the holes 52 in tubes 72, and continues through all of the tubes in box 12. As the water drips from one egg tube to the next, it is wicked into the holes by wicking material 76 to ensure that eggs within the tubes are moistened and cooled.
The eggs are thus kept at an acceptably low temperature, preferably between 35° and 45° Fahrenheit, during transporting. Further, the water passing over the eggs 64 prevents the eggs 64 from becoming overly dehydrated during transportation. The insulating properties of the box 12 and the cover 32 ensure that the ice 68 will not melt too quickly.
The temperature within the box 12 may be controlled even further by controlling the ambient temperature around the transportation and incubation container 10. For example, the container 10 may be transported in a refrigeration equipped truck or container and stored in a refrigerated warehouse.
Depending on the length of time that the eggs are transported, dehydration of the eggs of around 15% by weight can be expected. Therefore, when the container 10 reaches the hatchery, the eggs first need to be rehydrated to restore water lost during transportation and "equilibrated" to the water temperature of the hatchery. Gradually equilibrating the temperature of the eggs to the hatchery water temperature increases the likelihood that the eggs will survive transportation.
Both equilibration and rehydration may easily be accomplished with the present invention as follows. A hose is hooked up to the valve 70 of container 10, and water of approximately the same temperature as that of the eggs 64 in the container is introduced into the container through the inlet 20 until the water flows out the top of the container 10. The temperature of this flowing water is gradually (e.g., over the course of about one hour) increased until it is substantially the same as that of the water at the hatchery. The temperature of the eggs within the box is thus equilibrated to the temperature of the water at the hatchery.
At this point, the rehydrated eggs are typically disinfected. To this end, an iodine solution can be introduced through inlet 20 or poured over the eggs through the opening in the top of box 12. It is important that the eggs be rehydrated prior to sanitization because the iodine solution can kill the fish inside of a dehydrated egg.
After the eggs have been equilibrated, rehydrated, and sanitized, the container 10 can be used in its incubation mode to hatch the eyed eggs into sac fry 71 (FIG. 8B). The hatching process is well-known and will not be described in detail herein. As the sac fry 71 hatch from the eyed eggs, they swim toward the bottom 30 of the box 12.
After all of the eggs are hatched into sac fry, the box 12 is used in its grow-out mode to rear the developing fry. During the grow-out mode, any egg containers and ice trays are removed from the box 12. While water is introduced into box 12 through inlet 20 and circulated through the box and discharged out of the top of box 12 to keep feces, uneaten food, and other unwanted debris from accumulating in the box, to keep a liberal supply of oxygen in the water in which the fry are reared, and to control the temperature of that environment.
As the sac fry deplete the nutrients in the yolk sac, the resulting starter fed fry begin to swim to the surface of the water (FIG. 8C). Feed may be introduced into the container to allow continued rearing of the fry in the box 12. Again, water is continually flushed through inlet 20 into the box 12 and out of the top thereof. The fry may be grown out in this manner until their size requires that they be moved into a pen, tank, or stream.
Another important use of the egg tubes 78 described herein is as in-stream incubators for planting fish in spawning streams. Rather than incubating in container 10, the egg tubes 78 are removed from the container and placed in a stream. The egg tubes 78 are then secured in the stream by burying then in loose gravel, staking then to the stream bed, etc. The flow of water through the holes in the egg tubes 78 is sufficient to incubate the eggs and bring them to the point where they hatch. Once hatched, sac fry exit the egg tube through slots 52. This embodiment of the invention has the advantage that it eliminates the need for grow-out pens currently maintained at the headwaters of the spawning stream.
When the egg tubes 78 are to be planted in a spawning stream as just described, it is preferable that they be made out of biodegradable materials. Therefore, after the fish hatch from the egg, the egg tubes 78 disintegrate without further interference or effort by man.
To protect the eggs while they are incubating in the stream, the egg tubes 78 may be impregnated with a fungicide such as Vinyzene. The fungicide prevents the growth of fungus which would otherwise kill or damage the fish. Preferably, the fungicide is employed as part of the egg tube material or pellets or in a form that allows it to be slowly released to the eggs throughout the entire incubation period.
In this manner, the egg tubes 78 of the present invention decrease the costs and increase the survivability of fish planted at the headwaters of a spawning stream.
A third embodiment of the present invention is shown in FIG. 9. Elements of the third embodiment that are the same as those of the first embodiment will be given the same reference characters and will not be discussed in further detail.
Like the first embodiment of the invention, the third embodiment has an insulated shell or box 12. The interior of box 12 is divided into a water compartment 88 and a dry compartment 90 by a divider 92. The divider 92 provides an airtight, water-tight seal between compartment 88 and compartment 90.
The dry compartment 90 contains a pump 94, a filter 96, a cooler 98, an aerator 100, a battery 102, an output manifold 104, and input tubing 106. Water 108 in water compartment 88 flows through input tubing 106 to pump 94. The pump 94 pumps the water through the filter 96 to remove bacteria and other impurities from the water. The water then passes into the cooler 98 where the water is cooled so that its temperature is within the range of temperatures suitable for the type of fry being transported. The water is next aerated or oxygenated by aeration unit 102, after which the water flows into output piping 104.
Manifold 104 has outlet ports 110. The output ports 110 protrude through divider 92.
Each outlet port 110 terminates in a fixture 112 to which a fry-containing tube 114 is attached. The fixtures 112 allow water to flow from the outlet ports 110 of manifold 104 into the fry-containing tubes 114. As in the other embodiments of the invention, the fry-containing tubes 114 are perforated. The water is circulated from the fixtures 112 through the fry tubes 114, and out the tops 116 of those tubes as shown by arrows 118. Water consequently rises in the water compartment 88 to the level indicated by reference character 120. The fry in the perforated tubes are thus submerged in water during transport. Water discharged from tubes 114 flows into input tubing 106 and is recirculated.
The battery 102 is electrically connected to, and supplies motive force for, pump 94, cooler 98, and aeration unit 100, which is vented to the outside of the container shell 12.
Alternatively, one can employ compressed air or oxygen for aeration. The aeration unit 100 may comprise a compressed air tank with a valve that will allow the air to be introduced into the water flowing through the input tubing 106 at an appropriate rate.
The battery 102 may be of the rechargeable type, and a plug may be provided on the exterior of the box 12. This allows the battery to be recharged. Also, the battery can be conserved by operating the transporter/incubator on external power when such power is available.
The invention may be embodied in still other forms without departing from the spirit or essential characteristics of the present invention. The specifically disclosed embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description and the drawings. All changes which come within the meaning and the range of equivalency of the claims are therefore intended to be embraced therein.
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Methods and apparatus for transporting, incubating, and growing out the eggs of aquatic creatures. The apparatus includes an insulated container and a spacing structure which rests on the bottom wall of the container. One or more egg containers are placed on the spacing structure to keep water in the insulated container from drowning the eggs, and the container is iced. An inlet port is so located that water can be introduced into the box below the egg containers. The egg containers may be open trays or closed tubes. The apparatus may also include a pump, a filter, a cooler, and an aerater for recirculating water contained in the box during the transportation of fry.
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BACKGROUND OF THE INVENTION
The present invention relates to a method of reducing the halogen content in a particulate polyolefin formed by catalytic polymerization of an olefin in the presence of a Ziegler-Natta catalyst by subjecting the particulate polyolefin to a purifying treatment involving passage of gas therethrough.
In the polymerization of olefins using Ziegler-Natta catalysts, the particulate polyolefins usually obtained have a certain content of catalyst components depending upon the catalyst combination used and the polymerization conditions employed. Thus, in virtually all polyolefins of this kind there is a relatively high content of halogen, particularly chlorine. This means that the polyolefins must be treated to reduce the halogen content before they are further processed, as otherwise they would produce relatively severe corrosion in the machines used for converting the polyolefins. The presence of halogens also has a detrimental effect on the properties of the products made with polyolefins.
There are several well-known methods for reducing the catalyst and halogen contents of these polyolefins. On such method comprises dissolving the polyolefins, hydrolyzing and precipitating the catalyst components, filtering this system, and reprecipitating the polyolefins from the filtering solution. Another method consists of treating the particulate polyolefins with specific wash liquids. The third method involves the treatment of the particulate polyolefins with aqueous/alkaline solutions or sulfoxide in extruders. One highly effective extruder method is disclosed in U.S. Pat. No. 3,925,341 to Mueller-Tamm, Schick, Rau, and Hennenberger. This method involves treating the polyolefin with an alkylene oxide and water in an extruder. The halogen content is converted to alkylene halohydrin which is sufficiently volatile that it can be easily separated from the polyolefin.
Still another method for reducing the halogen content is the gas phase fluidized bed dechlorination method such as described in British Pat. No. 1,420,837 to Badische Anilin and Soda-Fabrik Aktiengesellschaft. According to that patent, particulate polyolefins are subjected to a purifying treatment involving the passage of gas therethrough, wherein the purifying treatment is carried out in a gas phase fluidized bed and the purifying gas used comprises a mixture of nitrogen, steam, and an alkylene oxide in a particular ratio. It is said therein that the method can reduce the halogen content to about 20 parts per million and it has been found that further modifications of the method can reduce the halogen content even further.
Significant amounts of alkylene oxide are consumed in the above method. Therefore, it definitely would be advantageous from a cost standpoint to recover as much of the alkylene oxide as is possible. It is well known that alkylene halohydrins can be converted to alkylene oxides by treating the halohydrins with caustic solutions. Indeed, there are a number of old industrial processes for manufacturing ethylene oxide from ethylene chlorohydrin. Those processes all utilize relatively highly concentrated solutions of ethylene chlorohydrin to produce ethylene oxide.
U.S. Pat. No. 1,446,872 to Brooks discloses a method for making ethylene oxide from ethylene chlorohydrin by reacting the chlorohydrin with a caustic alkali in the presence of as little water as possible. The patentee states that when the reaction is carried out in the presence of considerable water, very poor yields of oxide result. The patentee states that one part by weight of a solution containing 80% chlorohydrin and 20% water and 1 part by weight of solid caustic soda reacted together will produce the maximum theoretically possible yield of ethylene oxide. U.S. Pat. No. 3,886,187 to Bartholome, Koehler, Stoeckelmann, and May discloses a process for the continuous manufacture of propylene oxide by turbulent jet mixing of a propylene chlorohydrin solution with aqueous alkali, mixing with steam to produce a two-phase mixture and a special working-up process following turbulent passage through a reaction zone with a short residence time. It is said that propylene oxide is obtained in high yield and high space-time yield. The patentees state that the alkaline components are generally used in concentrations from 2 to 15 moles per liter of solution.
In the fluidized bed dehalogenation process, the concentration of alkylene halohydrin in the gas stream which is removed by volatization from the fluidized bed is very small. It has been found that when dilute solutions of alkylene halohydrin are treated with relatively highly concentrated caustic solutions such as those disclosed in U.S. Pat. Nos. 1,446,872 and 3,886,187 above, the reaction conditions favor the production of an undesirable amount of alkylene glycol rather than alkylene oxide. Aside from the fact that the production of oxide is preferred so that it can be recycled into the fluidized bed, the presence of glycol causes undesirable foaming which adversely affects the operation of the caustic scrubber where the halohydrin is contacted with the caustic solution. It has been unexpectedly found that by treating the dilute halohydrin solutions with dilute caustic solutions, the production of alkylene oxide can be maximized and the production of glycol and the foaming problems concurrent therewith can be minimized.
Therefore, it is an object of this invention to regenerate alkylene oxide so that it can be recycled to the fluidized bed dehalogenation apparatus. It also is an object of this invention to maximize the production of alkylene oxide in the caustic scrubber and thereby minimize the production of alkylene glycol therein. A further object of this invention is to minimize or eliminate foaming in the caustic scrubber.
SUMMARY OF THE INVENTION
The present invention relates to an improved method for reducing the halogen content of a particulate polyolefin formed by catalytic polymerization of an olefin in the presence of a Ziegler-Natta catalyst. This method comprises the steps of:
(a) causing the polyolefin in a dry state to flow into a gas phase fluidized bed,
(b) contacting the polyolefin at elevated temperature in the fluidized bed with a gas comprising 0.05% to 0.2% alkylene oxide, 5% to 30% solvent, and the balance inert gas, preferably nitrogen, such that the alkylene oxide reacts with halogens present in the polyolefin to form alkylene halohydrin,
(c) removing the alkylene halohydrin from the fluidized bed thereby reducing the halogen content of the polyolefin,
(d) contacting the alkylene halohydrin with a caustic solution at a temperature of from 90° F. (32° C.) to 160° F. (71° C.), wherein the solvent is selected from the group consisting of alcohol and water and the concentration of the caustic is from 0.001 N to 1 N. and
(e) recovering alkylene oxide formed by the reaction of the alkylene halohydrin and the caustic solution.
The above-described method is particularly useful for reducing the halogen content of crystalline polypropylene. The preferred alkylene oxides for use in the present invention are ethylene oxide and propylene oxide. The preferred caustics for use in the present invention are selected from the group consisting of potassium hydroxide, sodium hydroxide, and calcium hydroxide.
The method of the present invention is particularly useful in producing alkylene oxides from dilute solutions of alkylene halohydrins. The gas stream leaving the fluidized bed contains only a very small concentration of alkylene halohydrin, most commonly in the range of from 50 ppm to 300 ppm. It has been found that only dilute caustic solutions can be used to regenerate alkylene oxide under these conditions because with higher concentrations of caustic an undesirable amount of alkylene glycol is formed and foaming occurs in the caustic scrubber. The method of the present invention can be utilized apart from the fluidized bed dehalogenation method described above.
DETAILED DESCRIPTION OF THE INVENTION
The particulate polyolefin, preferably polypropylene, is fed into a multi-stage agitated powder fluid bed system. The fluid bed can be operated in either batch or continuous mode. If it is operated in batch, no preheating of the polyolefin is necessary. However, if the fluid bed is operated continuously, it is desirable that the first section of the fluid bed be a preheating section. It is important that the internal system remain as close to adiabatic as possible. This can be accomplished either by a combination of insulation and heating applied to the external surface or by insulation alone.
The temperature in the fluidized bed is maintained in the range from 190° F. (88° C.) to 250° F. (121° C.) with the optimum temperature being about 230° F. (110° C.). If a temperature of less than 190° F. (88° C.) is used in the fluid bed system, an abnormally long residence time is required for dehalogenation. If temperatures too close to the melting point or softening point of the polyolefin are used, fouling of the fluid bed system can occur.
In general, the method of the treatment of the particulate polyolefins by gases flowing therethrough in the fluidized bed may be carried out in any conventional manner using any conventional apparatus for such gas phase fluidized bed processes. For instance, the inlet gas may be bubbled up through the powder from the bottom of the fluidized bed. The inlet gas should contain from 0.05% to 0.2% of an alkylene oxide, preferably ethylene oxide or propylene oxide. If the concentration of the alkylene oxide is allowed to go below 0.05%, the result is either an incomplete reaction or an abnormally long residence time in the bed before complete dehalogenation occurs. The moisture concentration in the inlet gas should be from 5% to 30%, with approximately 10% being the ideal concentration. The moisture concentration in the fluidized bed has a two-fold effect. First, it is necessary for the reaction of the residual halogen-containing Ziegler-Natta catalyst with the alkylene oxide to form alkylene halohydrin. It is theorized that the moisture reacts with active chlorine in the powder to form hydrochloric acid which then reacts with the alkylene oxide to form alkylene halohydrin. Second, it is necessary for adequate control of static electricity which can greatly inhibit the handling of particulate polyolefins. The remainder of the inlet gas should be comprised of an inert gas, preferably nitrogen, but only because of its availability and low cost.
The rate of gas load per unit weight of polyolefin may be varied within wide limits. In general, the rate is greater for polyolefins having a high original halogen content and also when the halogen content is to be reduced to a great extent and the gas has a low concentration of moisture or alkylene oxide. Superficial gas velocities in the fluidized bed are most appropriate at approximately 11/2 times the minimum fluidization velocities. The flow of the inlet gas through the powder and out of the top of the fluidized bed carries with it the relatively highly volatile alkylene halohydrin and thus most of the halogen content of the particulate polyolefin is removed.
The regeneration and recycling of the alkylene oxide are accomplished by contacting the effluent gases from the fluidized bed, which contain alkylene halohydrin, with a caustic solution. The amount of alkylene halohydrin which is contained within the effluent gases stream is quite small. The concentration usually varies from 50 ppm to about 300 ppm. The contacting may be accomplished by any suitable contactor for the intimate mixing of gas and liquid streams.
The effluent gases are preferably passed through a countercurrent packed bed caustic scrubber column where they come in intimate contact with a dilute caustic solution. The packing in the column may be any conventional packing for use in such columns, such as pall rings, Intalax® saddles, Berl saddles, and Raschig rings. Flow redistributors in the column may be used to prevent the solution from running down the inside surfaces of the column. The solvent for the caustic solution may be either water or an alcohol with volatility such that the alkylene oxide recycle stream leaving the scrubber column contains 5% to 30% vaporized alcohol. Alcohols which fit this description include n-butyl, sec-butyl, isobutyl, and t-amyl alcohols as well as 2-pentanol. Conventional caustics such as sodium hydroxide, potassium hydroxide, and calcium hydroxide may be used in the caustic scrubber in a concentration of from about 0.001 N to about 1 N. The preferred concentration for the caustic is 0.01 N to 0.1 N and the optimum appears to be approximately 0.04 N.
If the concentration of the caustic is less than 0.001 N, then the reaction of alkylene halohydrin to alkylene oxide is incomplete. Increasing the caustic concentration up to and above 1 N results in some improvement in the conversion of alkylene halohydrin to alkylene oxide but greatly increases the losses of alkylene oxide to alkylene glycol. The rates of reaction of alkylene halohydrin to alkylene oxide and alkylene oxide to alkylene glycol are both dependent upon the hydroxide ion concentration. Use of low hydroxide ion concentrations allow one to control the reactions in the scrubber so that the conversion of alkylene oxide to alkylene glycol proceeds slowly, preventing the loss of the desired alkylene oxide. If the hydroxide concentration and the residence time are kept low, the production of alkylene oxide will be maximized.
The temperature in the caustic scrubber column can range from about 90° F. (32° C.) to about 160° F. (71° C.). At temperatures below 90° F. (32° C.), the moisture concentration in the fluid bed is so low that static electricity becomes a problem. The optimum temperature for the column is approximately 110° F. (43° C.) when water is used as the solvent. The temperature of the scrubber column, as well as having a distinct effect upon the reaction of alkylene halohydrin to alkylene oxide or the undesirable alkylene glycol, also controls the moisture concentration of the inlet gas to the fluidized bed after recycle from the scrubber column. The temperature of the scrubber column is used as the primary humidification control in the system. A temperature of 100° F. (38° C.) corresponds to approximately 9% moisture in the inlet gas to the fluidized bed depending upon the system pressure. The upper temperature limit is optional depending upon how much moisture is desired in the system. At higher column temperatures, water will condense in the cooler areas of the system and cause corrosion problems. A higher scrubber column temperature provides higher moisture concentrations but also causes a higher percentage of alkylene oxide in the scrubber to be converted to alkylene glycol. This, of course, is undesirable because less alkylene oxide is produced for recycle to the fluid bed. In addition, the tolerance of the scrubber column to the resulting alkylene glycol is much less and foaming becomes a serious problem at elevated temperatures. Foaming occurs as a result of bubbles of the inert gas forming and rising to the liquid surface in a liquid whose viscosity prevents displacement of the bubble wall and its rupture. Foaming does not occur as a result of alkylene glycol formed in any one pass through the system, but rather as a result of a build-up in the solvent which is constantly recycled throughout the system.
Propylene oxide is the preferred alkylene oxide for use in the present invention because it is less toxic than some other alkylene oxides as is its glycol. Ethylene oxide is also advantageous because it is relatively inexpensive. Nitrogen is the preferred inert gas because of its availability and low cost. Potassium hydroxide and sodium hydroxide are also preferred for their availability and relatively low cost.
As stated above, the solvent for the caustic for the scrubber column may be either water or alcohol. The use of alcohol provides the additional advantage that no alkylene glycol is produced and consequently there is no problem of foaming in the scrubber column. However, only alcohols with a volatility such that the alkylene oxide recycle stream leaving the scrubber column contains 5% to 30% vaporized alcohol may be used in this invention because if the volatility is too low the concentration of alcohol in the recycle stream will be less than 5% and if it is too high, the concentration will be more than 30%.
The variables discussed above may be adjusted to make the process work with different column sizes and gas flow rates. Such adjustments are within the expertise of skilled engineers.
EXAMPLE I
Polypropylene powder is fed into a multi-stage ebullient fluidized bed from a powder hopper through a feeder. The bed is divided into five sections, a preheating section which is 63/4 inches long and 4 inches deep, and 4 sections in the reaction zone which are each 4 inches long and 4 inches deep. The bed is 5 feet high and has a 11/2 foot overhead volume expansion zone. The powder enters the fluid bed near the top and enters the preheating zone which is held at a temperature of 230° F. (110° C.). The purpose of the preheating zone is to heat the powder for faster reaction of chlorine and propylene oxide to propylene chlorohydrin. The temperature in the remainder of the fluid bed is held at 230° F. (110° C.) by use of external insulation and heating on the external surface. The depth of powder in the fluid bed is maintained at 4 feet in the preheating zone and 21/2 feet in the reaction zone. The residence time of the powder in the bed is 50 minutes.
A gas stream comprising 89.9% nitrogen, 10% water, and 0.1% propylene oxide enters the fluid bed at the bottom through numerous apertures. The gas is heated to a temperature of 240° F. (116° C.) prior to its introduction into the fluid bed. The gas flow through the fluid bed is 24.4 cubic feet per minute.
The effluent gases containing propylene chlorohydrin, which has been formed by the reaction of propylene oxide and chlorine in the propylene powder, exit at the top of the fluidized bed. This gas stream is filtered and sent to a caustic scrubbing column. The effluent gas stream contains 75 ppm propylene chlorohydrin.
The caustic scrubber column is a 6-inch normal diameter, 15-foot vertical tower packed with 1-inch ceramic Super Intalox® saddles and having ring-shaped flow redistributors spaced at 33/4 feet. The caustic solution in the column is a solution of potassium hydroxide in water at a concentration of 0.04 N. The temperature of the column is maintained at approximately 110° F. (43° C.). The effluent gas stream from the fluid bed flows into the bottom of the column and the caustic solution flows in at the top of the column. The gas stream exiting from the top of the scrubber column contains 0.1% propylene oxide and is recycled to the gas inlet of the fluid bed. Only 25 ppm/hour of propylene glycol is produced in the scrubber column and very little foaming occurs.
The chlorine content of the polypropylene powder is reduced from 400 parts per million to 50 parts per million. Almost all of the propylene oxide which is fed into the fluid bed is recovered in the gas outlet stream of the caustic scrubbing column.
EXAMPLE II
The procedure of Example I is repeated under the following conditions:
Fluid bed preheating zone temperature--216° F. (102° C.)
Fluid bed reaction zone temperature--221° F. (105° C.)
Fluid bed powder depth--3 feet (all sections)
Powder residence time--52 minutes
Inlet gas stream composition--7.5% isobutyl alcohol, 0.1% propylene oxide, 92.4% nitrogen
Inlet gas stream temperature--252° F. (122° C.)
Gas flow--26.2 cubic feet per minute.
Propylene chlorohydrin concentration in effluent gas stream--less than 75 ppm
Caustic solution--0.04 N potassium hydroxide in isobutyl alcohol
Scrubbing column temperature--124° F. (51° C.)
The chlorine content of the polypropylene powder is reduced from 358 ppm to 85 ppm. No propylene glycol forms and there is no foaming because there is no water in the system.
EXAMPLES III-V
30 milliliters per minute of a 0.004 N solution of sodium hydroxide in water flows downwardly through a 2-foot high scrubber column packed with less than 1/4-inch crushed ceramic saddles. 0.136 cubic feet per minute of nitrogen containing propylene chlorohydrin is bubbled upwardly through the column. The temperature is measured at the liquid inlet (T 1 ), one inch down from the liquid inlet (T 2 ), one inch up from the gas inlet (T 3 ), and three inches up from the gas inlet (T 4 ). The inlet and outlet concentrations of the gas stream are measured to determine the conversion of propylene chlorohydrin (PCH) to propylene oxide (PO). The following Table A shows the result for three different sets of temperatures.
TABLE A__________________________________________________________________________ PCH in PO out PCH outT.sub.1 (°F.) T.sub.2 (°F.) T.sub.3 (°F.) T.sub.4 (°F.) (ppm) (ppm) (ppm)__________________________________________________________________________Ex. III95 (35° C.) 94 (34° C.) 85 (29° C.) 87 (31° C.) 74 11 8Ex. IV 115 (46° C.) 115 (46° C.) 119 (48° C.) 124 (51° C.) 81 56 --Ex. V 155 (68° C.) 156 (69° C.) 122 (50° C.) 137 (58° C.) 180 93 9__________________________________________________________________________
The results indicate that the conversion of propylene chlorohydrin to propylene oxide proceeds reasonably well at this low caustic concentration and that it is better at higher temperatures.
EXAMPLES VI-IX
The procedure of Example III is repeated with a 0.047 N solution of sodium hydroxide in water flowing into the column at a rate of 30 milliliters per minute. The gas stream flows at 0.116 cubic feet per minute. The results are set out in Table B.
TABLE B__________________________________________________________________________ PCH in PO out PCH outT.sub.1 (°F.) T.sub.2 (° F.) T.sub.3 (°F.) T.sub.4 (°F.) (ppm) (ppm) (ppm)__________________________________________________________________________Ex. VI 85 (29° C.) 85 (29° C.) 84 (29° C.) 85 (29° C.) 146 45 7Ex. VII109 (43° C.) 109 (43° C.) 104 (40° C.) 109 (43° C.) 143 85 6Ex. VIII147 (64° C.) 150 (66° C.) 124 (51° C.) 136 (58° C.) 164 155 6Ex. IX158 (70° C.) 160 (71° C.) 129 (54° C.) 141 (61° C.) 198 141 --__________________________________________________________________________
The results indicate that the conversion is very good at this concentration, especially at the higher temperatures.
EXAMPLES X-XII
The procedure of Example III is repeated with a 0.4 N solution of sodium hydroxide in water flowing at 36 milliliters per minute. The gas stream flows at 0.124 cubic feet per minute. The results are set out in Table C.
TABLE C__________________________________________________________________________ PCH in PO out PCH outT.sub.1 (°F.) T.sub.2 (°F.) T.sub.3 (°F.) T.sub.4 (°F.) (ppm) (ppm) (ppm)__________________________________________________________________________Ex. X 97 (36° C.) 97 (36° C.) 92 (33° C.) 95 (35° C.) 155 93 6Ex. XI114 (46° C.) 114 (46° C.) 113 (45° C.) 114 (46° C.) 229 218 --Ex. XII150 (66° C.) 155 (68° C.) 126 (52° C.) 140 (60° C.) 155 158 --__________________________________________________________________________
The results show that the conversion proceeds very well at this high concentration. This experiment is not operated at conditions which will produce foaming since it occurs only after the concentration of propylene glycol in the recycled water builds up over a period of time.
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An improved method for reducing the halogen content of a particulate polyolefin formed by catalytic polymerization of an olefin in the presence of a Ziegler-Natta catalyst is taught which comprises the steps of causing the polyolefin in the dry state to flow into a gas phase fluidized bed, contacting the polyolefin in the fluidized bed with a gas comprising 0.05% to 0.2% alkylene oxide, 5% to 30% water, and the balance inert gas such that the alkylene oxide reacts with halogens present in the polyolefin to form an alkylene halohydrin, removing the alkylene halohydrin from the fluidized bed and thus reducing the halogen content of the polyolefin. The improvement comprises regenerating the alkylene oxide by contacting the inert gas containing alkylene halohydrin with a caustic solution in alcohol or water and recovering therefrom alkylene oxide formed by the reaction of the alkylene halohydrin and the caustic solution.
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FIELD OF THE INVENTION
This invention relates to a saw machine (gang saw) for example wherein sheets or billets of wood material are cut into strips by an assembly of multiple circular saw blades arranged in side-by-side spaced relation, and more particularly it relates to a method and apparatus for removing and replacing the saw assembly in the machine.
BACKGROUND OF THE INVENTION
A saw machine or gang saw typically includes an arbor rotatively driven by its connection at one end to a motor. The other end is rotatably supported by a bearing mount provided in a removable gate. A sleeve is slidably mounted on the arbor (at the gate end) and is keyed to the arbor. Saws and spacers are mounted on the sleeve and fixed thereto in a desired spaced relation. The saws, spacers and sleeves together with end nuts holding the spacers and saws onto the sleeves are referred to as the saw assembly.
When the saws become dull or the spacing arrangement is to be changed, it is necessary to remove the entire assembly from the arbor including the sleeve, spacers and saws. The assembly is slid off the gate end of the arbor and a new assembly is mounted in its place.
The saw assembly as described above is often heavy, the blades have sharp edges and the area around the saw assembly as mounted in the saw machine is crowded. Typically the saw assemblies are manually removed. The assemblies can weigh as much as or even more than 400 pounds. Manually removing the assemblies is hard work, dangerous and time consuming. Accordingly, it is an object of the present invention to mechanize the saw assembly changing procedure and thereby reduce the danger of injuries and also enable a more rapid changing time.
BRIEF DESCRIPTION OF THE INVENTION
The present invention in its preferred embodiment includes a specialized cart. The cart includes holding lugs (holders) that are elevated into engagement with the end nuts used to hold the saw assembly together. The gate is removed and a shaft extension is abutted against the arbor. Hydraulic cylinders are activated to pull the cart from a position under the arbor to a position under the shaft extension and thereby slide the saw assembly off the arbor and onto the shaft extension. The shaft extension with the saw assembly thereon is retracted from the arbor end. The saw assembly is then engaged by an overhead crane which removes the old assembly including the shaft extension and transfers it to a changing station. A new assembly mounted on a further shaft extension is placed on the cart. The free end of the shaft extension is advanced into engagement with the arbor end. The cart is then shoved back under the arbor which shoves the assembly off of the shaft extension and onto the arbor. The shaft extension is disconnected and withdrawn from the arbor, the gate is closed and with the arbor thereby fully supported by the bearing mount of the gate, the lugs of the cart are retracted. The cart remains dormant under the arbor until the next changeover.
Whereas the above description applies to a bottom gang saw, e.g., where the wood billets are moved across the top of the saws, a modification thereof makes it applicable also to overhead edge easer saws. The embodiment which is disclosed in the detailed description which follows utilizes both, the edge easer saw being used to provide a finishing bevel in the upper edges of the to-be-cut lumber pieces as will be explained further in the detailed disclosure which follows.
Whereas the above carrier for the bottom saw assembly is referred to as a cart, the upper carrier is referred to as a sled to differentiate the two. As explained above, the cart stays in place under the saw assembly during operation of the gang saw. This has the advantage that support lugs need only be retracted a slight amount and otherwise would have to be retracted the depth of the saws to allow the cart to slide out from under the saw assembly. As will be appreciated, the cart never has to slide relative to the saw assembly.
The sled has to contend with the anvil which supports the billet as the billet is moved through the overhead saws. The sled is thus designed to slide on the anvil and under the saw assembly. The upper saw assembly has smaller diameter blades and thus retraction of the lugs is not a problem. Also, the saw assembly is much lighter in weight and the movement of the lugs can be manually manipulated, e.g., through the use of camming levers. The sled is hydraulically shoved under the saw assembly along the anvil and when in place, an operator through the use of the camming levers raises the lugs into place under the end nuts. The shaft extender is placed against the arbor and the saw assembly is removed from the arbor much in the same manner as explained for the cart.
A further improvement is directed to the saw assembly itself. Saw assemblies are commonly kept to a "manageable" length and for most applications contemplated herein, the desired length is longer than the manageable length. Thus, the saw assembly is commonly split, i.e., having two sleeves that are placed end to end on the arbor. The split creates problems when organizing the saw blades and spacers for different sawing patterns.
The present invention provides as an alternative saw assembly, spacers that are sized and configured to fit directly onto the arbor, e.g., having a center opening with keyways that are matched to the arbor, and which interfit together with a saw blade therebetween, the saw blade rotatably fixed to the spacers. The entire assembly can be pulled apart and restructured with different spacers to achieve any desired sawing pattern. The arbor extension includes keys similar to the arbor and the entire assembly of spacers and saws is slid off the arbor and onto the arbor extension in the manner described above.
The structure and operation briefly described above will become more clearly understood and appreciated upon reference to the detailed explanation that follows and the drawings which are referred to therein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a saw machine including saw blade assemblies as contemplated for changing by the present invention;
FIG. 2 is a gang saw assembly as taken on view lines 2--2 of FIG. 1;
FIG. 3 is an edge easer saw assembly as taken on view lines 3--3 of FIG. 1;
FIGS. 4, 5 and 6 schematically illustrate a saw changer of the present invention changing the gang saw assembly of FIG. 1;
FIGS. 7 and 8 schematically illustrate a saw changer of the present invention changing the edge easer saw assembly of FIG. 1;
FIG. 9 is a side view of a saw machine and saw assembly changer for changing both assemblies of the saw machine;
FIG. 10 is a view taken on lines 10--10 of FIG. 9;
FIG. 11 is a side view of a modified saw assembly;
FIG. 12 is an exploded view of the saw assembly of FIG. 11;
FIG. 13 is a side view of a saw blade mounted to the saw assembly;
FIG. 14 is an end view of one of the spacers of the saw assembly; and
FIG. 15 is a section view of an arbor to which the saw assembly of FIGS. 11-14 is fit.
DETAILED DESCRIPTION
The invention will first be described in general by reference to the schematic illustrations of FIGS. 1-8. With reference to FIG. 1, a conveyor 10 conveys a series of billets 12, e.g., eight feet in length and two inches high (the dimensions shown in the figure) and four feet in width. The billets 12 are passed from the conveyor 10 onto an anvil 14 and through an edge easer assembly 16 and then a gang saw assembly 18. With the billet 12 sawed into lumber pieces of the desired dimension, e.g., two inches by four inches by eight feet, the lumber pieces 12' are taken away by conveyor 20 for storage or further processing.
The gang saw assembly 18 is illustrated in cross section in FIG. 2 as indicated by section lines 2--2 in FIG. 1 and the edge easer machine 16 is illustrated in cross section in FIG. 3 as indicated by section lines 3--3 in FIG. 1.
With reference to FIG. 3, the edge easer machine 16 includes a motor 22 including a drive shaft 24 coupled to one end of an arbor 26. The arbor 26 is rotatably supported at its other end by a removable gate 28. Surrounding the arbor 26 are a pair of sleeves 30a and 30b which are keyed to the arbor and rotate with the arbor. Surrounding the sleeves 30 are edge easer blades 32 spaced apart by spacers 34. The blades 32 are rotatably fixed to the sleeves and end nuts 36 secure the blades and spacers to the sleeves. The sleeves 30, spacers 34, edge easer blades 32 and end nuts 36 are secured together for removal from the arbor as a unit and are referred to herein as an edge easer blade assembly. (The edge easer blades provide a shallow V-shaped groove in the top of the billet whereat the cut lines will be made by the gang saw to provide the lumber pieces 12' with beveled edges on the top edges of the pieces.)
The gang saw of FIG. 2 is similarly constructed. A motor 38 includes a drive shaft 40 which rotatably drives an arbor 42. The arbor 42 is rotatably supported at its opposite end by a removable gate 44. Sleeves 46a and 46b are key fit to the arbor 42 and saw blades 48 and spacers 50 are mounted to the sleeve and fixed to the sleeve by end nuts 52. The sleeves 46, spacers 50, saw blades 48 and end nuts 52 are secured together in the manner of the edge easer blade assembly. They are removable from arbor 42 as a unit and they are referred to herein as a saw assembly. (The blades 48 are provided with a cutting section 48a that provides a beveled edge on the bottom side of the lumber pieces similar to that of the top side provided by the edge easer blades.)
As previously explained, the invention is directed to the apparatus and process for changing the saw assembly. (In this context, the edge easer blade assembly is considered a saw assembly). A saw assembly, e.g., as illustrated in FIG. 2 and as described in the previous paragraph, is not new. Changing of the saw assemblies was previously accomplished by removing the gate 44 and manually sliding the assemblies, first the assembly of sleeve 46b, and then the assembly of sleeve 46a, off the arbor. Provision was made for supporting the assembly at the unsupported end (due to removal of gate 44) to alleviate bending and thereby binding of the sleeves on the arbor. The process was difficult, time consuming and dangerous. The present invention automates the process and is schematically illustrated in FIGS. 4-6.
Reference is made to FIG. 4 which illustrates the saw machine of FIG. 2 and including a schematic illustration of the saw blade changer of the present invention. In the illustration of FIG. 4, the saw machine is in operational mode. A movable cart 54 is mounted on tracks 56. A hydraulic hoist 58 is mounted at each end of the cart and a saddle holder 60 is mounted on each hoist 58. The holders 60 are configured to fit under and behind the end nuts 52. As will be appreciated, the hoists 58 are hydraulically operated to raise the saddle holder 60 into engagement with the end nuts to both support the weight of the saw assemblies and to trap the assemblies between the holders.
Reference is now made also to FIGS. 5 and 6. Positioned in spaced relation at the free end of the saw machine (the end opposite motor 38) is a power unit 62. The power unit 62 includes a first hydraulic cylinder 64 which is provided with a mandril 66 that releasably holds a shaft extender 68. The power unit 62 includes a second hydraulic cylinder 70 which is connected at 72 to the cart 54. Compare FIGS. 4 and 5. As will be noted, gate 44 has been removed, the hydraulic hoists 58 have raised the saddle holder 60 into engagement with end nuts 52, mandril 66 has been advanced by cylinders 64 to advance the shaft extender into abutting engagement with the exposed end of arbor 42, cylinder 70 has been activated to draw cart 54 toward the power unit 62 and in the process slide the saw assemblies from the arbor onto the shaft extender 68.
FIG. 6 illustrates the process of exchanging the shaft assemblies. Now compare FIGS. 5 and 6. An overhead hoist 74 including grapple lines 76, is engaged with the saw assembly still mounted on the shaft extender 68, and then first cylinder 64 retracts to release mandril 66 from the shaft extender 68. The hoist 74 then lifts the saw assembly and shaft extender off the saddle holders 60, carries the assembly to a work station, picks up a replacement saw assembly and shaft extender and returns to the position illustrated in FIG. 6.
It will be appreciated that the above-described process is then reversed. The mandril 66 is advanced to engage the shaft extender, the grapple lines are released, the replacement shaft extender is engaged with the arbor end, the cylinder 70 is activated to slide the saw assembly onto the arbor 42, the mandril is retracted, gate 44 is closed to support the arbor end, and the saddle holders are retracted to place the saw machine back to its operating condition of FIG. 4.
The procedure for changing the edge easer assembly is similar to that of the saw assembly and is illustrated in FIGS. 7 and 8. The primary difference is that a sled 78 is used instead of the cart and it is not left under the assembly during operation. FIG. 7 illustrates the condition during operation. Thus, the sled has to be slid under the blade assembly after the gate 28 is removed. The sled 78 is supported on the anvil 14 and moved back and forth by a third cylinder 80 of power unit 62. The sled and its holders 82 are designed to have a low profile to fit under the blades 32. These blades are, however, substantially smaller in diameter than blades 48 of the gang saws. The edge easer assembly is not as heavy and the holders 82 are manually cam actuated into position to support end nut 36 as generally indicated in FIG. 8. Shaft extender 84, held by mandril 86 and activated by the cylinder 88, is abutted against the arbor 26, and cylinder 80 is actuated to draw the edge easer assembly onto the shaft extender 84. The process is otherwise a repeat of the process described for FIGS. 4-6 except, of course, the sled 78 is withdrawn prior to closing of gate 28 with FIG. 7 illustrating the position of operation for the edge easer.
FIG. 9 illustrates a saw machine incorporating both the overhead edge easer and the gang saw including the components for changing the saw assemblies of each, as schematically illustrated and described for FIGS. 4-8. In FIG. 9, most of the structure of the saw machine is removed for clarity. Those skilled in the art will appreciate that the saw machine is of standard construction and that the invention involves a saw blade changing mechanism. Thus, the drive motors, frame, shroud and input and output conveyors are not included in the illustration and will not be described.
Referring to FIG. 9, the edge easer assembly 16 and gang saw assembly 18 are illustrated in operative positions. Not shown is the anvil 14 which establishes the feed path for the billets 12. Dash lines 14' identify the level at which the billets would be fed through the saw machine. The arbors 26 and 42 are supported by a motor at one end and a gate at the opposite end and neither is illustrated in FIG. 9. The reader is referred to FIGS. 2 and 3 for illustration of these components.
The cart 54 is illustrated in its normal position (during operation of the saw machine) in dash lines and in its retracted position in solid lines. The cart 54 would only appear in the retracted position during changeover. The solid line position is believed to best illustrate the manner by which the cart is controlled in its movement on the rails 56 which dictates the path, and by the cylinder-piston 70. A control panel 90 controls actuation of the cylinder-piston 70 as does it control other automated mechanism of the changeover system.
A shaft extender 68 is illustrated suspended above the cart 54 and is held by the mandril 66 engaged by the piston or rod of cylinder 64. The free end of the shaft extender 68 is sectioned to illustrate a pocket 92 in the end of the shaft extender that receives the conical end 94 of the arbor 26 for coupling the shaft extender and arbor during transfer of the saw assembly.
The sled 78 is coupled to the piston of cylinder 80 at 96 for moving the sled 78 into and out of position under the edge easer assembly 16. The various frame components employed for supporting the cylinders and selected mechanism is generally identified by the reference number 98.
Attention is now directed to FIG. 10 as taken on section lines 10--10 of FIG. 9 (but again with certain of the structure removed for clarity). FIG. 10 is provided to illustrate the mechanism associated with the cart 54 and sled 78 for grasping and supporting the saw assembly. Thus, the view of FIG. 10 assumes that the cart and sled are both in place under the saw assemblies and the holders are raised into position and supporting the saw assembly.
Referring first to the gang saw assembly 18, the dash line illustrates the periphery of the saw blade 48. Teeth 48a bevel the edges of the lumber pieces 12' as previously explained. Rails or tracks 56 support the wheels 100 of the cart 54. As illustrated, hoists 58 raise and lower holders 60 that are raised into engagement with end nut 52. Expansion and contraction of lift 102 produces raising and lowering of the holders 60. Note finger portion 61 of holder 60 that overlaps the edge of end nut 52. A similar finger portion 61 overlaps the opposite end nut and in combination insures movement of the saw assembly with the cart.
With reference now to the edge easer assembly 16, the sled 78 is provided with bearing strips 104 that facilitate sliding movement of the sled across the anvil 14. The profile of the sled as illustrated in FIG. 9 is low enough (except the "free" end which does not slide under the assembly) to slide under the blades for placement of the holder 82 under the end nuts 36. Note finger portions 83 in dash lines which are similar to finger portions 61 of holders 60. The holders 82 pivot from a position just below the blades into engagement with the end nuts. The pivoting is accomplished manually using the levers 106. As will be noted, the levers 106 are pivoted to the dash line position to pivot the holders against the nut. The levers are pivoted to an over-the-center position and the holders are held in place by the downward pressure applied by the weight of the saw assembly. Whereas the levers are provided only on the free end of the sled, accessible for manual pivoting, the lever action is transferred to the holders at the opposite end via a shaft that extends between the holders and which are not shown.
Sleeveless Saw Assembly
Attention is now directed to FIGS. 11-15. Illustrated is a saw assembly comprised of saw blades 108 and center spacers 110. The spacers 110 are provided with a center bore 112 and key slots 114. FIG. 15 illustrates a cross section of the arbor 42 which is provided with keys 43. The spacer center bore 112 fits onto the arbor 42 with the keys 43 aligned and fitted to the key slots 114. (In the prior saw assembly, it is the sleeve that is provided with key slots and fitted to the arbor.)
Each of the center spacers is configured to have a projecting flange 116 at one end, and an inset 118 at the other end sized to fit the flange 116. The saw blade 108 has a center bore 120 that also fits the flange 116. In assembly, a saw blade 108 is placed over the flange 116 of a center spacer, a pin 122 is inserted through a hole 124 in the blade and into an aligned hole 126 in the flange side of the spacer. The next spacer 110 is fitted with its inset nested into the flange 116 of the first spacer and abutted against the saw blade 108. A pin hole 128 in the inset side of the spacer is fitted to the pin 122. This process is repeated until all of the spacers and saw blades are assembled. Note, however, that the pin may be fixedly mounted, e.g., in hole 126 and the blade and next spacer simply fit onto the pin.
The illustration of FIGS. 11-12 show chippers 130, 132 and end spacers 134, 136 assembled to each end of the center spacer-saw blade assembly. Although not shown, this would be accomplished by simply abutting the end components as mounted on an arbor or arbor extension.
It will be appreciated that the spacers provide the function of the spacers and sleeve of the prior embodiment, and end spacers 134, 136 function as the end nuts. Thus, spacers 134, 136 are slightly greater in diameter and are adapted to receive the holder 60 (or 82 in the case of the edge easer) for sliding the entire assembly on and off the arbor/arbor extension. In a known manner, the entire saw blade assembly when assembled to the arbor for cutting operation, is clamped together by securing nuts that are threadably engaged with the arbor at each end thereof.
As will be appreciated, the components are not otherwise secured together and the assembly of components is moved as a unit by the cart/sled holders. The components are readily disassembled to allow sharpening or other maintenance and readily reassembled onto an arbor extension. The arbor extension is preferably provided with keys that line up the components to enable easy movement onto the arbor keys. Changing the spacing between saw blades is readily completed by replacing the spacers and the assembler need not be concerned about where the saws or spacers are located as in the embodiments employing sleeves.
With the above description, those skilled in the art will readily be able to practice the invention. The invention is not, however, limited to the specific details as illustrated in FIGS. 9 and 10 as there are many forms that various ones of the components can take. The invention is the automation of the saw assembly changing process without substantially redesigning the basic saw machine. The cart and sled can be readily added to existing saw machines and these units provide support for the assemblies and through the power and controls of the power unit, the cart and sled can be manipulated into and out of the saw machine. This enables the use of overhead cranes to move the saw assembly between work stations and a minimal amount of effort is required. It will also be appreciated that the changing process is readily accomplished in a far shorter time than has been previously provided through manual manipulation.
The invention is accordingly encompassed by the definition of the claims appended hereto.
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A saw changer for changing a saw assembly mounted on an arbor of a saw machine. A carrier is positioned for powered sliding movement axially along the saw assembly from a position under the arbor to a position free of the arbor. The carrier includes holders that are raised into position for holding the saw assembly and through powered axial movement of the carrier, for removing the saw assembly from the arbor. Upon removal, the saw assembly is lifted from the carrier and a replacement saw assembly is mounted on the carrier for placement onto the arbor.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to via etching in semiconductor wafers. In particular, the present invention relates to a method of monitoring the depth of the vias etched in a wafer.
BACKGROUND OF THE INVENTION
[0002] A via is a vertical microscopic tunnel that penetrates selected inter-metal dielectric layers (IMDs) on the surface of a semi-conductor wafer and is filled with a conductive filler to provide an electrical flow path. Typically, the via is connected to a conductive layer at both its ends.
[0003] Vias are etched into a dielectric layer by exposing selected areas on the surface of the dielectric layer to etching processes. Where vias are not to be formed, the surface is covered with an etch-resistant material during etching, which is removed after the vias are etched. How deeply a via is etched into one or more dielectric layers depends on factors such as etch method, etch rate and etch time.
[0004] When the etch time is insufficient, the via does not penetrate sufficiently through the dielectric layer, or layers, into contact with an underlying conductive layer or device element. Therefore, vias are sometimes slightly over-etched to ensure that the vias are cleared of all dielectric material.
[0005] Several methods may be used to monitor sufficient via depth, such as profilometry, X-ray Scanning Electron Microscopy (X-SEM), Atomic Force Microscopy (AFM) and via resistance measurement. However, profilometry has limited accuracy in profiling surface features having dimensions as small as that of a via. SEM techniques are sample destructive and slow, since the IMD has to be cut to reveal the via cross-section, and are therefore unsuitable as quick means of quality control. AFM requires tedious changing of cantilever tips and is too troublesome to be incorporated into a manufacturing process for quality control. Via-chain resistance measurement is the most commonly used quick-detection technique for monitoring good via connections, which would mean that the vias are not under-etched. However, if the via connections are bad, i.e. have high resistance, via-chain resistance measurement cannot distinguish whether the bad connection is due to under-etching, or via-misalignment leading to non-contact with the underlying conductive layer. Furthermore, via-chain resistance measurement cannot tell us how much via depth is short in the event of under-etching.
[0006] It is, therefore, desirable to provide a method that is sensitive and quick in response for selectively detecting under-etching or via misalignment. It is preferable if the method is also able to indicate by how much the via depth is short of reaching the target depth.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a method for monitoring via depth in inter-metal dielectric layers (IMDs) on a semi-conductor wafer. It is an object of the present invention to provide an improved method for of monitoring via depth.
[0008] The invention proposes in one aspect the use of capacitance to monitor via depth or placement.
[0009] The invention proposes in another aspect a method for determining a property of a via in a wafer comprising the steps of using the via as a first capacitive member, providing a second capacitive member, applying an electrical potential difference across the via and the corresponding capacitive member, measuring the resultant capacitance between the via and the second capacitive member and determining the property of the via from the capacitance.
[0010] In one specific embodiment, capacitance is obtained between vias separated into two groups, each group representing one of two capacitive plates. In another embodiment, all the vias are charged with the same charge, in bias as a capacitive plate against a conductor having the opposite charge being the corresponding capacitive plate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings, in which
[0012] FIG. 1 is a schematic diagram of a dielectric layer in a wafer having vias.
[0013] FIG. 2 is an isometric view of an embodiment of the present invention.
[0014] FIG. 3 is a schematic side view of the embodiment of FIG. 2 .
[0015] FIG. 4 is a schematic plan view of the embodiment of FIG. 2 .
[0016] FIG. 5 is a further isometric view of the embodiment of FIG. 2 .
[0017] FIG. 5 a shows a plot of via-Critical Dimension against capacitance according to the embodiment of FIG. 2 .
[0018] FIG. 6 is a schematic side view of another embodiment of the present invention.
[0019] FIG. 7 is a further schematic view of the embodiment of FIG. 6 .
[0020] FIG. 8 is an isometric view of the embodiment of FIG. 6 .
[0021] FIG. 9 shows a plot of via-Critical Dimension against capacitance according to the embodiment of FIG. 6 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0022] FIG. 1 illustrates two inter-metal dielectric layers 13 , 19 (IMD) of a semi-conductor wafer 10 having vias 11 etched through a first dielectric layer 13 into contact with a conductive layer 15 laid on the second dielectric layer 19 . In a downstream process, the vias would be filled with conductive fillers before a further conductive layer (not shown) is laid on the first dielectric layer 13 . It is important that a via thoroughly penetrates the dielectric layer 13 in order to contact conductive layers 15 on both ends.
[0023] FIG. 2 is a schematic view of an embodiment 20 of the invention, which uses inter-via capacitance to monitor via depth. Three dielectric layers 13 , 13 a , 19 on a wafer is shown, the top two layers 13 , 13 a having vias 11 a , 11 b etched therethrough. The vias 11 are filled with the conductive fillers after etching to become conductive leads to the conductive layer 15 in the bottom-most dielectric layer 19 . However, the vias 11 a , 11 b are stop-etched, i.e. under-etched, as they are not completely etched through the second layer 13 a into contact with the conductive layer 15 . To determine the depth of the vias 11 a , 11 b , two metallic electrical contacts, one being a positive connection 21 and the other the corresponding negative connection 23 , are put into contact with the vias 11 a , 11 b . A voltage is applied to the electrical contacts 21 , 23 and a resultant potential difference exists between the non-contacting vias 11 a , 11 b . The vias are thus electrically charged, the longitudinal surface of each via being charged with opposite charges. Therefore the longitudinal sides of one of the vias behaves as a positive plate 11 a of a capacitor and that of the other via as the corresponding negative plate 11 b.
[0024] Capacitance between two oppositely charged plates is defined as:
C = ɛ A d ( 1 )
Where,
C=capacitance (fF). A=total overlap area between a positive and a negative plate (μm 2 ). ε=dielectric permitivity of vacuum between capacitive plates, e.g. 8.854×10 −3 (fF/μm) for vacuum. d=distance between the overlapping areas (μm).
[0029] Equation (1) shows that the larger the area of overlap between two capacitive plates of opposite charges, the larger the resultant capacitance. Therefore, the depth of the vias 11 a , 11 b , which is directly proportional to the area of overlap at the sides of the vias 11 a , 11 b , directly correlate to the resultant capacitance.
[0030] FIG. 3 is a plan view of an embodiment which corresponds to the embodiment of FIG. 2 , showing how, instead of just two vias 11 a , 11 b , two groups of several vias 11 a , 11 b are used as capacitive plates. The electrodes 21 , 23 are comb-shaped and are distributed parallel to a dielectric layer 13 underneath. Each electrode 21 , 23 has fingers 31 interspersed with the fingers 31 of the other electrode 21 , 23 . Each finger 31 is also configured to contact a plurality of vias such that when a voltage is applied to the electrodes 21 , 23 , the vias are separated into two groups having opposite charges.
[0031] FIG. 4 shows an isometric view of the embodiment 20 of FIGS. 2 and 3 . In practice, however, the total capacitance exerted between the electrodes and vias is a sum of both inter-via capacitance and inter-electrode capacitance. Thus, the capacitance between only the vias 11 a , 11 b is obtainable by subtracting the inter-electrode capacitance from the total capacitance.
[0032] Referring to FIG. 5 which represents the embodiment of FIG. 2 schematically and which corresponds to FIG. 3 when viewed from the direction indicated by the arrow ‘A’, the inter-electrode capacitance is:
C 1 = K ɛ lt 1 d 1 ( 2 )
Where
C 1 =capacitance between the electrodes 21 , 23 . K=relative dielectric permitivity of the dielectric film between the electrodes 21 , 23 , e.g. air. ε=dielectric permitivity of vacuum, 8.854×10 −3 fF/μm 2 . l=the overlapping distance (μm) between two electrodes 31 of opposite charges. t 1 =height of the electrodes (μm). d 1 =distance between the positive and negative electrodes 11 a , 11 b (μm).
[0039] The inter-via capacitance can thus be obtained by subtracting the inter-electrode capacitance from the total capacitance:
C Total = K ( ɛ lt 1 d 1 + ɛ n m ( t 2 · x ) d 2 ) = C electrode + K ɛ n m ( t 2 · x ) d
∴ C Total - C electrode = K ɛ n m ( t 2 · x ) d
C via = K ɛ n m ( t 2 · x ) d . ( 3 )
where
C electode =capacitance between the electrodes 21 , 23 , as obtained from equation (2) C Total =total capacitance between the electrodes 21 , 23 and vias 11 a , 11 b as measurable. C via =capacitance between the vias 11 a , 11 b. K=relative dielectric permitivity of the dielectric material between the vias 11 a , 11 b and between the electrodes 21 , 23 . K value is assumed to be the same in this embodiment for both the materials between the vias and between the electrodes, even though air exists between the electrodes while a dielectric material exists between the vias. ε=dielectric permitivity of vacuum, 8.854×10 −3 fF/μm 2 . l=the overlapping distance (μm) between two electrodes 31 of opposite charges. t 2 =etch depth of the vias (μm). m=the number of metal fingers on each comb 21 , 23 n=the number of vias 11 on each comb finger, m x=the average diameter of the via, i.e. Final Inspection Critical Dimension (FICD or via width). d 1 =distance (μm) between a pair of positive and negative electrodes 11 a , 11 b, d2=distance (μm) between two corresponding vias 11 a , 11 b d=distance (μm) between two corresponding vias 11 a , 11 b (d2) and also distance between the corresponding electrodes 21 , 23 (d1), assuming d=d1=d2.
[0053] The present embodiment 20 therefore allows the depth, t2, of vias to be monitored by inter-via capacitance by re-arranging equation (3)
t 2 = C via · d K ɛ n m x ( 3.1 )
[0054] For a more accurate measurement, a calibration is obtained to correlate via depth, or via-Critical Dimension (CD), to inter-via capacitance. FIG. 5 a is a plot of equation (3), where critical dimensions of vias correlates to the inter-via capacitance depending on the via depth. FIG. 5 a is obtained by substituting the following example values into equation (2) to get C 1 =1312.29 fF:
[0055] K=4.15,
[0056] ε=0.008854,
[0057] l=100,
[0058] t 1 =100,
[0059] d 1 =0.28.
and by substituting the following example values into equation
k ɛ n m ( t 2 · x ) d 2
to get 21199 (t 2 .x) fF:
[0060] M=500
[0061] n=300
[0062] K=4.15
[0063] ε=0.008854
[0064] d=0.26
[0065] Substituting the values obtained above into the formulae (3) gives the following:
C= 21199( t 2. x )+1312 (3.2)
[0066] Using equation (3.2) to plot capacitance against via width (x), for every 0.2 um increment in via depth (t 2 ) provides Table 1 and the graph of FIG. 5 a .
TABLE 1 x = Via diam- eter or t 2 = etchdepth width 0.8 1 1.2 1.4 1.6 1.8 2 0.2 4703.8 5551.8 6399.8 7247.7 8095.7 8943.6 9791.6 0.22 5043.0 5975.8 6908.5 7841.3 8774.0 9706.8 10639.6 0.24 5382.2 6399.8 7417.3 8434.9 9452.4 10470.0 11487.5 0.26 5721.4 6823.7 7926.1 9028.4 10130.8 11233.1 12335.5 0.28 6060.6 7247.7 8434.9 9622.0 10809.2 11996.3 13183.4 0.3 6399.8 7671.7 8943.6 10215.6 11487.5 12759.5 14031.4 0.32 6738.9 8095.7 9452.4 10809.2 12165.9 13522.6 14879.4 0.34 7078.1 8519.7 9961.2 11402.7 12844.3 14285.8 15727.3 0.36 7417.3 8943.6 10470.0 11996.3 13522.6 15049.0 16575.3
[0067] If the vias 11 are thoroughly etched through the dielectric layer 13 into contact with the lower conductive layer 23 , the capacitance would drop as the charge is conducted away. However, if the vias are etched to a sufficient depth but are misaligned, such that one or more vias do not come into contact with the underlying conductive layer 23 , i.e. via misalignment, the capacitance remains high as a potential difference remains between the vias. Therefore, unlike via resistance measurement, the present embodiment indicates whether the cause of a bad connection is due to under-etching or misalignment.
[0068] FIG. 6 shows another embodiment 60 of the present invention, wherein the vias 11 are not separated as two oppositely charged plates to obtain inter-via capacitance. Instead, all the vias 11 are charged with the same charge from one top electrode 61 , which is biased against an opposing electrode 63 underneath the vias 11 . The bottom electrode 63 is a conductive metal layer and has an area that spans underneath the vias 11 . The under-etched vias 11 therefore form several parallel capacitive plates corresponding to the bottom electrode 63 . Typically, the opposing electrode has a thickness of 2×IMD thickness, e.g. about >15000 A.
[0069] Capacitance of parallel plates adds up according to the following relationship:
C parallel =C 1 +C 2 +C 3 + . . . C n
where
[0070] C parallel is total capacitance; and
[0071] C 1 , C 2 , C 3 to . . . C n are capacitors in parallel up to a total number of n capacitors
[0072] Therefore, the capacitance between the vias and the oppositely charged bottom electrode 63 can be treated mathematically as between one combined via and the bottom electrode 63 , as illustrated in FIG. 7 .
[0073] FIG. 8 shows an isometric view of the embodiment of FIG. 6 . The vias 11 are etched through a dielectric layer 13 , filled with a conductive filler, and is in contact with an electrode 61 of one charge. An opposing electrode 63 is beneath the vias so that there is a resultant capacitance between the vias 11 and the electrode 63 when a potential is applied thereto,
[0074] Therefore, the depth of the vias 11 , d 3 , relates to the distance, d 2 , between the plates of a capacitor. According to equation (1), capacitance increases as d decreases. The efficiency of the etching process on the depth of the vias can therefore be monitored by the via-electrode capacitance.
[0075] However, the total capacitance in the configuration of this embodiment 60 is a sum of the capacitance between the top electrode 61 and the bottom electrode 63 in areas where there is no via, and the capacitance between the vias 11 and the electrode 63 where the are vias 11 . Therefore, in order to obtain the capacitance between only the vias 11 and the bottom electrode 63 , the capacitance between the top electrode 61 and the bottom electrode 63 has to be subtracted from the total capacitance.
[0076] The capacitance between the electrodes 61 , 63 without the presence of vias 11 is defined by:
C electrodes = K ɛ A d 1 ( 4 )
where,
C electrode =capacitance between the electrodes 61 , 63 . A=area of overlap between the plates, μm 2 ε=dielectric permitivity of vacuum, 8.854×10 −3 fF/μm 2 . K=relative dielectric permitivity of the dielectric film between the electrodes 21 , 23 . d 1 =distance (μm) between the electrodes 61 , 63
[0082] Accordingly, the capacitance between the vias and the bottom electrode 63 , C via , can be found thus:
C Total = ɛ ( A - n x 2 ) d 1 + ɛ nx 3 d 3 - d 1
C Total = K ɛ A d 1 - ɛ nx 2 d 1 + ɛ nx 2 d 3 - d 1
C Total = K ɛ A d 1 - ɛ nx 2 1 d 1 + 1 d 3 - d 1
C Total = C electrode - K ɛ nx 2 1 d 1 + 1 d 3 - d 1
C Total = C electrode - K ɛ nx 2 1 d 3 - d 1 - 1 d 1
∴ C Total - C electrode 1 = K ɛ nx 2 d 3 1 ( d 1 - d 3 ) d 1
C via = K ɛ nx 2 d 3 1 ( d 1 - d 3 ) d 1 ( 5 )
where,
C electrode =capacitance between the electrodes 61 , 63 . C Total =total capacitance between the electrodes and vias 61 , 11 , 63 . C via =capacitance between the vias 11 and the bottom electrode 63 . K=relative dielectric permitivity of the dielectric film between the electrodes 61 , 63 and vias 11 . ε=dielectric permitivity of vacuum, 8.854×10 −3 fF/μm 2 . d 1 =distance (μm) between the electrodes 61 , 63 d 2 =distance (μm) between the bottom of the vias 11 and the lower electrode 63 . d 3 =etch depth of the vias=d 1 −d 2 (μm) n=the number of vias 11 on each comb finger, m x=the bottom surface width of the circular via. For simplicity, the area of the bottom of the via is approximated to be x 2 in this embodiment. In practice, the value depends on via dimension (μm 2 ).
[0093] FIG. 9 is a plot of equation (5), where critical dimension (FICD, or width of the Via plug) of the vias has a correlation to via capacitance depending on the via depth. Therefore the depth of the vias 11 can be monitored based on the capacitance between the vias 11 and the bottom electrode 63 .
[0094] Substituting the following example values into equation (4) to obtain C1=174.97 fF:
[0095] n=50000
[0096] K=4.15
[0097] ε=0.008854
[0098] A=100*100
[0099] d=2.1
[0100] Substituting the following example values into equation (5)
C Total = K ɛ nx 2 d 3 1 ( d 1 - d 3 ) d 1 + C electrode 1
[0101] d 1 =IMD total thickness=2
[0102] K.ε.n=50000×0.008854×4.15=1837.205
gives
C Total = 1837 x 2 d 3 0.5 ( 2 - d 3 ) + 174.9
or
C Total = 918 x 2 d 3 ( 2 - d 3 ) + 174.9 ( 5.1 )
[0103] Using equation (5.1) to plot capacitance against via width (x), for every 0.2 um increment in via depth (d 3 ) provides Table 2 and the graph of FIG. 9 .
TABLE 2 X = Via diameter or d 3 = etch depth width 0.8 1 1.2 1.4 1.6 1.8 0.1 181.0 184.1 188.7 196.3 211.6 257.5 0.2 199.4 211.6 230.0 260.6 321.8 505.4 0.3 230.0 257.5 298.8 367.7 505.4 918.5 0.4 272.8 321.8 395.2 517.6 762.4 1496.8 0.5 327.9 404.4 519.2 710.4 1092.9 2240.4 0.6 395.2 505.4 670.6 946.0 1496.8 3149.2
[0104] A quick and sensitive method of detecting under-etch has been disclosed. In particular, the embodiments provide a method of monitoring via depth using capacitance. As the embodiments monitor via depth in a quick, simple and non-destructive way, they can be used on every wafer during wafer manufacturing for quality control.
[0105] Other than monitoring via depth, the embodiments can be used to monitor depth and alignment of other etched features on an IMD, such as via contacts with the wafer surface (instead of with an underlying metal layer), Dual Damascene vias, Local Interconnects, etc.
[0106] Where the via depth is known, the embodiments can also be used for determining the dielectric constant of the dielectric layer. The embodiments can also be used for comparing microloading effects between alignment mark and via features. The embodiments can also be used to monitor via depth consistency in a situation where the thickness of the dielectric layers on different wafers vary and where performance varies between etch machines. Therefore, recipe setups between machines can be obtained quickly. Furthermore, wafer-wafer or lot-lot comparisons can be made using the embodiments to control consistency in product quality.
[0107] Tables 1 and 2, as well as the graphs of FIGS. 5 a and 9 show that the present embodiment is also useable to monitor the diameters of vias, as well depths. The correlation can be used to derive etch depth and, subsequently, calculating the via width. On obtaining the via width and the etch depth, the proportion of the measured capacitance contributed by the via width can be isolated from the capacitance contributed by the etch depth.
[0108] Although only several embodiments are described, it should be understood that the embodiments described herein are but embodiments of underlying concepts of the invention. Alternatives to the embodiments, though not described, are intended to be within the scope of this invention as claimed.
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A method for monitoring the depth of at least one via ( 11 ) in a wafer comprising the steps of arranging the via ( 11 ) as a capacitive plate ( 21 ), providing a corresponding capacitive plate ( 23 ), applying an electrical potential difference to the via ( 11 ) and the corresponding capacitive plate ( 23 ), measuring the resultant capacitance between the via ( 11 ) and a corresponding capacitive plate ( 23 ) and determining the depth of the at least one via ( 11 ) by the capacitance.
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BACKGROUND OF THE INVENTION
This invention relates to distortion generators for compensating the characteristics of unavoidable nonlinearities present in nominally linear systems such as amplifiers.
Copending U.S. patent application Ser. No. 07/772,207, filed Oct. 7, 1991 in the name of Wolkstein, describes a modern communications satellite which provides several broadband repeater channels. As described therein, the communications satellite receives from an earth station a plurality of signals within a cumulative frequency band, processes the received signals, as by low-noise amplification, filtration and block conversion to another frequency, and retransmits the processed signals to the same or another location.
FIG. 1 illustrates, as described in the abovementioned Wolkstein application, a satellite body 6 in accordance with the prior art, upon which are mounted a polarizing grid arrangement 8, vertically polarized receiving antenna 12V and horizontally polarized receiving antenna 12H. Receiving antennas 12V and 12H are coupled to vertical and horizontal signal processing arrangements 10V and 10H, respectively, located within body 6. Signal processing arrangements 10V and 10H process the received signals to produce signals to be retransmitted, which are broadcast by transmitting antennas 32V and 32H, respectively. Signal processing arrangement 10H is similar to vertical processing unit 10V, so only processing unit 10V is described.
The nature of the signals arriving at the satellite may be understood by reference to FIG. 1b. The vertically-polarized signals arriving at antenna 12V by way of polarizing grid 8 includes a plurality of signals centered at different frequencies f1, f2, f3. The amplitude spectra of various of these signals are designated V1, V2, V3 in FIG. 1b. Some of the signals arriving at antenna 12H of FIG. 1a, with horizontal polarization are illustrated (in dashed lines) as H1, H2 in FIG. 1b. In a typical satellite system, there may be 10 or more vertical (V) and 10 or more horizontal (H) channels, with their frequencies of operation interleaved as shown in FIG. 1b. The bandwidth of a signal such as signal V2 may be sufficient to carry a television channel, or more. Thus, the bandwidth of a signal such as V2 may be 6 Mhz or more. Vertical processing channel 10V of FIG. 1a may, as a consequence, receive 10 or more signals V1, V2, V3 . . . V N , each six or more Mhz wide, which are separated from each other by a like amount. Thus, the total frequency bandwidth occupied by the vertical signals may be 120 Mhz or more, calculated as [10(V) +10(H)]×6. The center frequency of the 120 Mhz band may be, for example, at 14 GHz.
The 10 or more vertical signals V1, V2 . . . received by antenna 12V of FIG. 1a are coupled to an input filter 14 of channel 10V, for reducing noise and preventing interference. Filter 14 is a bandpass filter with a bandwidth substantially equal to the total bandwidth of the vertical signals. The filtered signals are coupled from input filter 14 to a low noise amplifier (not illustrated) if required and then to a block converter including a mixer 16 and a local oscillator 18. The frequency of local oscillator 18 is selected to convert the 14 GHz center frequency to some other center frequency, such as 12 GHz. The downconverted 12 GHz signals are applied over a transmission path 20 to a multiplexing (MUX) filter 22. Multiplexing filter 22 separates signals V1, V2, V3 . . . from each other in accordance with their frequencies. Multiplexing filter 22 is the starting point for a plurality of separate channels designated generally as 1, 2, . . . 3, 4. If there are 10 vertical signals V1, V2, V3 . . . then the number of channels in signal processor 10V is also 10. The signal in each of channels 1, 2, . . . 3, 4 is one of the signals V1, V2, . . . In effect, filter 22 is a source of signals at a plurality of different frequencies, driving a like plurality of separate channels.
In general, the signals on channels 1, 2, . . . 3, 4 in FIG. 1a are amplified, the distortion generated due to the amplification is compensated, and the amplified and distortion corrected signals are applied to a combiner or demultiplexer 30, which may be a filter similar to filter 22 operated in reverse, or it might be a group of hybrid combiners which do not discriminate based upon frequency. The combined signals at the output of combiner 30 are applied to a transmitting antenna 32V for transmission back to an Earth station, or possibly to another satellite.
System considerations such as the signal strength of the signal available at the satellite, the receiving antenna gain, and the transmitting antenna gain and field strength required to reach the ground station establish the overall power gain which must be provided in each channel between receiving antenna 12V and transmitting antenna 32V.
Within any channel 1, 2, . . . 3, 4 of FIG. 1a, the signal is processed by the cascade of a driver amplifier (DA) 34, a distortion linearizer such as a predistortion equalizer (PDL) 36, and a power amplifier or final amplifier (FA) 38. For example, as illustrated in FIG. 1a, the cascade of a DA 34 2 , PDL 36 2 and FA 38 2 amplifies the signals for channel 2. As illustrated in FIG. 1a, an additional cascade of a DA 34 5 , PDL 36 5 , and FA 38 5 is connected in cascade, to define an extra or supernumerary "channel" designated 5. Channel 5 is not connected for handling signal, but instead represents a reserve cascade which may be substituted into any of the other channels in which the cascade may become defective. To this end, connection between input filter 22 and the inputs of the various channel cascades 34, 36, 38 is provided by means of an input switch arrangement designated 24, and connection between the outputs of final amplifiers 38 and combiner 30 is provided by an output switch arrangement designated as 28. A switch control arrangement illustrated as 26 gangs the input and output switches for simultaneous operation, and responds to signals in response to evidence of failure, generated on the ground or autonomously by control circuits within the spacecraft itself. Thus, in the event that the cascade of DA 34 1 , PDL 36 1 , and FA 38 1 fails completely or becomes degraded, the reserve cascade including DA 34 5 , PDL 36 5 , and FA 38 5 can be substituted therefor, with the cascade of DA 34 1 , PDL 36 1 , and FA 38 1 being removed from on-line use. Naturally, additional redundant units may be provided, and if the number of failures should exceed the number of redundant units, the switching arrangement including 24, 26 and 28 may move operable cascades from lower-priority uses to higher-priority uses. In order to be switchable to obtain this level of reliability, each cascade must have an instaneous frequency bandwidth covering the cumulative or total bandwidth of the vertical signals V1, V2, V3, . . .
As further described in the aforementioned Wolkstein application, modern broadband final amplifiers are recognized as having very similar distortion characteristics among themselves. The switching arrangement is repositioned by Wolkstein as in FIG. 2a so that the distortion equalizers are fixedly associated with the individual channel, rather than being switchable together with the amplifier. As a result, the distortion equalizer may be designed and optimized during manufacture for the relatively narrow bandwidth of the channel, rather than for the total bandwidth of all the channels.
Elements of FIG. 2a corresponding to those of FIG. 1a are designated by the same reference numerals. In FIG. 2, each cascade of a driver amplifier 34, predistortion equalizer 36, and final amplifier 38 is redistributed relative to FIG. 1 so that the driver amplifier and predistortion limiter are fixedly associated with each channel, between the multiplexing filter 22 (the effective input of the channel) and the input of switching arrangement 24. Thus driver amplifier 34 1 and predistortion linearizer 36 1 are cascaded between the channel 1 output of multiplexing filter 22 and input switch 24. As illustrated in FIG. 2a, switch arrangement 23 connects final amplifier 38 1 in channel 1. The net gain in channel 1 between the channel 1 output of multiplex filter 22 and the channel 1 input of combiner 30 is identically the same as in the arrangement of FIG. 1a (assuming, of course, that the elements themselves are identical). Similarly, the gains through each of the channels of FIG. 2a are the same as in FIG. 1a. However, only the final amplifiers 38 are required to have the cumulative bandwidth of all the vertical-polarization channels if the redundancy scheme so requires, while the driver amplifiers and predistortion linearizers require only the relatively narrow channel bandwidth. For the previous example of 10 vertical channels, each with 6 MHz bandwidth, the driver amplifiers and predistortion linearizers are required to have only a 6 MHz bandwidth in the arrangement of FIG. 2a, compared with a bandwidth of 120 MHz in the prior art arrangement of FIG. 1a. It should be noted that the block conversion reduces the center frequency but not the cumulative bandwidth, so the percent bandwidth is increased by the block conversion.
FIG. 2b is a simplified block diagram of a portion of the arrangement of FIG. 2a, as described by Wolkstein. In particular, predistortion linearizer 36 may include a linearizer 46, which may be a conventional linearizer such as is described in U.S. Pat. No. 5,038,113 issued Aug. 6, 1991 in the name of Katz et al. As illustrated in FIG. 2b, linearizer 46 is bypassed by a controllable switch 48, in order to switch the linearizer out of service. This may be desired, for example, when the following amplifier is to amplify FM-modulated signals such as TV video, which has lesser linearity requirements than multicarrier operations, so the amplifier can be run at a higher output level. Those skilled in the art realize that while switch 48 is illustrated by a mechanical switch symbol, switches adapted for GHz (or higher) frequency ranges must be used when appropriate and may be electronic rather than mechanical in nature. Further, in order to avoid impedance perturbations, a switch such as 48, bypassing linearizer 46, may also include, for impedance improvement, other switch portions intended for disconnecting linearizer 46 from the line when bypass switch 48 is closed. Wolkstein suggests improving reliability by using redundant linearizers. Enhanced system reliability is desired.
SUMMARY OF THE INVENTION
A FET linearizer includes a controllable signal path extending between source and drain electrodes. As described in the Katz et al '113 patent, the gate is coupled by a predetermined impedance to a reference potential. In one embodiment, the impedance is an inductance in series with a variable capacitor. A direct bias voltage is applied between the gate and the controlled current path, which voltage is selected, in conjunction with the gate impedance, to impress a desired degree of distortion on signals traversing the controllable source-to-drain (or drain-to-source) controllable path. As described in the Katz et al patent, the FET linearizer may be operated in transmissive and reflective modes. In accordance with the invention, reliability is enhanced and weight and complexity are reduced in a transmission-type FET linearizer, by selectively operating the FET in a first distortion correcting mode generally as described in the Katz et al patent, and in a second mode which may be characterized as an ON mode, in which the FET acts as an essentially linear transmission path. In a particular embodiment of the invention, the ON mode is selected by connecting the FET gate to reference potential.
DESCRIPTION OF THE DRAWING
FIG. 1a is a simplified block diagram of a prior art spacecraft communication system, and FIG. 1b illustrates a simplified portion of an amplitude-frequency spectrum associated with the arrangement of FIG. 1a;
FIG. 2a is a simplified block diagram which illustrates a portion of a spacecraft communication system as described in the aforementioned Wolkstein application, and FIG. 2b is a portion therefore;
FIG. 3 is a simplified schematic diagram of a FET translation circuit according to the invention which operates in two modes, a distortion mode and a linear mode;
FIG. 4 is a simplified schematic diagram of an alternate arrangement of a portion of FIG. 3;
FIG. 5 is a simplified schematic diagram of an alternate arrangement for coupling bias to the FET of FIG. 3;
FIG. 6a is a plot of phase response versus frequency of the arrangement of FIG. 3 for linear or ON and nonlinear operating modes, and FIG. 6b is a corresponding amplitude plot.
DESCRIPTION OF THE INVENTION
The invention recognizes that switch 48 bypassing the linearizer 46 of FIG. 2b can be implemented as a transmission FET. Such a FET is itself inherently very reliable when, in normal operation, gate current does not flow. The parts count can be reduced, and overall reliability thereby enhanced, by using the distortion equalizer FET for the additional purpose of passing signal therethrough in a linear manner. Thus, the "switch" and the "linearizer" use much of the same structure, the parts count and weight are reduced, and reliability is enhanced. The parts count and weight reduction are significant when, as in the satellite of FIGS. 1a and 2a, twenty or more channels are used, each with a linearizer.
FIG. 3 is a simplified schematic diagram of a dual-mode FET translation circuit according to the invention, which performs the same functions as the apparatus of FIG. 2b but with a reduced parts count. In FIG. 3, a distortion generator 380 as described in Katz et al, U.S. Pat. No. 5,038,113 includes a FET 388 with source electrode 382, drain electrode 384, and gate electrode 386. Source electrode 382 is coupled (by matching networks, if needed) to an input port 390, and drain electrode 384 is similarly coupled to an output port 392. A gate-to-ground (or gate-to-reference) impedance 302 is connected between FET gate electrode 386 and ground 304. As described in detail in Katz et al '113, appropriately selected gate impedances, together with a gate bias voltage, cause the FET to controllably distort signals travelling from input port 390, and through the FET source-to-drain controllable (channel) 326 to output port 392. As also described therein, direct gate voltage (also known as direct current or dc) is applied between gate electrode 386 and controllable path 326 by a generator, designated generally as 310 in FIG. 3.
Generator 310 of FIG. 3 includes a source of direct voltage illustrated by a battery symbol 312. The direct voltage is selected in a manner represented by a potentiometer designated 316 and an associated movable "wiper" 318. Those skilled in the art know that these are only symbolic representations, and that in actuality more complex or electronically commanded sources are ordinarily used when the voltage is to be selected, and that once the operating point of a particular FET has been established, the variability feature is unnecessary and may be dispensed with. The selected direct bias voltage is generated on wiper 318 of generator 310. As so far described, the arrangement of FIG. 3 corresponds to the Katz et al '113 description.
As illustrated in FIG. 3, wiper 318 is connected to gate electrode 386 by a switch represented as a mechanical switch element 350 which is movable between positions contacting a first switch terminal 352 and a second switch terminal 354. In the position of switch element 350 which is illustrated in FIG. 3, the direct bias voltage is coupled from wiper 318, through an isolation apparatus illustrated as a resistor 320, to gate electrode 386. In order for the gate voltage to be applied across the gate (386)-to-channel (326) controllable path 326, a circuit is completed by the connection of an electrode (not separately designated) of battery 312 to ground or common return 304, together with the load impedance, represented by a resistor 300, coupled between output port 392 and ground. If there is no direct-current path between ground and source 382 or drain 384, a radio-frequency choke (RFC) or other impedance elements constituting a bias tee may be coupled from one or both electrodes to ground, as suggested by RFC 356 coupled from source 382 to ground. Also, the linearizer FET 388 may be bridged by an impedance for further control of the nonlinearity, as described in a copending application of Katz et al entitled, "Wideband Transmission-Mode FET Equalizer", as suggested by inductor 358, having terminals 358a and 358b , connected between source electrode 382 and drain electrode 384.
In accordance with the invention, the bias voltage is changed by operation of switch 350, to decouple gate 386 from that bias voltage (produced by generator 310) which sets conductive path 326 into a desired nonlinear condition, and to instead couple the gate to a source of voltage which causes conductive path 326 to take on essentially a linear conducting condition, corresponding to the ON or conducting condition of switch 48 of FIG. 2b. As illustrated in FIG. 3, the voltage coupled by switch 350 to gate electrode 386 is 0 volts or ground. Thus, in the alternate position (not illustrated in FIG. 3) movable switch element 350 makes contact with switch terminal 354, which is connected to ground 304. Consequently, in the described alternative position of switch element 350 in FIG. 3, gate electrode 386 is connected to ground by way of its isolation circuit 320, switch element 350 and terminal 354. With gate electrode 386 at ground potential and drain electrode 384 also at ground potential as to direct current because of the characteristics of load impedance 300 (or because of RFC 356 and inductor 358, the FET assumes a linear ON operating mode, in contrast to the nonlinear operating mode when switch element 350 is in the illustrated position to apply bias voltage to gate electrode 386.
Those skilled in the art will recognize that certain simplifying assumptions have been made in the above description. One simplification is to assume that the gate current is zero, and that the impedance of load impedance 300 is small enough so that the bias current flowing therethrough results in no voltage drop. While not strictly true, the direct gate current can be expected to be in the microampere range, or less, and for typical load impedances of 50 or 75 ohms in microwave circuits, or even for a few hundred ohms, the voltage offset attributable to drop across the load impedance is negligible by comparison with the gate bias voltages near the one-volt level.
For a Nippon Electric type NE673 GaAs FET, the ON mode occurs at or near 0 volts, and a nonlinear operating mode, useful for predistortion of signals in the 11 to 13 GHz range, occurs at about -0.9 volts. The bias which results in useful nonlinear operation occurs near pinchoff of this FET, and varies from FET to FET and with the desired degree of nonlinearity. To indicate the general range of voltages in this particular application, bias voltages from about -0.8 to about -1.4 volts have provided satisfactory nonlinearity with this type of FET, and voltages of 0 to about +0.3 volts are satisfactory for the ON operating mode.
FIG. 4 is a simplified schematic diagram of a portion of the arrangement of FIG. 3, with a switched bias source which would be suitable for applying a voltage in the range of 0 to about +0.3 volts in the ON operating mode. Elements of FIG. 4 corresponding to those of FIG. 3 are designated by like reference numerals. In FIG. 4, an additional voltage source which is positive with respect to ground is represented by a battery 412. A further potentiometer 416 is connected between the positive terminal of source 412 and ground, and its movable element 418 selects the desired positive bias voltage for the ON operating mode and supplies it to switch terminal 354. In the illustrated position of movable switch element 350, the operating bias near -0.9 volts for the nonlinear operating mode is supplied to gate electrode 386, and in the alternate position of switch element 350, the ON mode bias voltage in the range of 0 to +0.3 volts is coupled from switch terminal 354 to gate electrode 386.
In operation of the communication systems of FIGS. 1a or 2a with switched linearizers as illustrated in FIG. 3 or FIG. 3 with FIG. 4, conventional command channels (not illustrated) are used to send commands from a ground station to the satellite to control the "position" of movable switch element 350 between its position for nonlinear mode operation and its alternate "linear" ON operating mode.
FIG. 5 is similar to FIG. 3, and corresponding elements are designated by the same reference numerals. In FIG. 5, gate electrode 386 is connected to ground by a gate-to-ground impedance 302, which is galvanically conductive (i.e. conducts direct current). Thus, gate electrode 386 is connected to ground for direct voltage. In order to apply a bias voltage which makes gate electrode 386 negative with respect to a source or drain electrode, the bias voltage source 510, which is represented as including a positive source 512 with potentiometer 316 producing the selectable voltage or wiper 318, is coupled to terminal 352 of switch 350. The bias voltage is coupled through switch 350 (in the illustrated position), by way of an isolation device illustrated as a resistor 520, to drain electrode 384. If needed, as for example if load impedance 300 significantly loads bias source 510, a decoupling capacitor (also known as a coupling capacitor), illustrated as 522, may be interposed between drain electrode 384 and output port 392. The same may be done, instead or in addition, in relation to the source electrode 382 and port 390, if required.
FIG. 6a plots signal phase versus frequency over the range of 12.25 to 12.75 GHz for the structure of FIG. 3, in the nonlinear and linear ON modes. In FIG. 6a, plot 610 represents the phase angle versus frequency of the structure of FIG. 3 at a gate bias voltage of about -0.9 volts (nonlinear mode), at relatively low linearizer input signal levels (-25 dBm), while plot 612 represents relatively high input levels (in the vicinity of 0 dBm). As illustrated, plot 610 deviates by no more than about 5° over the 12.25 to 12.75 GHz frequency band. At the high input power level, the phase shift differs from that at low input power levels by about 45°. Plot 614 represents the phase of the structure of FIG. 4 with the gate at zero volts (the ON condition), at both high and low input signal levels. As illustrated, there is no change in phase over the frequency band as a function of signal level, which means that the apparatus is linear. Also, the phase shift is essentially zero degrees in the ON mode.
FIG. 6b plots output amplitude versus frequency over the range of 12.25 to 12.75 GHz of the structure of FIG. 3. Plot 616 represents the amplitude response at the relatively low -25 dBm input signal level at a gate bias voltage of about -0.9 volts, while plot 618 represents the 0 dBm input signal level. As illustrated, the loss decreases by about six dB for an increase of about 25 dB in input signal level. Plot 620 represents the amplitude response at zero gate volts at both input signal levels -25 dBm and 0 dBm. It is clear that there is no amplitude difference, and the FET operates linearly.
Other embodiments of the invention will be apparent to those skilled in the art. For example, rather than sending commands to switch element 350 from a ground station, an autonomous control system may make the selection in response to operating conditions. Also, the voltage generated by battery 312 (or the position of movable wiper 318) or the electronic equivalent, may be adjusted from the ground to vary the amount of nonlinearity in the nonlinear operating mode to compensate for changes in nonlinearity of the associated amplifier which may result due to aging or other effects.
Since the FET is ordinarily essentially symmetrical, the source and drain electrodes may be interchanged.
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A communications system includes a transmission channel in which, for efficiency, a processor such as an amplifier is operated in a nonlinear mode. When the signal is modulated in a manner which is affected by the nonlinearity of the processor, such as a multicarrier modulation, a distortion linearizer is used. The distortion linearizer incluees the source-to-drain conductive channel of a FET. The gate of the FET is coupled to ground by an impedance which may be a low inductance, and the gate is biased relative to the channel, possibly near pinchoff, to cause the channel to exhibit desirable gain expansion and phase shifts in response to signal input level, which are selected to compensate the distortion of the nonlinear processor. When the signal is modulated in a manner which is not significantly affected by the nonlinearity of the processor, as for example frequency modulation, the distortion linearizer is switched to a linear or ON mode, in which the amplitude and phase are invariant with signal level. The switching is accomplished by adjusting the gate-to-channel voltage.
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BACKGROUND OF THE INVENTION
The present invention relates to a control arrangement for controlling the operation of a grabbing crane for handling bulk material, particularly a bridge grabbing crane for loading and unloading bulk material into and from a ship.
DE-AS No. 10 82 837 discloses an arrangement for controlling the operation of a grabbing crane in which the position of the grab bucket is remotely displayed by means of a television camera and a television screen. The actual position of the crane carriage within a range defined by markings on a stationary part of the crane in the field of view of the camera is displayed on the screen together with markings corresponding to those on the crane. It is the crane operator's responsibility to move the grab bucket so that its actual position is always within the marked range.
DE-PS No. 26 42 181 describes a device for displaying the position of the grab bucket on a display which is divided into a multiplicity of fields each containing two light-emitting diodes. One of the two light-emitting diodes is always driven by a set or desired-value transmitter and the other light-emitting diode by an actual-value transmitter, so that the desired and actual positions of the grab bucket are each represented by a light spot travelling across the display as the grab bucket moves. To initiate a loading or unloading process, the crane operator places the grab bucket on the bulk material through manual control and aligns a scaled template which corresponds to the cross section of a ship's hold on the display screen in accordance with the displayed actual position of the grab bucket. This enables the crane operator to set the desired values required for operation of the grab bucket within the template. The respectively set initial desired values are retained for several grabbing cycles as controlled by a marking-line computer. However, the operating range of the grab bucket cannot be determined with sufficient accuracy by approaching a target position only once and aligning the template on the display screen in dependence thereon to insure that collisions of the grab bucket with edges of the ship's hatches do not occur.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the present invention to control a grabbing crane so as to avoid collisions of the grab bucket with the enclosure it is loading or unloading.
It is another object of the present invention to display a permissible operating range of the grab bucket to scale on a display.
According to the invention, the upper edges of the enclosure, e.g. the hatch of a ship's hold, are displayed as bars on a display. The invention will hereinafter be described with reference to a ship's hold and its hatch. The bars are generated from actual horizontal and vertical positions of the grab bucket. The actual values corresponding to those positions are determined by positioning the grab bucket at the hatch edges after approaching the hatch edges of the ship from the shore and water sides with the grab bucket open. Desired values corresponding to the desired position of the grab bucket are compared with the actual values which are used as limiting values. If a desired value exceeds a limiting actual value, the respective drive is prevented from moving the grab bucket to the precise desired location.
A desired path of the bucket derived from a marking line computer for example can be compared with the actual values. If the desired path indicates a collision, i.e. it intersects with any of the actual values, the respective drive is prevented from moving the bucket along the collision path.
The image of the grab bucket can be displayed to scale and corresponding to its actual position. A scale image of the hold, desired values and actual values in digital form, and a desired path can also be displayed.
The above and other objects, aspects, features and advantages of the invention will be more apparent from the following description of the preferred embodiments of the invention taken in conjunction with the accompanying drawings and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of examples and not limitation in the FIGURE of the accompanying drawing which is a schematic diagram of an arrangement for controlling the operation of a grabbing crane according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The arrangement according to the invention for controlling the operation of a grabbing crane includes pickups 1 and 2 which provide information of the horizontal and vertical position of the grab bucket. This information of the actual position of the grab bucket is used to provide values corresponding to limiting horizontal and vertical positions of the grab bucket by visually locating the grab bucket at the extremes of the hatch of the hold it is loading or unloading. The values derived from the pickups at those extremes are denoted limiting actual values. The limiting actual values are compared with the values of a desired grab bucket position. When a desired value exceeds a limiting actual value, the corresponding drive to the crane is overrode or controlled via its drive control 22 and/or 23.
More specifically, the output of a pickup 1 coupled to the horizontal drive of the trolley carriage of a loading bridge (not shown) is fed as the actual value of the trolley carriage horizontal position directly to a receiver 7 which includes a display such as a cathode ray tube. The pickup output is also fed to the drive control 22 for the carriage and is set into an actual-value memory 5 via a key 3. In a similar manner, the output signal of a pickup 2 coupled to the vertical drive of the grab bucket, i.e. the drive for the lifting and holding mechanism for the bucket, is fed directly to the receiver 7 and to a drive control 23 for the holding mechanism. The output of pickup 2 is further set into an actual-value memory 6 via a key 4.
The output of each actual-value memory is connected to a different actual-value input of the receiver 7 and to a common first comparator 21. The output of each actual value memory is also connected to a respective second comparator 16, 19. The comparators 16 and 19 compare the stored actual values of the trolley carriage horizontal position and the stored actual values of the grab bucket vertical position, respectively, with the counts of respective desired-value counters 14 and 17. Both desired-value counters are connected to and receive desired values from a desired-value transmitter 13 which can be operated manually, or if desired, by a control mechanism to input the desired values to the counters. With each desired-value counter 14, 17 is further associated a desired-value memory 15, 18, respectively, the output signal of which is fed to the receiver 7 and, in dependence upon the output signal of the comparator 16 or 19, to the respective drive control 22, 23.
By means of a selector switch 20, one of the marking lines stored in a marking-line computer is set into the common comparator 21. The output signal of this comparator acts directly on the drive controls 22 and 23.
The receiver 7 includes a digital display of the desired values 24, 25 and of the actual values 26, 27 of the horizontal position of the carriage and the vertical position of the grab bucket, respectively. The image 9 of the grab bucket is displayed on the display of the receiver 7 to scale, in its opened or closed configuration, and in accordance with its actual position. In addition, a scale image of the stationary hold 12 which is to be loaded or unloaded is displayed on the display of the receiver 7. Furthermore, a marking line 8 selected by the crane operator via selector 20 is displayed on the receiver. Two bars 10, 11 derived from stored actual values of the grab bucket position are also displayed on the receiver. The bars 10, 11 represent the upper edges of the hatch and correspond to the horizontal and vertical position of the hatch and its width.
To fix the permissible operating range of the grab bucket in the interior of the hold, the position of which relative to the loading bridge is unknown and can change, the grab bucket is controlled manually by the crane operator such that it is brought in its opened configuration as close as possible to the edge of the hatch first on the shore side and then on the water side of the ship. The actual values of the carriage horizontal travel and the holding mechanism vertical travel corresponding to these two approach positions of the grab bucket are set into the actual value memories 5 and 6, respectively, by operation of the keys 3 and 4 by the crane operator. The bars 10 and 11 corresponding to the approach positions are displayed on the receiver display in accordance with the output signals of the actual-value memories, thereby indicating the permissible operating range of the grab bucket. Within the operating range fixed by the bars, the crane operator can select any desired point by setting a desired value, for example from the desired value transmitter 13, accordingly. The counts of the desired-value counters 14, 17 set by the desired-value transmitter 13 are compared in the comparators 16, 17, respectively, with the actual values set into the actual-value memories 5, 6, respectively. If any desired value set by the crane operator exceeds a stored actual value, then the respective comparator blocks transmission of the portion of the desired value exceeding the actual value from the desired-value memory to the respective drive control.
If the crane operator preselects by means of the selector switch 20, a marking line from a marking line computer which intersects, for instance, one of the two bars 10 and 11 on the display, thus indicating the possibility of a collision of the grab bucket with a hatch edge, the output signal of the comparator 21 obtained from a comparison between the desired values corresponding to the marking line with the actual values stored in the memories 5 and 6 causes the two drive controls 22 and 23 to interrupt movement of the grab bucket.
In automatic operation, a control mechanism advantageously takes over the control of the carriage and holding mechanism drives and the opening and closing of the grab bucket. Except for selection of the marking lines, fully automatic operation of the device is thereby possible.
Pendulum oscillations of the grab bucket are damped or suppressed by means known to those of skill in the art.
The pickups, comparators, memories, counters, drive controls, and the desired value transmitter are per se conventional and known to those of skill in the art. Marking line computers and receiver/displays are also per se conventional and known to those of skill in the art.
The advantages of the present invention, as well as certain changes and modifications of the disclosed embodiments thereof, will be readily apparent to those skilled in the art. It is the applicant's intention to cover by his claims all those changes and modifications which could be made to the embodiments of the invention herein chosen for the purpose of disclosure without departing from the spirit and scope of the invention.
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An arrangement for controlling movement of the grab bucket of a grabbing crane used for loading and unloading bulk material into and from ships is disclosed. Collisions of the grab bucket with the ship's superstructure and the hatch edges are avoided according to the invention by approaching the hatch edges with the grab bucket open and displaying the actual values so obtained as bars representing the horizontal position and width of the hatch on a display. To avoid collisions, the grab bucket drives are switched off if any desired value, set manually or by a marking line computer, exceeds an actual value.
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BACKGROUND OF THE INVENTION
The present invention relates to a circulating fluidized bed reactor and a convertible combustion method applicable thereto.
The development of new regulations limiting greenhouse gas emissions, including carbon dioxide in fossil fuel power plants, is leading to the implementation of technologies for capturing the carbon dioxide present in the flue gases that are produced as a result of the combustion of fuel in the presence of air.
The technology frequently used to capture carbon dioxide consists of scrubbing the flue gases that have been diluted with nitrogen from the air employed for combustion purposes using solvents, which absorb the carbon dioxide and then restore the carbon dioxide as a concentrated carbon dioxide gas stream after the solvent has been regenerated by the heating thereof.
Such technology for its implementation consumes considerable energy and substantially decreases the efficiency of the fossil fuel power plants where such technology is utilizes, that is, decreases the efficiency of such fossil fuel power plants by more than fifteen percentage points.
U.S. Pat. Nos. 4,498,289 and 5,175,995 teach the use of oxygen as an oxidizer instead of air in boilers wherein steam is produced.
The advantage of using oxygen rather than air as an oxidizer is the reduction, going as far as the complete removal thereof, of the nitrogen, which is employed for purposes of diluting the carbon dioxide present in the flue gases and which originates from the nitrogen present in the air employed for combustion purposes as well as the substantial reduction in the size of the equipment required for such a purpose, thereby resulting in a flue gas flow rate that is approximately 35%-40% of the typical flue gas flow rate when air is employed for combustion purposes.
The application of this principle to a circulating fluidized bed boiler is disclosed in patent U.S. Pat. No. 6,505,567. According to the teachings of this document, a steam generator having a fluidized bed furnace includes means for introducing substantially pure oxygen into said steam generator.
The advantage of such a circulating fluidized bed technique is alleged to be that it permits the extraction of the heat in the circulating solids loop and the maintenance of a low combustion temperature, independently of the oxygen content of the oxidizer that is being utilized for combustion purposes. Hence such a technique is particularly attractive and serves to maximize the amount of oxygen in the oxidizer that is being utilized for combustion purposes, while at the same time minimizing the size of the circulating fluidized bed boiler, the size thereof being dependent directly on the flow rate of the flue gases that are produced during combustion.
However, according to this prior art, there are no teachings of any means that would be capable of being employed for purposes of effectively converting a circulating fluidized bed reactor, which is designed to utilize air for combustion purposes into a circulating fluidized bed reactor that is capable of utilizing oxygen for combustion purposes.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a circulating fluidized bed reactor, which has been designed specifically to operate with air being employed for combustion purposes and, with a minimum of structural modifications, permitting the conversion thereof into a circulating fluidized bed reactor that can effectively be operated with oxygen and recycled carbon dioxide being employed for combustion purposes.
For this purpose, the present invention proposes that a circulating fluidized bed reactor, which has been designed to be supplied with air to be used for combustion purposes, is capable of being converted to operate such that an oxygen-rich mixture is capable of being employed therein for combustion purpose. In accordance with the present invention, such a circulating fluidized bed reactor comprises a reaction chamber horizontally bounded by vertical walls, at least two centrifugal separators and a heat recovery element referred to hereinafter as a heat exchanger cage. Continuing such a circulating fluidized bed reactor also comprises means for introducing a fluidization gas into the reaction chamber thereof using at least one wind box located under the reaction chamber for purposes of maintaining a circulating fluidized bed of particles in said reaction chamber, means for transferring gas that must be dedusted from the reaction chamber to the separators, means for discharging the particles separated from the separators and means for transferring the dust-free gases from the separators to the heat exchanger cage. Thus, a circulating fluidized bed reactor is provided that is characterized in that
said reaction chamber comprises at least one partially internal vertical partition wall forming two subchambers communicating together and each communicating with at least one separator, and said heat exchanger cage comprises a partially internal vertical partition wall forming two subcages communicating together and each communicating together with at least one separator,
such that these partition walls are arranged in order to create a passage for the flow of the flue gases into one of said subchambers and into one of said subcages when the operation involves the feed of oxygen into the reaction chamber.
According to a preferred embodiment of the present invention, the cross-section of one of said subchambers is between 60 and 65% of the total cross section of said reaction chamber, the cross-section of the other subchamber being between 35 and 40% of the total cross-section of said reaction chamber, and with said oxygen-rich mixture being comprised of 70% of oxygen and 30% of recycled carbon dioxide.
Preferably, said wind box is divided into two sub-boxes by a wall placed in the same plane as said partition wall of the reaction chamber.
In the case in which the circulating fluidized bed reactor of the present invention also comprises at least two external beds, and each of them is designed to receive the particles leaving each separator via a solid particle fed channel and each of them is comprised of a wall which may be common with said reaction chamber. Additionally, a siphon arrangement is advantageously placed at least partially inside said reaction chamber along the length of said partition wall thereof, which may be common with said external beds and with said reaction chamber.
Preferably, the open area of said external beds are oversized in order to provide a free space for adding 10 to 20% of heat exchanger area.
The fuel feed lines are preferably oversized.
According to one exemplary embodiment of the present invention, the circulating fluidized bed reactor comprises a reaction chamber horizontally bounded by vertical walls, two centrifugal separators and a heat exchanger cage located behind the reaction chamber, and with the two separators being lateral and each having a common vertical wall with the side walls of the heat exchanger cage and the partition wall of the reaction chamber extending perpendicular to the front wall of the reaction chamber and with the partition wall of the heat exchanger cage extending parallel to the partition wall of the reaction chamber.
According to another exemplary embodiment of the present invention, the circulating fluidized bed reactor comprises a reaction chamber horizontally bounded by vertical walls, n centrifugal separators provided with flue gas outlet ducts operative for connecting each pair of separators to a rear heat exchanger cage and a heat exchanger cage located behind the reaction chamber, n being greater than or equal to 2, and wherein the reaction chamber's vertical side walls may be common with a vertical side wall of a set of n/2 separators, and wherein the partition wall of the reaction chamber is parallel to the front wall of the reaction chamber and the partition wall of the heat exchanger cage is parallel to the partition wall of the reaction chamber.
In the embodiment that is described above, preferably, the two flue gas outlet ducts, which connect each set of separators to the rear exchanger cage, are equipped with a vertically and parallelly extending partition wall.
The present invention further encompasses a method for converting a circulating fluidized bed reactor as indicated above, in order to permit such a circulating fluidized bed reactor's operation with a combination of both oxygen and recycled carbon dioxide. Such a method is characterized in that said method comprises the following conversion steps:
complete and sealed closure of the vertical partition wall of the reaction chamber to form two independent subchambers, one of which, being referred to as the combustion subchamber, is designed to function as a combustion chamber to which oxygen is supplied, and the other of which, being referred to as the cooling subchamber, is designed to be operative to cool the fluidization gases of the external beds, and complete and sealed closure of the vertical partition wall of the heat exchanger cage to form two independent subcages.
According to a preferred embodiment of this method of the present invention, such a method also comprises the following conversion steps:
disabling of the solid particle feed to the corresponding separator or separators, or disabling of the external bed(s) connected to the cooling subchamber, and blocking of the passage between the external bed(s) and the cooling subchamber, and on each side of the reaction chamber, connections are made in series of the solid particle feed channels of all the existing external beds, and the feed from one of the external bed(s) is connected to the combustion subchamber, and equipping all of these connections with control valves.
Advantageously, the method in accordance with the present invention further includes a step of installing a siphon arrangement so as to be located at least partially inside the reaction chamber along the length of the partition wall thereof. which may be common with the external beds and with the reaction chamber.
Preferably, the method of the present invention comprises the following conversion steps:
blocking of the outlet openings of the siphon arrangement inside the cooling subchamber, and forming openings in the ceiling and/or the walls of the siphon arrangement inside the cooling subchamber, and fluidizing the siphon arrangement in order to thereby ensure a longitudinal transfer of the solids present in this siphon arrangement.
The method of the present invention may also include the step of blocking all of the fuel and secondary air feeds to the cooling subchamber.
The present invention also encompasses a circulating fluidized bed reactor, which is designed to be fed with an oxygen-rich mixture, and which is capable of being converted in accordance with the method that has been described above.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described below in greater detail with reference to Figures of the Drawing wherein preferred embodiments of the present invention are illustrated.
FIGS. 1 and 2 are perspective views of a first embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIGS. 3 and 4 are perspective views of a first embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention, wherein the reaction chamber thereof and the heat exchanger cage thereof are illustrated as being opened in order to thereby provide an interior view thereof; and
FIGS. 5A to 5C are horizontal cross-sections of the upper portion of a first embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIG. 6 is a schematic and partial perspective view of a first embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIGS. 7A and 7B are vertical and horizontal cross-sections of a first embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIGS. 8A and 8B are also vertical and horizontal cross-sections of a first embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIG. 9 is a perspective view of a second embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIG. 10 is a horizontal cross-section of the upper portion of a second embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIGS. 11A to 11C are horizontal cross-sections of the upper portion of a second embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention; and
FIG. 12 is a cross-section of the bottom portion of a second embodiment of a circulating fluidized bed reactor constructed in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
According to the first embodiment of the circulating fluidized bed reactor of the present invention as described herein and as illustrated in FIGS. 1 to 8 of the Drawings, the circulating fluidized bed reactor is of the type similar to that which is described and illustrated in patent document WO 03/038338 that has been filed by the same Assignee as the present patent application.
To this end, this circulating fluidized bed reactor comprises a reaction chamber 1 horizontally bounded by vertical walls, two centrifugal separators 2 A and 2 B and a heat recovery element referred to herein as a heat exchanger cage 3 , which is located behind the reaction chamber 1 . This circulating fluidized bed reactor further comprises means for introducing a fluidization gas into the reaction chamber 1 for purposes of maintaining a circulating fluidized bed of particles in this reaction chamber 1 . A wind box 4 located under the reaction chamber 1 is utilized for this purpose. This circulating fluidized bed reactor also comprises means for transferring from the reaction chamber 1 to the separators 2 A, 2 B the gas, which must be dedusted, means for discharging the particles separated from the gas in the separators 2 A and 2 B, and means for transferring the dust-free gases from the separators 2 A and 2 B to the heat exchanger cage 3 . This circulating fluidized bed reactor also comprises two external beds 5 A and 5 B, each of which is designed to receive via a solid particle feed channel the particles leaving each of the separators 2 A and 2 B. Each of the external beds 5 A and 5 B has a wall, which is common to the reaction chamber 1 as well.
The two separators 2 A, 2 B extend laterally, and they each have a vertical wall, which is common with the side wall of the heat exchanger cage 3 .
According to this first embodiment of the present invention, this circulating fluidized bed reactor is designed to be supplied with air that is to be used for combustion purposes, but is also capable of being converted in order to be able to operate when supplied with an oxygen-rich mixture for combustion purposes, in an efficient manner and with a minimum number of conversion operations being required in order to achieve this result.
Preferably, such an oxygen-rich mixture consists of 70% oxygen and 30% recycled carbon dioxide.
Continuing, as illustrated in FIGS. 3 to 5 of the Drawings, the reaction chamber 1 comprises a partial internal vertical partition wall 10 that functions to divide the reaction chamber 1 into two subchambers 1 A and 1 B, which communicate with one another and with each also in communication with one of the separators 2 A and 2 B. The heat exchanger cage 3 comprises a partial internal vertical partition wall 30 that functions to divide the heat exchanger cage 3 into two subcages 3 A, 3 B, which communicate with one another and with each also in communication with at least one of the separators 2 A and 2 B.
The partition wall 10 of the reaction chamber 1 extends perpendicularly to the front wall of the reaction chamber 1 and the partition wall 30 of the heat exchanger cage 3 extends parallel to the partition wall 10 of the reaction chamber 1 .
Generally speaking, these partition walls 10 , 30 are arranged in such a manner as to define a cross-section of one of the subchambers, that is, subchamber 1 B and one of the subcages, that is, subcage 3 B in accordance with when the combustion is being conducted with an oxygen feed to the reaction chamber 1 . Advantageously, the cross-section of one of said subchambers, that is, subchamber 1 A is between 60 and 65% of the total cross-section of the reaction chamber 1 , while the cross-section of the other subchamber, that is, subchamber 1 B is between 35 and 40%.
The partition walls 10 , 30 , as shown in the Figures of the Drawings, extend from the ceiling to the bottom of the reaction chamber 1 and the heat exchanger cage 3 , respectively, and provide for the existence of a free passage in the bottom of the reaction chamber 1 and/or the heat exchanger cage 3 , respectively. As a variant thereto, the partition walls 10 and 30 may provide for the existence of a free passage in the upper portion of the reaction chamber 1 and/or of the heat exchanger cage 3 or the partition walls 10 and 30 may take the form of walls wherein several openings are provided therein, with such openings being distributed or not along their height and being located or not along their entire width.
In the heat exchanger cage 3 , the exchangers may be arranged parallel to the front wall of the reaction chamber 1 so that the exchangers pass through the partition wall 30 of the heat exchanger cage 3 in a sealed manner, as shown in FIG. 5A of the Drawings. A single row of collectors C is then necessary, with the collectors C being arranged on a side edge of the heat exchanger cage 3 along with steam dedusting apparatus (cleaners) D for cleaning the two subcages 3 A and 3 B and the exchangers.
The exchangers may also be arranged parallel to the front wall of the reaction chamber 1 so that they do not pass through the partition wall 30 of the heat exchanger cage 3 , as shown in FIG. 5B of the Drawings. Two rows of collectors C 1 , C 2 are then necessary, with each being located on one side edge of the heat exchanger cage 3 along with steam dedusting apparatus (cleaners) D for the cleaning of the two subcages 3 A and 3 B and the exchangers.
The exchangers may also be arranged perpendicular to the front wall of the reaction chamber 1 , as shown in FIG. 5C of the Drawings. Two rows of collectors C are then necessary, with the collectors C being arranged behind the heat exchanger cage 3 along with the steam or infrasonic dedusting apparatus (cleaners), according to the spacing between the exchangers, for purposes of effecting therewith the cleaning of the two subcages 3 A and 3 B and the exchangers.
The wind box 4 , clearly visible in FIG. 6 of the Drawings, is divided into two sub-boxes 4 A, 4 B by a wall 40 , which is located in the same vertical plane as the partition wall 10 of the reaction chamber 1 .
As a variant thereto, it may suffice for the wind box 4 to be pre-equipped for subsequent segmentation during the conversion of the circulating fluidized bed reactor.
As shown in FIGS. 7A and 7B of the Drawings, a siphon arrangement 6 is located inside the reaction chamber 1 along the length of the wall that is common with the external beds 5 A, 5 B and the reaction chamber 1 . In unconverted operation, that is, when air is being employed for combustion purposes, the siphon arrangement 6 does not have any specific function to perform other than to provide for the passage of the solids from the external beds 5 A and 5 B to the reaction chamber 1 via the outlet openings 6 A that are arranged along the entire width of the reaction chamber 1 . However, the siphon arrangement 6 may also be installed without departing from the essence of the present invention during assembly of the reactor chamber 1 , when the reaction chamber 1 is being operated with air being employed for purposes of combustion, in order to decrease and simplify the changes that need to be made in order to effect the conversion of the circulating fluidized bed reactor from operation with air for combustion purposes to oxygen for combustion purposes.
As a variant thereto, this siphon arrangement 6 may also be installed subsequently without departing from the essence of the present invention during the conversion of the circulating fluidized bed reactor from firing with air to firing with oxygen.
As shown in FIGS. 8A and 8B of the Drawings, the open areas of the external beds 5 A, 5 B are oversized in their length, in order to thereby provide free space. As will be described more fully hereinafter, the vaporization and/or superheat exchangers will in fact need to be added to the external beds 5 A and 5 B for purposes of the conversion of the circulating fluidized bed reactor to enable oxygen and recycled carbon dioxide to be employed for combustion purposes.
Furthermore, the fuel feed lines are oversized to permit the full passage of the fuel into the subchamber 1 B after such conversion to oxygen and recycled carbon dioxide firing. The same is also true for the fuel transport apparatus, which must allow for a total injected flow rate into the subchamber 1 B after such conversion to oxygen and recycled carbon dioxide firing.
The circulating fluidized bed reactor as previously described herein is designed to be operated when air is being employed for combustion purposes. Due to a number of changes, which will now be described, such a circulating fluidized bed reactor is capable of being converted to operate with oxygen and recycled carbon dioxide being utilized for combustion purposes. The general principles upon which this conversion is based are to use a single subchamber of the reaction chamber as a firebox or combustion chamber, to use the separator connected to said reaction chamber for the separator's primary function of separating gases and solids, to recover the gases leaving said separator in a subcage of the exchanger cage, to recover the solids leaving said separator in the two external beds connected for the parallel flow of the solids and connected at the outlet of said combustion chamber for transferring the solids, and connected at the outlet of the other subchamber, referred to herein as the cooling chamber, for transferring thereto the fluidization gas, that is, preferably, nitrogen.
For this purpose, the method of converting a circulating fluidized bed reactor as described above, to permit it's the circulating fluidized bed reactor's operation with oxygen and recycled carbon dioxide, comprises the following conversion steps:
effecting a sealed closure of the vertical partition wall 10 of the reaction chamber 1 to form two independent subchambers, one 1 B, referred to herein as the combustion subchamber, having a cross-section of between 35 and 40% of the cross-section of the reaction chamber 1 , which is designed to function as a combustion chamber that is supplied with oxygen and recycled carbon dioxide, and the other subchamber 1 A, referred to herein as the cooling subchamber, which is designed to be operative to effect the cooling of the fluidization gases from the external beds 5 A, 5 B, effecting a sealed closure of the vertical partition wall 30 of the heat exchanger cage 3 to form two independent subcages 3 A, 3 B, disabling of the solid particle feed to the corresponding separator 2 A, of the external bed 5 A that is connected to the cooling subchamber 3 A, such disabling can be performed by closing the solids flow control valve, which is provided to regulate the operation of the circulating fluidized bed reactor when air is being employed for combustion purposes or by dismantling said solids flow control valve and blocking off the corresponding line associated therewith, blocking off the passage between the external bed 5 A and the cooling subchamber 1 A, connecting in series the solid particle feed channels associated with the two existing external beds 5 A, 5 B, from the external bed 5 B to the external bed 5 A, which initially were connected to the combustion subchamber 1 A; equipping such connection of the solid particle feed channnels with a solids flow control valve, such as, for example, by utilizing for this purpose the solids flow control valve that was dismantled as described above. This solids control valve is to then be mounted at the end of the solid particle feed channel of the external bed 5 B, which has a common wall with the combustion subchamber 1 B, in order to thereby permit the controlled feed to be effected to the feed channel of the other external bed 5 A.
If the siphon arrangement 6 with its fluidization wind boxes 6 B has already been installed on the circulating fluidized bed reactor when the circulating fluidized bed reactor is operating with air before the conversion of the circulating fluidized bed reactor from air firing to oxygen and recycled carbon dioxide firing, this siphon arrangement 6 is modified in order to ensure that the outlet of the external beds 5 A and 5 B, there is the required separation of the solids circuit and the fluidization gas circuit of the external beds, the latter preferably being nitrogen, in the following manner:
blocking off the outlet openings 6 A of the siphon arrangement in the cooling subchamber 1 A, creating openings at the inlet, in the ceiling and/or one wall of the siphon arrangement 6 . which is installed in the cooling subchamber 1 A, effecting the fluidization of the siphon arrangement 6 to produce a longitudinal transfer of the solids in the siphon arrangement 6 in the direction extending from the external bed 5 B adjacent to the cooling subchamber 1 A to the external bed 5 A adjacent to the combustion subchamber 1 B, with this fluidization being accomplished through the use of recycled carbon dioxide and/or steam.
If the siphon arrangement 6 has not been installed in the circulating fluidized bed reactor when the circulating fluidized bed reactor is operating with air before the conversion thereof to oxygen and recycled carbon dioxide firing, a siphon arrangement 6 with its fluidization wind boxes 6 B, having the characteristics to which reference has been had hereinbefore, that is, having outlet openings for solids and outlet openings for gases, will need to be installed in the reaction chamber 1 .
In the case in which the wind box 4 has not already been provided with a partition wall, the wall 40 will need to be so mounted. Only the sub-wind box 4 B, which is located under the subchamber 1 B, is used in this connection and when so used is fluidized with oxygen and/or recycled carbon dioxide.
A device for intermittent extraction of any material deposits may be provided, without departing from the essence of the present invention, in the bottom of the other sub-wind box 4 A, which is located under the cooling subchamber 1 A. Such an extraction device may also be provided, without departing from the essence of the present invention, in the bottom of the cooling subchamber 1 A and close to the siphon arrangement 6 at the outlet of the separator 2 A, such as to be designed to be traversed by the fluidization gases from the external beds 5 A and 5 B.
The conversion method in accordance with the present invention also comprises the blocking off of all the fuel and secondary combustion air feeds of the cooling subchamber 1 A, whether these feeds are located in the reaction chamber 1 or in the siphon arrangement 6 . The secondary combustion air feeds of the combustion subchamber 1 B are equipped with oxygen-rich mixture injection rods.
Additional vaporization and/or superheat exchangers, of about 10 to 20% capacity, are installed in the free space of the external beds 5 A, 5 B. After conversion to oxygen and recycled carbon dioxide firing and during such operation with an oxygen-rich mixture, such vaporization and/or superheat exchangers are intended to function to replace the internal heat exchanger area of the cooling subchamber 1 A which is no longer used. Such vaporization and/or superheat exchangers are made to discharge into the shield circuits in order to thereby avoid the need for a circulating pump.
Downstream of the heat exchanger cage 3 , the initial flue gas circuit is used to process the gases that are discharged from the external beds 5 A and 5 B. A separate circuit is added after conversion to oxygen and recycled carbon dioxide firing in order to thereby process the flue gases containing carbon dioxide and steam that originate from the oxygen-rich fuel combustion circuit. This added separate circuit consists of ducts, gas-gas heat exchangers, filtration devices, fans and condensers that are designed to be operative to function as a carbon dioxide processing train before the compression of the carbon dioxide for transport purposes.
In the second embodiment as described hereinafter and as illustrated in FIGS. 9 to 12 of the Drawings, the circulating fluidized bed reactor is of a similar type as that described in patent document WO 2004/036118 filed by the same Assignee as the present patent application.
According to this prior document wherein a modular system is employed, a circulating fluidized bed reactor may comprise a reaction chamber horizontally bounded by vertical walls, n centrifugal separators that are provided with flue gas outlet ducts connecting each pair of such separators to a rear heat exchanger cage and an exchanger cage located behind the reaction chamber 1 , and with the reaction chamber 1 having each of it's the reaction chamber's vertical or side walls positioned so as to be common with a vertical or side wall of a set of n/2 separators.
The embodiment, which is specifically described in accordance with the preferred version thereof, is the embodiment wherein for such separators, n=4, but the present invention, without departing from the essence thereof, applies equally to the general case wherein for such separators, n is greater than or equal to 2.
This modular circulating fluidized bed reactor in accordance with the present invention comprises a reaction chamber 1 , which is horizontally bounded by vertical walls, two to six separators depending on the size of the circulating fluidized bed reactor, the embodiment of the present invention, which is being described here has four centrifugal separators 2 A to 2 D, and a heat recovery element, referred to herin as a heat exchanger cage 3 that is located behind the reaction chamber 1 . This circulating fluidized bed reactor further includes means for introducing a fluidization gas into the reaction chamber 1 and for maintaining a circulating fluidized bed of particles in this reaction chamber 1 . This circulating fluidized bed reactor also includes means for transferring the gas that must be dedusted from the reactor chamber 1 to the separators 2 , means for discharging the particles separated from the separators 2 , and means for transferring the dust-free gases from the separators 2 to the heat exchanger cage 3 . This circulating fluidized bed reactor may also include, without departing from the essence of the present invention, two to six beds, with the specific embodiment that is being described here having four external beds 5 A to 5 D, each of which is designed to receive particles leaving each of a corresponding separator via a solid particle feed channel, and each possibly having a common wall with the reaction chamber 1 .
Each of the vertical walls or side walls of the reaction chamber 1 may be common with a vertical or side wall of a pair of separators.
According to the present invention, such a circulating fluidized bed reactor, which is designed to be supplied with air for combustion purposes is capable of being converted so as to be able to be made to operate when firing an oxygen-rich mixture, in an efficient manner and with a minimum number of conversion operations being required in order to accomplish this result.
Preferably, such a oxygen-rich mixture consists of 70% oxygen and 30% recycled carbon dioxide.
Continuing, as illustrated in FIGS. 10 and 11 of the Drawings, the reaction chamber 1 includes at least one partial internal vertical partition wall 10 that is operative to form two subchambers 1 A and 1 B, which communicate with one another, and which also each communicate with side separators. The heat exchanger cage 3 includes a partial internal vertical partition wall 30 that is operative to form two subcages 3 A, 3 B, which communicate with each other, and which also each communicate with the separators.
The partition wall 10 of the reaction chamber extends parallel to the front wall S 1 of the reaction chamber 1 , while the partition wall 30 of the heat exchanger cage e extends parallel to the partition wall 10 of the reaction chamber 1 .
In general, the partition walls 10 , 30 are so arranged such as to thereby define a cross-section of the subchamber 1 B, and one of the subcages, that is, subcage 3 B when the mode of operation involves oxygen being supplied to the reaction chamber 1 .
Preferably, the cross-section of the sunvhamber 1 A is between 60 and 65% of the total cross-section of the reaction chamber 1 , while the cross-section of the subchamber 1 B is between 35 and 40%. Also, preferably the cross-section of the subcahe 3 A is between 60 and 65% of the total cross-section of the heat exchanger cage 3 , while the cross-section of the subcage 3 B is between 35 and 40%.
The partition walls 10 , 30 , as shown in the Figures of the Drawings, extend from the ceiling to the bottom of the reaction chamber 1 and heat exchanger bed 3 , respectively, so as to thereby provide a free passage in the bottom of the reaction chamber 1 and/or of the heat exchanger cage 3 . As a variant thereto, the partition walls 10 , 30 may also be made to provide a free passage in the upper portion of the reaction chamber 1 and of the heat exchanger cage 3 or the partition walls 10 , 30 may take the form of walls wherein several openings, are or are not distributed along their height and are or are not arranged along their entire width.
In the heat exchanger cage 3 , the exchangers may be arranged so as to extend perpendicular to the front wall S 1 of the reaction chamber 1 and may be made to pass through the partition wall 30 of the heat exchanger cage 3 in a sealed manner, as illustrated in FIG. 11A of the Drawings. In such a case, a single row of collectors C is then necessary, and such collectors C can be arranged on either the front edge of or behind the heat exchanger cage 3 .
The exchangers may also be arranged so as to extend perpendicular to the front wall of the reaction chamber 1 and not be made to pass through the partition wall 30 of the heat exchanger cage 3 in a sealed manner, as illustrated in FIG. 11B of the Drawings. In such a case, two rows of collectors C 1 and C 2 are then necessary, with such collectors C being arranged on the front and back edges of the heat exchanger cage 3 .
The exchangers may also be arranged so as to extend parallel to the front wall S 1 of the reaction chamber 1 such that the exchangers do not pass through the partition wall 30 of the heat exchanger cage 3 , as illustrated in FIG. 11C of the Drawings. In such a case, two rows of collectors C 1 , C 2 are then necessary, with each being arranged on one side edge of the heat exchanger cage 3 .
According to this embodiment of the present invention, the lower portion of the reaction chamber 1 may be of the type wherein an internal wall is formed in an upside-down V and comprises two fluidization hearths and two parallel wind boxes 4 ′ and 4 ″, that are clearly visible in FIG. 9 of the Drawings.
Each of the boxes 4 ′ and 4 ″ in turn is divided into two sub-boxes by a wall that is located in the same vertical plane as the partition wall 10 of the reaction chamber 1 .
As a variant thereto, it may suffice for the wind boxes 4 ′ and 4 ″ to be pre-equipped so as to be capable of subsequently being segmented when the circulating fluidized bed reactor is being converted from air firing to oxygen and recycled carbon dioxide firing.
As shown in FIG. 12 of the Drawings, two lateral siphon arrangements 6 ′ and 6 ″ may be arranged fully or partially in the reaction chamber 1 on the length of the wall closest to the external beds 5 A to 5 D or possibly can be made to be common with the lateral external beds 5 A to 5 D of the reaction chamber 1 . Prior to conversion, that is, when being operated with air firing, the siphon arrangements 6 ′ and 6 ″ do not perform any specific function other than to ensure the passage of the solids from the external beds 5 A to 5 D to the reaction chamber 1 via outlet openings suitably arranged for this purpose along the entire length of the reaction chamber 1 . The siphon arrangements 6 ′ and 6 ″ can be installed upon the assembly of the circulatimg fluidized bed reactor in order to thereby decrease and simplify the modifications required during the conversion of the circulating fluidized bed reactor from air firing to oxygen and recycled carbon dioxide firing.
As a variant thereto, such siphon arrangements 6 ′ and 6 ″ may be equally well installed subsequently during the conversion of the circulating fluidized bed reactor from air firing to oxygen and recycled carbon dioxide firing.
The open areas of the external beds 5 A to 5 D are oversized in their length in order to thereby provide a free space. As described hereinafter, vaporization and/or superheat exchangers will in fact have to be added in these external beds 5 A to 5 D in order to allow for the operation with oxygen and with recycled carbon dioxide.
As illustrated in FIG. 10 of the Drawings, the two upper flue gas outlet ducts connecting each pair of separators 2 A, 2 B and 2 C, 2 D to the back exchanger cage are equipped with a vertical and partial partition wall 7 , 8 of which their back edge is in the same plane as that of the partition wall 30 of the heat exchanger cage 3 .
Furthermore, the fuel feed lines are oversized in order to thereby permit the full passage of the fuel after conversion in the combustion subchamber 1 B. The same applies to the fuel transport apparatus which must permit a total injected flow rate after conversion in the combustion subchamber 1 B.
A reactor as previously described is designed to operate with air. Thanks to a number of changes which are now described, it can be converted so as to operate within an oxygen-rich mixture. The general principle of this conversion is to use a single subchamber of the reaction chamber as a firebox or combustion subchamber, to use the two separators connected to it in their primary gas and solids separation function, to recover the gases leaving these separators in a subcage of the exchanger cage, to recover the solids leaving these separators in the two corresponding external beds connected to the other external beds to be traversed in parallel by the solids each with its adjacent bed and connected at the outlet of said combustion chamber for transferring the solids thereto and connected at the outlet of the other subchamber, called the cooling subchamber, for transferring thereto the fluidization gas, that is preferably nitrogen.
For this purpose, the method for converting a circulating fluidized bed reactor as described above, in order to permit its operation with oxygen and recycle carbon dioxide, comprises the following conversion steps:
complete and sealed closure of the vertical partition wall 10 of the reaction chamber to form two independent subchambers, one 1 B, called the combustion subchamber, with a cross section of between 35 and 40%, designed to form a combustion chamber fed with oxygen and recycled carbon dioxide, and the other 1 A, called the cooling subchamber, designed to cool the fluidization gases of the external beds 5 A, 5 B, 5 C, 5 D, complete and sealed closure of the vertical partition wall 30 of the cage to form two independent subcages 3 A, 3 B, disabling of the solid particle feed by the two corresponding separators 2 A and 2 C, of the two external beds 5 A and 5 C connected to the cooling subchamber 1 A, this disabling performed by closure of the valve provided to control the reactor in operation with air or by dismantling this valve and blocking the corresponding line, blocking of the passage between these two external beds 5 A and 5 C and of the cooling subchamber 1 A, on each side of the chamber, connection in series of the solid particle feed channels of all the existing beds from the external bed connected to the combustion subchamber 1 B; a valve, for example, the one dismantled above, is then mounted at the outlet of the feed channel of each external bed having a common wall with the combustion subchamber 1 B, to permit controlled feed of the other bed of each pair, the two adjacent beds thereby being traversed in parallel by the solids, equipping of this connection with a solids flow control valve.
If the two siphon arrangements 6 ′ and 6 ″ have already been installed on the reactor before conversion, these siphon arrangements are modified by the following operations, in order to ensure at the outlet of the external beds, the separation of the solids circuit and the fluidization gas circuit of the external beds, that is preferably nitrogen:
blocking of the outlet openings of each siphon arrangement 6 ′, 6 ″ in the cooling subchamber 1 A, making of openings at the inlet, in the ceiling and/or one wall of each siphon arrangement 6 ′, 6 ″ in the cooling subchamber 1 A, fluidization of each siphon arrangement 6 ′ 6 ″ to produce a longitudinal transfer of the solids in these arrangements, in the direction going from the beds 5 A, 5 C adjacent to the cooling subchamber to the beds 5 B, 5 D adjacent to the combustion subchamber; this fluidization being performed by recycled carbon dioxide and/or steam.
If the siphon arrangement has not been installed on the reactor operating with air before conversion, a siphon arrangement with its wind boxes having the above characteristics, that is outlet openings for solids and outlet openings for gases according to the subchamber, is installed in the reaction chamber.
If the two wind boxes 4 ′ and 4 ″ have not already been equipped with a partition wall, this wall is mounted. Only the two sub-boxes located under the combustion subchamber 1 B are used and fluidized with oxygen and recycled carbon dioxide.
The partition walls 7 , 8 of the flue ducts are blocked at their end O in the cyclones so that the sub-lines supplying the subcage 3 B may retain part of the flue gases leaving the back cyclones 2 B, 2 D.
A device for intermittent extraction of any deposits can be provided in the bottom of the cooling subchamber 1 A and the other sub-boxes located under the cooling subchamber 1 A. Such an extraction device may also be provided close to the siphon arrangement at the outlet of the separators 2 A and 2 C designed to be traversed by the fluidization gases of the external beds.
The conversion method also comprises the blocking of all the fuel and secondary combustion air feeds of the cooling subchamber 1 A, whether these feeds are located in the reaction chamber or in the siphon arrangement. The secondary combustion air feeds of the combustion subchamber 1 B are equipped with oxygen-rich mixture injection rods.
Additional vaporization. and/or superheat exchangers, of about 10 to 20%, are installed in the free space of the external beds 5 A, 5 B, 5 C, 5 D. After conversion and during operation with an oxygen-rich mixture, these exchangers replace the internal heat exchange area of cooling subchamber 1 A which is no longer used. These exchangers can discharge into the shield circuits to avoid the need for a circulating pump.
Downstream of the exchanger cage 3 , the initial flue gas circuit is used to process the gases discharged from the external beds. A separate circuit is added to process the flue gases containing carbon dioxide and steam and originating from the oxygen-rich fuel combustion circuit. This added circuit comprises ducts, gas-gas heat exchangers, filtration devices, fans and condensers toward a carbon dioxide processing train before compression for transport.
While several embodiments and variations of the present invention have been shown it will be appreciated that modification thereof, some of which have been alluded to hereinabove, may still be readily made thereto by those skilled in the art. It is, therefore, intended that the appended claims shall cover the modifications alluded to herein as well as all the other modifications that fall within the true spirit and scope of the present invention.
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A circulating fluidized bed reactor is provided that includes a reaction chamber having a vertical partition wall forming two independent subchambers that include a combustion subchamber and a cooling subchamber. A combustion fluidizing gas is provided to the combustion subchamber to maintain a circulating fluidized bed therein. At least one centrifugal separator receives flue gas from the combustion subchamber and separates particles from the flue gas. At least one external bed receives the particles from the at least one centrifugal separator and provides the particles to the combustion subchamber. An external bed fluidizing gas is provided to the external bed to fluidize the particles therein. The cooling subchamber cools the external bed fluidizing gas received from the external bed. A heat exchanger cage receives the flue gas from the centrifugal separator and the external bed fluidizing gas from the cooling subchamber.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 13/963,448 filed on Aug. 9, 2013 (U.S. Pat. No. 8,966,822, issued Mar. 3, 2015); which claims the benefit of U.S. Provisional Application No. 61/681,863, filed on Aug. 10, 2012. The entire disclosure of the above application is incorporated herein by reference.
FIELD
[0002] The present disclosure relates to an air and/or debris dam for moving coil balance assembly for a hung window. More particularly, the disclosure pertains to a device located between the carrier and a mounting location of a moving coil window balance assembly that travels within the jamb channel of a window frame assembly to inhibit airflow and/or the deposition of dust and/or debris in the jamb channel.
BACKGROUND
[0003] This section provides background information related to the present disclosure which is not necessarily prior art.
[0004] Modern window assemblies in residential, commercial and industrial buildings may include one or more window sashes that are movable within a window jamb. Window sashes that move vertically to open and close often include two or more window balance assemblies. The balance assemblies urge the window sash upward (i.e., toward an open position for a lower sash or toward a closed position for an upper sash) to assist a user in moving the window sash and to retain the window sash at a position selected by the user.
[0005] The window jambs are positioned on either side of the window sash and form jamb channels in the window frame along which the window balance carrier traverses as the window sash is opened and closed. Adequate clearance is provided in the jamb channels to permit the carriers to move freely up and down. As a result of the movement of the carriers, however, there is a “chimney effect” that permits air and airborne dust and debris to flow into and through the jamb channel. This potentially adversely impacts the free movement of the window sash in the jamb channel. For example, as dust or dirt particles enter the jamb channel, they can deposit on the walls of the jamb channel. An increase in friction between the carrier and the jamb, or some other interference or degradation in the free movement of the carrier, may result causing the force needed to move the window sash to increase.
SUMMARY
[0006] This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
[0007] In one aspect, the present disclosure provides an air and debris dam that primarily serves to obstruct airflow through the jamb channel and provide a barrier to inhibit the proliferation of debris in the jamb channel.
[0008] In another aspect of the present disclosure, an air and debris dam can be included as a separate component installed after construction of the window assembly or as part of a window balance assembly that is installed during construction of the window assembly.
[0009] In another aspect of the present disclosure, an air dam and a debris dam can be individual components of a window balance assembly, or can be combined into a single component.
[0010] An air and/or debris dam for moving coil balance assembly for a hung window is provided. The air and/or debris dam can be located between the carrier and a mounting location of a moving coil window balance assembly. The air and/or debris dam can travel within the jamb channel of a window frame assembly to inhibit airflow and/or the deposition of dust and/or debris in the jamb channel.
[0011] In yet another aspect, the disclosure provides an air and debris dam for installation in a jamb channel of a hung window assembly between a carrier assembly of a moving coil balance assembly and a tilt latch of a window sash. The jamb channel can have a width and a depth and be defined by a first wall, a second wall opposite the first wall, and third and fourth walls disposed perpendicular to the first and second walls. The first wall can have a vertically extending slot. The air and debris dam can include a base portion having a generally rectangular prism geometry having a first dimension corresponding to the width of the jamb channel, and a second dimension corresponding to the depth of the jamb channel.
[0012] The air and debris dam can be movable vertically upward in the jamb channel in response to the carrier assembly bearing against lower end of the base portion and movably vertically downward in the jam channel in response to the tilt latch bearing against upper end of the base portion.
[0013] The air and debris dam can be formed from a light-weight, cellular foam-type resilient material that is flexible and elastically deformable. The air and debris dam can include a projection portion projecting outward from the vertically extending slot when the air and debris dam is installed within the jamb channel.
[0014] In still another aspect of the disclosure, a window balance assembly for installation within a jamb channel of a window jamb in a hung window is provided and includes a carrier assembly configured to engage a window sash and housing a curl spring, a mounting bracket fixed to the window jamb, positioned vertically above the carrier assembly and configured to engage an uncurled end of the curl spring, and an air dam having a generally rectangular prism geometry. The air dam is positioned within the jamb channel between the carrier assembly and the mounting bracket. The air dam is independently movable along an uncurled portion of the curl spring between the carrier assembly and the mounting assembly. Further, the window balance assembly can include a debris dam having a generally rectangular prism geometry. The debris dam is positioned above the carrier. Each of the air dam and the debris dam can have an opening to enable the uncurled end of the curl spring to pass therethrough.
[0015] Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DRAWINGS
[0016] The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
[0017] FIG. 1 is a partial front view of a window assembly;
[0018] FIG. 2 is a partial view of the window assembly of FIG. 1 and incorporating the air and debris dam according to the principles of the present disclosure;
[0019] FIG. 3 illustrates a perspective view of a window jamb including an exemplary air and debris dam according to the principles of the present disclosure;
[0020] FIG. 4 shows exemplary air and debris dams according to the principles of the present disclosure;
[0021] FIG. 5 shows exemplary air and debris dams according to the principles of the present disclosure as installed in a window jamb;
[0022] FIG. 6 shows an exemplary air and debris dam according to the principles of the present disclosure as installed in a window jamb and acting as a barrier to debris;
[0023] FIGS. 7A and 7B illustrate a perspective view and a cross-sectional side view of one exemplary air and debris dam according to the principles of the present disclosure;
[0024] FIGS. 8A , 8 B and 8 C show a front view, a top view and a cross-sectional side view of another exemplary air and debris dams according to the principles of the present disclosure;
[0025] FIGS. 9A and 9B show a front view and a cross-sectional side view of still another exemplary air and debris dam according to the principles of the present disclosure;
[0026] FIG. 10 is an exploded perspective view of window balance assembly incorporating an air dam and a debris dam according to the principles of the present disclosure;
[0027] FIG. 11 is a perspective view of the window balance assembly of FIG. 10 in a shipping configuration; and
[0028] FIG. 12 is a perspective view of the window balance assembly of FIG. 10 in an installed configuration.
[0029] Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION
[0030] Example embodiments will now be described more fully with reference to the accompanying drawings.
[0031] Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
[0032] With reference to FIG. 1 , a window assembly 10 is provided that may include an upper sash 12 , a lower sash 14 , a pair of window jambs 16 , a window sill 18 , and two or more window balance assemblies or cartridges 20 . In the particular embodiment illustrated in FIG. 1 , the upper sash 12 is fixed relative to the window sill 18 (i.e., in a single hung window assembly). However, in some embodiments, the upper sash 12 may be movable relative to the window sill 18 between a raised or closed position and a lowered or open position (i.e., in a double hung window assembly). The lower sash 14 may be raised and lowered between open and closed positions and may be connected to the window balance assemblies 20 which assist a user in opening the lower sash 14 and maintain the lower sash 14 in a desired position relative to the window sill 18 .
[0033] As shown in FIGS. 1 and 2 , the lower sash 14 may include a pair of pivot bars 22 and a pair of tilt latch mechanisms 24 . The pivot bars 22 may extend laterally outward in opposing directions from a lower portion of the lower sash 14 and may engage corresponding ones of the window balance assemblies 20 . The tilt latch mechanisms 24 may extend laterally outward in opposing directions from an upper portion of the lower sash 14 and may selectively engage corresponding ones of the window jambs 16 . The tilt latch mechanisms 24 may be selectively actuated to allow the lower sash 14 to pivot about the pivot bars 22 relative to the window jambs 16 to facilitate cleaning of an exterior side of the window assembly 10 , for example.
[0034] It will be appreciated that in a double hung window assembly, the upper sash 12 may also be connected to two or more window balance assemblies to assist the user in opening the upper sash 12 and maintaining the upper sash 12 in a selected position relative to the window sill 18 . In such a window assembly, the upper sash 12 may also include tilt latches and pivot bars to allow the upper sash 12 to pivot relative to the window jambs 16 in the manner described above.
[0035] Each of the window jambs 16 may include a jamb channel 26 defined by a first wall 28 , a second wall 30 opposite the first wall 28 , and third and fourth walls 32 , 34 disposed perpendicular to the first and second walls 28 , 30 , as shown in FIG. 3 . The first wall 28 may include a vertically extending slot 36 adjacent the window sash. The slot 36 divides the first wall 28 into a first portion 28 - 1 and a second portion 28 - 2 . The window balance assembly 20 may be installed within the jamb channel 26 . The pivot bar 22 may extend through the slot 36 and into the jamb channel 26 to engage the window balance assembly 20 . The tilt latch mechanism 24 may also selectively engage the slot 36 to lock the lower sash 14 in an upright position ( FIG. 1 ).
[0036] Each of the window balance assemblies 20 may include a carrier 40 , a curl spring 42 , and a mounting bracket 44 . As shown in FIG. 11 , for example, the window balance assemblies 20 may be initially assembled and shipped in an uninstalled or shipping configuration and may be subsequently installed onto the window assembly 10 and placed in an installed configuration by a window manufacturer, a construction or renovation contractor, or a homeowner, for example.
[0037] The carrier 40 (also referred to as a shoe) may engage the lower sash 14 and house a curled portion 46 of the curl spring 42 . As shown in FIG. 3 , the mounting bracket 44 may engage an uncurled end portion 48 of the curl spring 42 and may be fixed relative to the window jamb 16 . The curl spring 42 may resist being uncurled such that the curl spring 42 exerts an upward force on the carrier 40 , thereby biasing the lower sash 14 toward the open position.
[0038] One aspect of the present disclosure is an air and debris dam 200 , 200 ′, 300 , 400 shown in FIGS. 2-9 . The air and debris dam 200 , 200 ′, 300 , 400 primarily serves to obstruct airflow through the jamb channel and provide a barrier to inhibit the proliferation of debris in the jamb channel.
[0039] The air and debris dam 200 , 200 ′, 300 , 400 is preferably formed from a light-weight, cellular foam-type material that is flexible and/or elastically deformable, yet resilient. In this respect, the air and debris dam 200 , 200 ′, 300 , 400 can be deformed for installation through the slot 36 in the jamb channel 26 of an assembled window 10 , and then return to its original size and shape once positioned in the jamb channel 26 . The cellular foam material resists the flow of air and can capture debris 50 , as shown in FIG. 6 .
[0040] The air and debris dam 200 , 200 ′, 300 , 400 is sized and shaped to fit generally snugly within the jamb channel 26 of the window jamb 16 . Several exemplary embodiments of an air and debris dam 200 , 200 ′, 300 , 400 are shown in FIGS. 2-9 . Referring now to FIG. 4 , air and debris dams having various geometries are illustrated. A first exemplary air and debris dam 200 includes a base portion 202 having a generally rectangular prism geometry. The width w and depth d of the base portion 202 substantially correspond to the width W and depth D of the jamb channel 26 . As such, when the air and debris dam 200 is installed in a window jamb 16 , no portion of the air and debris dam 200 extends beyond the jamb channel 26 and, therefore, the air and debris dam 200 does not come into contact with the lower sash 14 .
[0041] An alternative variation of the air and debris dam 200 ′ is shown in FIGS. 7A and 7B . In the air and debris dam 200 ′, the depth d of the base portion 202 ′ is greater than the depth D of the jamb channel 26 . Additionally, the air and debris dam 200 ′ includes one or more scribe cuts or slits 204 ′ in the inner surface 206 ′ (i.e., facing the window sash when installed) of the base portion 202 ′ that extend to a depth is less than the total depth d of the base portion 202 ′. The scribe cuts 204 ′ can extend in a direction parallel to one or both of a longitudinal X axis and a lateral Y axis. The depth s of the scribe cuts 204 ′ extend in a direction parallel to a Z axis. The scribe cuts 204 ′ enable portions of the air and debris dam 200 ′ to flex or deform relative to one another. As shown in FIG. 7B , then, when installed in a window jamb 16 the air and debris dam 200 ′ occupies the width W and depth D of the jamb channel 26 but also includes a portion 208 ′ that projects outward from the vertically extending slot 36 of the jamb channel 26 and inward toward the lower sash_ 14 . The first and second wall portions 28 - 1 and 28 - 2 compressibly engage inner portions 210 ′ such that inner portions 210 ′ are pressed directly against first and second wall portions 28 - 1 and 28 - 2 . The projection portion 208 ′ can contact or form a seal against the lower sash 14 .
[0042] A second exemplary air and debris dam 300 is shown in FIGS. 4 , 5 , 8 A, 8 B and 8 C. The air and debris dam 300 includes a base portion 302 having a generally rectangular prism geometry and a projection portion 304 extending generally perpendicularly from an inner surface 306 (i.e., facing the window sash when installed) of the base portion 302 , and also having a generally rectangular prism geometry. When installed in a window jamb 16 , the projection portion 304 of the air and debris dam 300 extends outward from the vertically extending slot 36 of the jamb channel 26 and inward toward the lower sash 14 , as shown in FIGS. 5 and 8C . The projection portion 304 of the air and debris dam 300 , therefore, can contact or form a seal against the lower sash 14 . The first and second wall portions 28 - 1 and 28 - 2 compressibly engage the inner surface 306 such that the inner surface 306 is pressed directly against the first and second wall portions 28 - 1 and 28 - 2 .
[0043] It is understood by one skilled in the art that while the embodiment in this disclosure is directed toward a projection portion having a generally rectangular geometry, the geometry of the projection portion could also be circular, triangular, or another suitable shape. It is also understood that, while the embodiment in this disclosure shows the projection portion being integral with the base portion, the projection portion may be a separable piece from the base portion and may be selectively attached to and detached from the base portion as necessary or desired.
[0044] Still another exemplary air and debris dam 400 is shown in FIGS. 4 , 5 , 9 A and 9 B. The air and debris dam 400 includes a generally rectangular base 402 and an arcuate surface 404 opposite the base 402 . The air and debris dam 400 is dimensioned such that when the air and debris dam 400 is installed in a window jamb 16 , a central portion 406 of the arcuate surface 404 extends or projects outward from the vertically extending slot 36 of the jamb channel 26 and inward toward the window sash. The first and second wall portions 28 - 1 and 28 - 2 compressibly engage end portions 408 of the arcuate surface 404 such that the end portions 408 are pressed directly against first and second wall portions 28 - 1 and 28 - 2 . The central portion 406 of the arcuate surface 404 of the air and debris dam 400 , therefore, can contact or form a seal against the window sash, as shown in FIGS. 5 and 9B .
[0045] Referring now to FIGS. 2 and 3 , the air and debris dam 200 , 200 ′, 300 , 400 is positioned within the jamb channel 26 vertically above the carrier 40 of the window balance assembly 20 and below the tilt latch 24 of the window sash. The air and debris dam 20 is not fixed in the jamb channel 26 and it can freely move vertically within the jamb channel 26 . In this regard, vertical movement of the air and debris dam 200 , 200 ′, 300 , 400 within the jamb channel 26 results as the window sash moves vertically within the window jamb 16 . For the example of a single hung window, upward movement of the lower window sash 14 causes corresponding upward movement of the balance carrier 40 . As the balance carrier 40 moves in the jamb channel 26 , it bears against the lower end of the air and debris dam 200 , 200 ′, 300 , 400 and thereby urges the air and debris dam 200 , 200 ′, 300 , 400 upward. Correspondingly, downward movement of the lower window sash 14 causes downward movement of the sash tilt latch 24 , which bears against the upper end of the air and debris dam 200 , 200 ′, 300 , 400 thereby urging the air and debris dam 200 , 200 ′, 300 , 400 downward. The resiliency of the air and debris dam 200 , 200 ′, 300 , 400 enables it to maintain its geometry occupying the jamb channel 26 as it is urged by the carrier 40 and tilt latch 24 in the manner described.
[0046] The air and debris dam 200 , 200 ′, 300 , 400 can be a stand-alone component that is installed in the hung window separately from the window balance assembly 20 before or after construction of the window assembly 10 . Alternatively, the air and debris dam 200 , 200 ′, 300 , 400 can be installed at the same time as the window balance assembly 20 during construction of the window assembly 10 .
[0047] The air and debris dam can also comprise an air dam and a debris dam as two separate units. In this respect, another aspect of the present disclosure is shown in FIGS. 10-12 . As shown, the air dam and debris dam can be integrated with the window balance assembly. Referring to the exploded view of FIG. 10 , the window balance assembly 500 is shown to include a moving coil-type balance carrier 502 (such as that disclosed in International Publication No. WO 2011/100280 A1), a retaining bracket or bridle 504 , a debris dam 506 , an air dam 508 and a mounting bracket 510 (also such as disclosed in International Publication No. WO 2011/100280 A1). The air dam 508 and the debris dam 506 are each sized and shaped to fit generally snugly within the jamb channel 26 of the window jamb 16 .
[0048] As shown in FIG. 11 , the window balance assembly 500 can be packaged as a cartridge for easy shipping and installation. The bridle 504 is connected to the upper end of the carrier 502 at a base or platform portion 512 that nests with projections 514 formed in the upper end of the carrier's 502 housing. As shown in FIG. 10 , the air dam 508 includes openings or slits 507 and the debris dam 506 includes an opening or slit 509 . The slits 507 , 509 enable the air dam 508 and the debris dam 506 to slide over the legs 516 of the bridle 504 during assembly of the window balance assembly 500 . The debris dam 506 is first assembled and is adjacent to the carrier 502 . As shown in FIG. 10 , the slit 509 is oriented generally perpendicular to the loop portions 518 that are formed at the ends of the legs 516 of the bridle 504 . Consequently, when assembling the debris dam 506 over the bridle 504 , the loop portions 518 are oriented parallel to the slit 509 to enable the loop portions 518 to easily pass through the slit 509 . In this respect, it can be appreciated that the bridle 504 can be made from a flexibly resilient material, such as a thermoplastic, to enable the legs 516 and/or loop portions 518 to be reoriented to accommodate assembly of the debris dam 506 and thereafter return to their original orientation. Once the debris dam 506 is assembled to the bridle 504 , then, the loop portions 518 help prevent the debris dam 506 from disassembling from the bridle 504 .
[0049] The air dam 508 is thereafter assembled on top of the debris dam 506 . Also as shown in FIG. 10 , the slits 507 are oriented in the same direction as loop portions 518 that are formed at the ends of the legs 516 of the bridle 504 , such that the loop portions 508 can easily pass through the slits 507 after installation, so that the air dam 508 can freely move during operation of the window balance assembly.
[0050] The mounting bracket 510 then sits on top of the air dam 508 and is connected to the loop portions 518 formed at the ends of the legs 516 of the bridle 504 . In addition, as shown in FIGS. 11 and 12 , the air dam 508 and debris dam 506 also each include another opening or slit 520 , 521 at an end to enable the counter balance spring 522 to pass through them and connect to a hook portion 524 of the mounting bracket 510 .
[0051] As shown in FIG. 12 , at or after installation of the window balance assembly in a window jamb, the mounting bracket 510 is detached from the bridle 504 and a window sash is attached to the carrier 502 . The debris dam 506 is maintained in a close relative relationship to the balance carrier 502 by protrusions or barbs 526 included on the legs 516 or base portion 512 of the bridle 504 , or another suitable means for retaining a close relative relationship between the components. Consequently, the debris dam 506 moves up and down in the jamb channel 26 with the carrier 502 as the window sash is opened and closed. The air dam 508 , however, is not fixed in the jamb channel 26 or relative to the balance carrier 502 and it can freely move vertically within the jamb channel 26 as described above.
[0052] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.
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An air and/or debris dam for moving coil balance assembly for a hung window is disclosed. The air and/or debris dam is located between the carrier and a mounting location of a moving coil window balance assembly. The air and/or debris dam can travel within the jamb channel of a window frame assembly to inhibit airflow and/or the deposition of dust and/or debris in the jamb channel.
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FIELD OF THE INVENTION
[0001] This invention relates to a portable, potable water generator/dispenser capable of recovering liquid water for human use from the humidity of environmental air and sanitizing it for human use. The water generator of this invention draws in moisture-laden air from the surroundings and recovers liquid water by cooling the stream of air to below its dew point. The unit can be powered from electrical mains, single/3-phase, or portable generators, AC, 110-220 V, 50-60 Hz, DC power 60 V batteries or solar charged batteries. The preferred embodiment of the apparatus includes air filters of various types which remove suspended pollen or dust particles so that contaminants and undesirable impurities from the environmental air are not carried into the dew-forming section. The apparatus also includes heating and cooling devices, and ionizing and oxygenating subsystems. The most important feature of the basic unit and its variants are filtration and sterilization systems which provide purified liquid water free from contaminants and volatile organic compounds (VOC) as defined by National Science Foundation (NSF) Standard 53.
[0002] The external enclosure of the present apparatus may be a compact, attractive furniture-type wheeled design, one embodiment of which is further adapted to prevent or discourage entry of insects. The water generators of this invention employ ruggedized design and construction and certain embodiments are intended to operate unattended for extended periods in harsh, military-type environments such as peacekeeping actions, fires, earthquakes and weather disasters/emergencies. Emergency-use embodiments are prepared with a feed valve manifold connected to an input port; this permits selected or additional inputs of water from any source, such as a swimming pool, in emergency conditions such as a natural disaster. Other embodiments are intended to operate in land-transport vehicles, e.g., off-road, bus, train, seagoing vessels, recreational vehicles, business or home office environments. Further hybrid embodiments lend themselves to incorporation into icemakers, refrigerators, drink coolers, water coolers, window air conditioners, etc. Another embodiment includes an automated pressurized valve manifold, equipped with sensors to detect the amount of water being generated, connected to a pressurized municipal water supply to provide for admission of municipal water into the recirculating-purification system; this sub-system would be activated under atmospheric conditions which limit the generation of water from the environmental air. The manifold is pressurized either by the municipal water system or by an internal pump allowing for immediate dispensing of purified water at a drinking fountain or into a refrigerator's ice maker/chiller with or without electricity. Such embodiments include an electronic control, specifically a microprocessor, to sense critical operational parameters of the generator and to activate alternative modes of operation along with related visual and audible mode/status indicators. The electronic control also provides the timing to control recirculation within the apparatus to keep the water pure. When the storage tank is full there is also provision, which is automatically controlled, for actuating an electrically or manually operated valve to direct excess water being generated into an additional system or storage vessel. Still further, compact luggage-type embodiments can be provided for travel or sports use.
[0003] An air filter is used to remove suspended pollen or dust particles so that contaminants and undesirable impurities are not carried into the dew-forming section. The apparatus may have municipal water connected by quick disconnect fittings so it may be purified, filtered and dispensed when there is insufficient condensate. Both the condensate and the municipal water is filtered by a water filter certified to meet NSF-53 standards. The water from collected condensate and/or the municipal water is also purified in a bacteriostat which contains appropriate bacteria killing devices such as an ozone generator or an ultraviolet light. Further, the apparatus is a size and weight which makes it readily portable and capable of being hung on a wall, or placed on a sink top, in the attic, garage or other convenient location favorable for producing condensate. The apparatus has quick disconnect fittings for attaching one or more remote dispensers by flexible tubing. This embodiment also provides a recirculation loop and a computer programmed timer to control the compressor's off/on or reversal time interval to maximize condensate collection when the evaporator is freezing due to environmental conditions. Digital counters and a digital display contain a humidistat and thermostat, operation indicator lights, and digital counters to indicate system operation or the need for a filter change. Futher, the maximum condensate production for any model can only be determined by engineering tables and by testing the model in a controlled environment test chamber; such tests can include cyclical freezing and thawing of the evaporator and increasing the air flow over the evaporator. From the results of those tests, a computer program is written and programmed into a timer that controls the operation of the compressor for max zing condensate. The results of the tests also enable the creation of a graph which exhibits expected water production at various temperature/humidity combinations.
[0004] Additionally, various embodiments can be fitted with an input port for impure water for priming, or a self-priming pump to avoid the need for priming, for increased output capacity and for operation under conditions when environmental temperature and/or, humidity do not allow enough water to be generated. Various embodiments also allow for tailoring a water generator for specific use to increase efficiency and decrease manufacturing costs.
BACKGROUND OF THE INVENTION
[0005] The consensus of most medical experts is that water supply is the single most critical factor to human health. Over 400,000 people were stricken, 4,000 hospitalized and over 100 people died in Milwaukee in 1993 from Cryptosporidium, a bacterial contaminant in their city-treated drinking water. Natural Resources Defense Council estimates that in the US alone more than 900,000 become ill each year from water-borne disease and as many as 900 will die. There is also an increasing awareness that “bottled water” itself may be no safer than municipally treated water. Some citizens feel protected by household-type water filters. However, of the over 2,000 types/styles/sizes of filters now being sold to the public for additional treating of city water, only a few remove significant amounts of parasites, viruses, bacteria, pesticides and heavy metals. While contaminated water is harmful to adults, infants and young children are at much greater risk from drinking impure water, particularly water with high levels of heavy metals or radioisotopes. Therefore, it is essential that a filter, such as an NSF 53-compliant filter, be used to remove impurities and VOCs. In addition, operation of a water generator in the vicinity of a pesticide plant or during insect spraying, either from the air or truck mounted units, could place VOCs in the generated water. Also, if a generator without an NSF 53 filter is producing water when its host house is sprayed for pest control, the water could be severely contaminated with VOCs.
[0006] While the situation is bad in parts of the United States, it is worse in many other developed countries and critical in third-world countries. In developing nations, there is often at least intermittent electricity but no source for potable water. For clinics and hospitals in such remote areas, doctors and technicians need purified water for scrubbing and to prepare medicines. In the case of remote villages in developing countries, there is a need for a unit which generates and dispenses purified water, is easily moved, is relatively inexpensive to manufacture and which can operate from a variety of types of electrical power with a minimum of maintenance.
[0007] The most common potable water dispenser for use in the home and office is the 20-liter glass or plastic bottle placed on a gravity-flow dispensing stand. The bottles usually provide processed spring or well water and are generally sold with a representation of compliance with state and local health codes for potable water. One major drawback to “bottled water” is the fact that filled containers are heavy (approximately 25-30 kg) and awkward to change. Another problem is that algae can build up in the user's stand, necessitating periodic cleaning to maintain water purity. Relative to dissolved and suspended contaminants and undesired impurities, “bottled water” may be no safer than municipal water.
[0008] Today, 75% of American homes use chlorine-treated water. A problem that is just beginning to be recognized by the public is the reaction of chlorine with organic materials such as decaying vegetation. These reactions produce by-products known as halogenated organic compounds or trihalomethanes, which are known carcinogens. A recent study concluded that 18% of rectal cancers and 9% of bladder cancers can be attributed to by-products related to water chlorination.
[0009] At this time, the market for portable, potable water sources requires: (a) generation of high-quality water which is certifiably free of all impurities which are health hazards to infants and children in particular, (b) no necessity for storing and moving heavy bottles, (c) no requirement for expensive, complex maintenance procedures/cleaning, (d) low operating cost, (e) no special wiring/plumbing for installation, (f) attractive, office-furniture styling, (g) a more efficient water generator, (h) a low cost method of increasing the temperature/humidity range of condensate production, (i) a control and display panel indicating system operations, and (O) graphing abilities to indicate expected water production at various temperature/humidity conditions.
BACKGROUND ART
[0010] Current US Environmental Protection Agency (EPA) standards for impurities in primary and secondary drinking water are included as pp. 32-34 of the publication, “Drinking Water Treatment Units Certified by NSF International”, NSF International, Ann Arbor, Mich. (1995). These 1995 drinking water-standards of US Environmental Protection Agency, ANSI/NSF-53, are included herein by reference. The specific analytical chemistry methods for each impurity covered by NSF-53 are described in EPA publications in the US Federal Register. There are several US patents that are relevant in the field of art.
U.S. Pat. No. 3,675,442, issued July 1972 to Swanson (Swanson442); U.S. Pat. No. 4,204,956, issued May 1980 to Flatow (Flatow-956); U.S. Pat. No. 5,149,446, issued January 1991, to Reidy (Reidy-446); U.S. Pat. No. 5,106,512, issued April 1991 to Reidy (Reidy-512); U.S. Pat. No. 5,227,053, issued July 1993 to Brym (Brym-053); U.S. Pat. No. 5,259,203, issued November 1993 to Engel et al. (Engle-203); U.S. Pat. No. 5,301,516, issued April 1994 to Poindexter (Poindexter-516); U.S. Pat. No. 5,517,829, issued May 1996 to Michael (Michael-829); U.S. Pat. No. 5,553,459, issued September 1996 to Harrison (Harrison-459); U.S. Pat. No. 5,669,221, issued 23 Sep. 1997 to LeBleu et al. (LeBleu-221); U.S. Pat. No. 5,701,749, issued 30 Dec. 1997 to Zakryk (Zakryk-749); U.S. Pat. No. 5,704,223, issued 6 Jan. 1998 to MacPherson (MacPherson-223); U.S. Pat. No. 5,331,5830, issued 7 Apr. 1998 to Doke et al. (Doke-830); U.S. Pat. No. 5,845,504, issued 8 Dec. 1998 to LeBleu (LeBleu-504); U.S. Pat. No. 6,029,461, issued 29 Feb. 2000 to Zakryk (Zakryk-461); U.S. Pat. No. 6,182,453, issued 6 Feb. 2001 to Forsberg (Forsberg-453); U.S. Pat. No. 6,227,003, issued 8 May 2001 to Smolinsky (Smolinsky-003); U.S. Pat. No. 6,237,352, issued 29 May 2001 to Goodchild (Goodchild-352); and U.S. Pat. No. 6,289,689, issued 18 September 2001 to Zakryk (Zakryk-689).
[0030] Except for LeBleu-221, LeBleu-504, and Forsberg-453, also owned by an entity affiliated with the Applicant herein, none of the water generators disclosed in these publications are designed primarily as a dispenser and, none are designed as portable units. Swanson-442 provides a large, heavy apparatus, and specifically teaches that small, portable units are relatively inefficient.
[0031] None of the above references disclose all or even a majority of the following features or embodiments, many of which are described herein as optional depending on the climate or conditions under which the generator is operated:
Integral, external fluid-delivery valves and controls; Ion generator for discharged air stream, Insect-resistant port covers/screens, access doors, edge joints; Ultrasonic pest deterrent; Ozone generator for water sterilization treatment; Handle grips for easy movement by lifting or rolling; Medical/food-handling-type tubing and joints for water handling subsystems; Chemically-inert, thermally-conductive dew-collector surface films; Working fluids in heat absorbers which comply with 1996-edition DOE, EPA and ASHRAE standards/regulations (such as refrigerant fluid 406A); Ruggedized, long-life components and sub-systems; Safe, convenient dispensing height for hot or cold water; Electrostatic or conventional air filter with or without whistle alarm for blocked condition; High Efficiency Particulate Air (HEPA) filter certified to remove pollutants to a size of 0.3 microns; Night lights for controls and delivery valves for low-light situations; Air-heating strip and fan (for outside units); Water filter capable of meeting NSF-53 standards for VOCs; Recirculation of water during periods of generation or on a predetermined time-interval or waterflow basis; Provision for automatically-introducing municipal water during certain atmospheric conditions; Provision for changing output vibrational frequency of ultrasonic pest control; Provision for manual or automatic introduction of water from any source under emergency conditions; Audible and visual operational status/mode displays; Quick disconnect provisions for connection to existing appliances such as refrigerators, ice makers, and the like; Remote location of unit from its dispensers; Quick disconnect fittings to inlet water line for use of municipal water, after passed through the bacteriostat, when insufficient condensate is present; Various lengths of flexible water lines having quick disconnect fittings encircled by a sleeve for easy connection of the apparatus to remote dispensers; A leak detector which shuts off power if a leak is detected; A unit made portable by its small size and weight; A unit capable of mounting to a wall; A unit with a thermostatically controlled heater to prevent freezing in exposed locations; A means, including a quickly reversible refrigeration cycle, for alternately freezing and thawing the evaporator to produce condensate under normally undesirable conditions; Alternate sterilization methods including ozone generators for purifying and treating discharged air and negatively charging water; A UV canister optimally designed to require water flow through bacteria “killing zones” so as to maximized bacteria destruction; A UV canister having sensors to permit sufficient water flow as will maintain a constant water level in a storage tank; Provision for gravitational introduction of condensate from evaporator coils directly into a UV canister; Provision for sealed, disposable UV canister; An easily removable, easily cleaned storage tank; A secure tube for introduction of medicines directly into the cold water tank; Recirculation of water through storage tank and UV canister in isolation of a medicated/treated water; Multiple solid-core charcoal filters for removing VOCs; A means for mineralizing the pure condensate; A self-priming pump that will not destruct if run dry; A system to completely recirculate all water through the storage tank, UV canister, and all filters and components in a manner that disallows standing water; A pump sufficiently strong enough to permit circulation of water through solid-core filters and still allow rapid external dispensation of water; A heater for heating a room; A heater for heating air passing over the evaporator; Large wheels to facilitate movement of unit over uneven surfaces; Ground fault interruption circuitry; Multiple-speed squirrel cage fans; A means for oxygenating the processed water; NSF approved tubing rated at 400 p.s.i.; An air freshener tray for adding a pleasant scent to air reintroduced into a room; Child-proof valves for dispensing hot and/or cold water; Dual on/off switches: one manually- and one electronically-activated; Fuses and/or circuit breakers; A membrane switch panel to control the power, operational mode, fan speed, display, and timer function; A line so fitted as to permit attachment to a standard refrigerator ice maker; Insulation on cold lines to prevent “sweating” and moisture build-up; A unit of such size and weight as permits sink-top use; A water-generating apparatus integrated into a typical window air-conditioning unit; A means for purifying water by vaporization and condensation; and A reverse-osmosis membrane filter, waste water from which may be recycled.
[0091] The patent publications noted above generally disclose: (a) industrial water-condensation units designed to be permanently-attached to building air ducts or (b) water purifiers, not portable dispensers with optimized UV canisters, and (c) not with a quickly reversible refrigerant cycle to maximize water collection in low humidity and temperature. Details of some of these references are as follows:
[0092] Reidy-512 discloses a fixed-position, large-volume, high-rate water generator suitable for supplying drinking water to an entire office building, laundry, etc. The device is described as “having ducts for bringing this supply of ambient air to the device and for releasing the air back outside the device after it has, been processed”. The attached, permanent “ductwork” is characterized further as “extending through an outside wall of the structure or dwelling”. While sensors, indicators, interlocks, alarms for the UV lamps. air filters and water filters are mentioned briefly, other major components of the apparatus are usually characterized by single-word descriptions such as “air filter element”, “evaporator coils”, “condenser coils”, etc. In both Reidy-512 and Reidy-446 patents, the drain is located on the base of his water generator, a position which makes the drains completely unsuitable for dispensing water unless the machine is placed on legs or mounted in a cabinet. Reidy-512 teaches two passes of water past ultraviolet light tube to kill bacteria whereas the present apparatus provides for automatic, continuing recirculation of the water in the final delivery tank through a UV bacteriostat zone. Reidy-512 has a number of additional limitations and shortcomings: the user must set the humidistat and thermostat. No provision is made for insect proofing of the cabinet; and the gravity flow water filter is located under the collection pan and is severely limited in both flow rate and minimum pore size by the gravity-feed pressure head. In the apparatus of the present invention, water flows through a filter under pressure from a pump; this allows for high rates and small-pore, filter/adsorption media such as a porous-carbon block in the NSF 53 certified filter. The present invention also provides that liquid may be dispensed directly from the apparatus without having-to remove the storage tank whereas Reidy-512 requires that water be poured from the removed storage tank.
[0093] Poindexter-516 has no germicidal light nor a remote collection diverter valve. A drain is shown in FIG. 2 but none in FIG. 1 . The drain is shown on the bottom of the apparatus which, if on the floor, is essentially inoperable and, if raised on a stand, makes a top-heavy unit which would require permanent wall anchors.
[0094] Engle-203 is essentially two tandem dehumidifiers. A second-stage compressor with its condenser coil immersed in the storage tank produces heated water. One familiar with the art realizes that such heated water would never reach 75 C as does the heated water in the present apparatus. A further problem of locating the condenser coil in the storage tank is that it prevents removal of the tank for cleaning without opening the refrigerant system. Still further maintenance problems arise from the positioning of drains, i.e., there are no external dispensing valves and the drain valves are poorly located for replacing the valves because of the limited access inherent in their location.
[0095] Poindexter-516 describes a stainless-steel air-cooling coil and collection pan which adds significantly to the cost of manufacturing and does not specify the specific type of stainless steel, 314L, which is required for water handling in production facilities. The specification goes into great detail on the types of chemicals usable to clean areas which contact the water. In the present apparatus, the storage tank is completely removable and the condensate is sanitized by passing under the germicidal light several times.
[0096] Harrison459 uses a UV lamp tube to treat the discharge water stream. This indicates that bacteria and or algae may be growing within the unit or its plumbing connections. This unit also must be primed initially with approximately 10 liters of start-up water which can be a source of initial contaminants, such as VOCs which are neither removed nor broken down by either UV radiation or granular carbon charcoal. Whether this technology is compliant with NSF-53 remains a question. In the device, the compressor operates to maintain a cold set-point temperature within the water tank, i.e., the compressor operates to cool the fluid remaining in the tank even when the device is not actively producing water condensate. In contrast, the present invention saves energy by shutting off when it is not producing water. Further, the present invention may include a wheeled, furniture-type, user-friendly cabinet complete with carrying handles, disposable cups, related holders, diverter valve and air-filter blockage alert. Also, since the present invention is fitted with a gravity discharge or pressurized line, it is possible to draw water even in the event of a power failure. The Harrison-459 unit, which employs an electric solenoid valve, would not be able to deliver water in the absence of electrical main power.
[0097] Swanson-442 suffers from many of the same deficiencies as Harrison459; further, it also lacks an air filter or a UV disinfecting system. While Swanson-442 discharge device is shown on one figure, the location and operating parameters are not specified.
[0098] Brym-053 provides a UV-activated catalyst water purifier/dispenser for tap water (well or public supply) which can be installed below the counter or enclosed-in a cabinet. This unit merely treats water supplied to it, and in the process, a certain portion of the incoming flow is diverted to waste.
[0099] Michael-829 is primarily a device for producing and filtering “drinking” water across “activated charcoal” and a “plastic mesh micropore filter”. It is probably not compliant with NSF-53 standards for VOC removal. Further, it has no provision for continuing circulation of water in order to maintain purity, heater fan and/or hot-gas bypass.
[0100] The prior patents cited above generally use a typical refrigerant deicer system to keep their evaporators from freezing under low condensate flow rates, which can occur with cool ambient air. For example, Reidy-512 patent describes water production cessation at about 10 C. This limitation occurs because: (a) obtaining condensate is inefficient, (b) condensation is not cost effective at such low temperatures and (c) the evaporator tends to freeze over at lower temperatures. This limitation also occurs because of the design of the water generating device using a typical hot-gas bypass deicer which is not computer controlled for temperature/humidity combinations.
[0101] All of the devices cited are large capacity refrigerant gas dehumidifiers. The refrigerant gas from the compressor cools an evaporator coil and when ambient air is passed by the coil, moisture condenses out and drips to a collector below. When operated over extended periods or in cooler temperatures, the evaporator tends to freeze over due to low flow rate of condensate. In this situation, the compressor is designed to switch over to hot-gas bypass mode. A thermostat and/or humidistat control assists in determining when the compressor switches over. This on/off cycle during cooler temperatures drastically reduces production of water until the compressor eventually stops when temperature of incoming air is too low. However, the present system actually uses the freezing and thawing generated by quick reversal of the refrigeration cycle to produce condensate by one of several computer controlled options for alternately freezing and thawing condensate.
[0102] MacPherson-223 describes and claims a thermoelectric (TE) cooler attached to a medicine-cooler bag containing an insulin vial. Since the drug vial cooler disclosed is a non-circulating, closed, small-volume, sterile-fluid system, there are few similarities in structure or function compared to the present invention.
[0103] Zakryk-749 describes and claims a water cooler with a TE cooling junction integrated into the side walls of the holding tank. Because the TE apparatus of the invention is not described in detail, it is difficult to compare either its structure or function with the present invention.
[0104] Zakryk461 is a CIP of Zakryk-749. It further describes and claims the water cooler of the Zakryk-749 patent which further includes a water filter assembly. Again, however, the apparatus is not disclosed in detail, making it difficult to compare either its structure or function with the present invention.
[0105] Zakryk-689 further describes and claims the water cooler of the above Zakryk patents to include a sediment filter assembly. Here again, the apparatus is not technically described in a manner that would allow comparison of either its structure or function with the present invention.
[0106] Doke-830 describes and claims a TE apparatus integrated into an insulated picnic or food-transport container. Because the invention includes an air-circulation fan through the wall of the container, it is distinguishable in structure and function from the present invention.
[0107] Smolinksy-003 describes and claims a typical reversible heat pump system enabled to collect, under certain conditions, excess refrigerant to improve efficiency. The described apparatus does not extract water from air as does the present invention. The present invention, although utilizing in some embodiments a typical reversible heat pump system, does not provide for a tank for excess refrigerant. Rather, the present invention utilizes a flow rafter to increase cooling efficiency.
[0108] Goodchild-352 describes an apparatus for generating water from air and dispensing potable water, and further claims a hot gas injection system to prevent freezing of condensate on the evaporator such that generation of water from ambient air at temperatures as low as 50° F. is enabled. The present invention, in contrast, uses a flow rafter expansion valve to encourage freezing of condensate on the evaporator, and then reverses the heat pump cycle to thaw the condensate, or ly uses a heating strip to raise the temperature of the air passing over the evaporator.
[0109] Finally, Forsberg-453 describes the basic apparatus upon which the present invention improves. The present invention further claims an UV canister optimally designed for maximum bacteria destruction, as well as means for medicating, mineralizing, and oxygenating the extracted water. Worldwide Water, Inc., the owner of Forsberg-453, is affiliated with the Assignee/Applicant of the present invention.
DISCLOSURE OF THE INVENTION
[0110] The present invention is an apparatus to generate drinking water by condensation of moisture from the atmosphere. Alternative embodiments allow tailoring of the system for maximum production and efficiency in varied climates, temperatures and/or settings. Various options for obtaining pure water are utilized as it becomes increasingly more difficult to remove moisture from low humidity or temperature atmospheric conditions. In low humidity conditions, provision is made for automatically purifying municipal water. The system also utilizes the tendency of evaporators to freeze at lower temperatures. By specifically controlling the freezing and thawing, condensate can be produced in temperatures lower than the temperature at which most dehumidifiers automatically turn off.
[0111] The water generator of the present invention operates within a closed housing and incorporates dispensing subsystems to deliver water directly to the external dispensing valves. It is not necessary to open the housing every time a small quantity of water is desired. The housing panels and various openings of outdoor embodiments of the present invention are fitted with tight-sealing flanges to prevent insect infestation and environmental contamination of the water; alternatively, such units may be fitted with an ultrasonic insect deterrent. Any dispenser that is designed to work in remote, harsh environments must be designed so that the outside envelope is infrequently opened and then only for maintenance.
[0112] The dew-forming surfaces of the present invention are preferably plated with gold to increase the rate of heat transfer. Metals other than gold may be used to achieve a similar result. For example, silver plating works just as well, but tends to oxidize in an unsightly fashion. However, such plating is a vast improvement over the prior art of coating the dew-forming surfaces with food-grade materials such as Teflon®, which tend to reduce (i.e. insulate) rather than increase the rate of heat transfer.
[0113] For embodiments intended for use in a home or office, certain of the insect and dust-sealing features may be omitted and the cabinet implemented with attractive, furniture-type styling. To make the present water generator-dispenser more desirable for office or home use, the unit can be fitted with subsystems for producing water at three temperatures, i.e., hot, cold and ambient. Cooling of the water is accomplished by adding a secondary heat absorber source; this absorber may incorporate reverse-cycle cooling or other alternatives such as Peltier-effect or chemical/magnetic cooling effects. Insulation may be provided to surround the cold refrigerant lines of the secondary heat absorber source to reduce or eliminate moisture “sweating” and buildup inside of the housing. Another method of chilling water is by incorporating a thermoelectric probe-module as a second heat absorber; the unit is mounted on the outside of the tank and cooled by a fan.
[0114] To produce hot water, a heating element is placed within a heated, food-type, stainless steel tank with an insulating jacket is added. An alternate method of supplying heated water for delivery from an external valve is to provide an in-line, resistance-heated tube of sufficient length to heat water being delivered from the cold-temperature zone of the cold water tank to the hot-water external valve. Also, an electrically or manually controlled diverter valve may be installed to allow pumping into a container outside the housing. Incorporated is a secure tube to permit introduction of medicines and/or vitamins into a separate water tank in fluid communication with the storage tank. This feature is particularly helpful in undeveloped regions where mass medical treatment of an entire household or village is desired; accordingly, the bulk water may be treated via the secure tube. The present invention permits recirculation of the condensate without disturbing the medicinated/treated water. For convenience, the storage tank is easily removed: the storage tank lid has attached to it all of the storage tank sensors, which lid is lifted out of the way to permit removal of the storage tank tub without disconnecting either connected tubing or sensors.
[0115] The present invention is adapted to be connected to municipal water to provide treated water even in conditions when it is not possible to provide a sufficient quantity of water by condensation, and is further adapted to be able to accept, under emergency conditions, water from a source such as a swimming pool and purify it to emergency drinking-water standards for a temporary period. Accordingly, a membrane filter or solid core charcoal filter to remove heavy metals and other toxic substances is connected in line with the external water inlet to ensure purity. The present invention may be so embodied that water purity may be obtained by vaporizing incoming water for passage over the water-condensing surfaces and so into the circulation of the system For added health benefit, an oxygenator may be included to introduce oxygen into the water prior to dispensation.
[0116] The preferred embodiment of bacteriostat of the present invention is an ultraviolet light (UV) canister designed to optimize the killing effect of the UV radiation. The canister is shaped to surround a UV-radiating bulb so as to direct the liquid condensate into the zone of effective bacteria destruction. The interior surfaces of the canister walls are coated with a highly reflective material. This reflective feature is primarily to reflect UV radiation back into the “killing” zone to so intensify the destructive aspect of the UV radiation, and to prevent degradation of the material of the structure of the present invention by such radiation. The UV canister may be provided in a sealed, disposable unit so placed for quick replacement of the UV canister without the necessity of opening the sealed housing.
[0117] An alternate embodiment of the present invention incorporates an attractive closed housing which is considerably smaller than the basic embodiment of the invention. The invention is much lighter incorporating only the essential features necessary for producing and dispensing water. To enable a smaller housing and lighter device, the UV bulb is placed within the storage tank.
[0118] In another embodiment, the present invention is adapted for integration with a typical window air-conditioning unit. The evaporator of the air-conditioning unit coincides to the dew-forming surfaces of the present invention; the remaining components of this embodiment are fitted into an enlarged air-conditioning unit platform Alternatively, the apparatus is separately attachable to a window air-conditioning unit so as to enable use of the present invention with different models of window air-conditioners. Water is generated when the air-conditioning unit is in use.
[0119] To achieve water production in lower temperatures, the unit is allowed to freeze and thaw. Optimally, a computer-controlled flow rafter expansion valve is physically installed in addition to the typical expansion valve, but utilized in the alternative, to lower the pressure of the refrigerant in the evaporator and thereby encourage the freezing of the condensate. The refrigeration cycle is then quickly reversed to heat the dew-forming surfaces thereby thawing the frozen condensate. The thawed condensate drips into the collector, and water-bearing air is again passed over the dew-forming surfaces to be frozen again in cyclical fashion. In an alternative preferred embodiment, the thawing of the frozen condensate may be done by hot gas reversal, varying head pressures, and/or heaters.
[0120] If there is insufficient water production or if it is desired to attach the unit to a home refrigerator ice maker/chiller, a municipal water inlet line may be incorporated by quick disconnect fittings. Accordingly, municipal water pressurizes the refrigerator's dispensing system by passing municipal water through the NSF 53 filter and before reaching a storage tank. Further, a recirculation loop is employed to enable circulation of purified water into the UV canister to prevent bacteria build-up. Remote dispensers are connected to the apparatus by flexible tubing having quick disconnect fittings. The distance between the apparatus and its remote sensors may accordingly be varied by simply changing the length of flexible tubing. A sleeve encircles the flexible tubing such that the tubing may neatly and unobtrusively be attached to a wall. To prevent dust and pollen from entering the system, a High Efficiency Particulate Air (HEPA) filter or other electrostatic air filter is used. An air ionizer may be used to further assist in removing particulate matter from the intake air and treating the discharged air. Because the water generated is so pure, it may also be desirable to add minerals into the water. Accordingly, a mineralizing cartridge may be placed into the recirculation loop to achieve the desired mineral concentration.
[0121] The water generator/dispenser of the present invention fills a long-felt need for emerging countries and indeed many places in the world. The objects and advantages of the present invention include:
(a) providing a means for obtaining and dispensing potable water from a portable apparatus that is consistent with the decor of an office or home yet requires no permanent external plumbing or air duct; (b) providing an apparatus for heating and chilling potable water collected from the atmosphere; (c) providing an apparatus which can operate indoors or outdoors so as to be available to operate in remote areas; (d) providing an apparatus which can easily be assembled from sealed, ruggedized modules; (e) providing a cabinet apparatus with small or large wheels that is portable, i.e., can be rolled about on packed earth, pavement, bare floor, carpeted surfaces, or uneven surfaces; (f) providing an apparatus which-can be operated from a DC electrical supply by attaching solar-electrical generating panels or by variable-frequency, variable AC voltages, single- or 3-phase mins power, 50/60 Hz or AC electrical power generated from wind-driven generators; (g) providing an apparatus that has minimal chance of water contamination from VOCs, insects or rodents; (h) providing an apparatus of simple modular construction designed for operation over extended time periods without operator attention; (i) producing high-quality, purified water on-demand and/or at timed intervals by preparing the unit with medical-grade, NSF rated, 400 p.s.i. tubing and including an inert surface coating on the dew-forming surface; (j) producing liquid-water condensate at low air temperatures just above freezing by use of an air-heating strip, hot gas bypass, or utilization of a reversible refrigeration cycle; (k) dispensing potable water at a convenient height for adults or children or persons in wheelchairs; (l) producing contaminant-free potable water while running unattended in open air for extended periods of a month or more above freezing temperatures; (m) producing high-quality, potable water in varied environments such as offices, houses, or undeveloped locations; (n) providing a water generator/dispenser which is easily portable both indoors and outdoors; (O) providing options for dispensing potable water at three different temperatures, ambient, approximately 5 C cool and approximately 80 C warm; (p) producing potable water near or below the cost per gallon of bottled water; (q) producing high-quality potable water within latest ASHRAE and US federal standards for cooling and refrigerant apparatus; (r) providing a water generator/dispenser that can be easily transported by two adults using integral carrying handles; (s) providing a water generator/dispenser in which the exhausted air is filtered to remove dust, pollen, and airborne particles; (t) providing a water dispenser from which incoming air is charged with negative ions to facilitate particle separation, and negatively charge the discharged air; (u) providing a water generator/dispenser which will not produce or deliver condensate if the subsystem for killing microorganisms fails; (v) providing a water generator/dispenser having easily changed air filters; (w) providing a means without permanent plumbing to connect the apparatus to remote dispensers; (x) providing a means, without permanent plumbing, for connecting municipal water to the apparatus such that municipal water is automatically dispensed after purification if there is insufficient condensate; (y) providing a recirculation loop to periodically circulate treated water to prevent bacteria in response to a predetermined command, in a manner that allows no storage tank water to remain uncirculated; (z) providing an apparatus which is sized to facilitate moving, and mounting on a wall or upon a sink top; (aa) providing an apparatus with a combined condensate collector and storage tank; (bb) providing a means for protecting the apparatus from freezing; (cc) providing a sleeve for encircling exposed flexible tubing; (dd) providing a means for automatically activating and deactivating the pump upon the opening/closing of a dispenser; (ee) providing a means for automatically activating freezing and thawing cycles to produce maximum condensate for various marginal temperature/humidity conditions; (ff) providing audible and visual operational status/mode displays; (gg) providing an ozone generator for purifying and treating discharged air; (hh) providing a UV canister optimized for maximum bacteria destruction; (ii) providing a secure tube for introduction of medication into the extracted water; (jj) providing for a recirculation system that does not disturb medicated water; (kk) providing for an easily removed, easily cleaned storage tank with self-sealing gaskets; (ll) providing for multiple solid-core charcoal filters for removal of VOCs; (mm) providing for mineralization of the extracted water; (nn) providing a self-priming pump that will not destruct if run dry, of sufficient pressure capability to enable use of solid core filters; (oo) providing an integral heater for heating a room; (pp) providing high voltage ground fault interruption circuitry; (qq) providing low voltage components; (rr) providing for reduction in noise by use of multi-speed squirrel cage fans; (ss) providing an oxygenator for adding oxygen to extracted water; (tt) providing an air freshener means for scenting air reintroduced to a room; (uu) providing for child-proof safety valves; (vv) providing for both manually and electronically operated power switches; (ww) providing for fuses and/or circuit breakers; (xx) providing for easily cleaned electrical membrane switches; (yy) providing for insulation of cold lines to reduce or eliminate “sweat” or moisture buildup; (zz) providing a means for attachment and use of a typical refrigerator-mounted ice maker; (aaa) providing for reduction in noise by use of a hermetically sealed compressor cover; (bbb) providing for a gold-plated dew-forming surface for enhanced heat transfer, or other such metal for similar result; (ccc) providing for purification of water by vaporization; (ddd) providing for integration of a water-generating apparatus with a typical window air-conditioning unit; and
(eee) providing for sealed, disposable UV canister.
[0178] Still further objects and advantages will become apparent from a consideration of the ensuing description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0179] FIG. 1 is a schematic flow diagram of an embodiment of a system of the present invention to UV treat, filter, mineralize, medicinize/treat and further recirculate pressurized, potable water.
[0180] FIG. 1A is a schematic flow diagram of an embodiment of a system of the present invention to UV treat, filter, mineralize, medicinize/treat and further recirculate pressurized, potable water.
[0181] FIG. 2 is a detailed cut-away side view of a UV canister of the present invention, including UV bulb, mirrored surface, and electrical connections.
[0182] FIG. 3 is a view of a unit of the present invention depicting the housing, and the arrangement of various elements.
[0183] FIG. 4 is a depiction of a typical flow rafter expansion valve as utilized in the present invention.
[0184] FIG. 5 is a schematic flow diagram of an embodiment of a system of the present invention utilizing a reverse-osmosis membrane filter as a water filtration means where waste water from the membrane filter is discarded.
[0185] FIG. 6 is a schematic flow diagram of an embodiment of a system of the present invention utilizing a reverse-osmosis membrane filter as a water filtration means where waste water from the membrane filter is reclaimed.
[0186] FIG. 7 depicts a typical window air-conditioning unit having an integrated water generating and filtration system of the present invention including a membrane filter and pump, further adapted for intake of externally-supplied water to supplement condensate generation.
[0187] FIG. 8 depicts a typical window air-conditioning unit having an integrated water generating and filtration system of the present invention that includes a solid-core charcoal filter, a cold water tank with an integrated Peltier ice finger, and spigots for dispensing water.
[0188] FIG. 9 depicts the placement of an enlarged, assembled typical window air-conditioning unit, into which the present invention has been integrated, in a typical window.
[0189] FIG. 10 is a schematic diagram of an embodiment of a system of the present invention wherein cooled air from a refrigerant evaporator passes over a refrigerant condenser to remove heat from the condenser, and a hermetically sealed compressor cover reduces compressor noise and increases compressor efficiency.
[0190] FIG. 11 is a schematic flow diagram of a countertop-sized system of the present invention utilizing a reverse-osmosis membrane filter as a water filtration means.
[0191] FIG. 12 is a schematic flow diagram of an alternate preferred embodiment of the present invention utilizing a vaporization tank wherein impure external water may be vaporized for subsequent passage over the dew-forming surfaces.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0192] The elements and components of the present invention lend themselves most particularly to application and use in conjunction with a system of the type described in detail in U.S. Pat. No. 6,182,453, issued to Frank Forsberg and assigned to Worldwide Water, Inc., the entire disclosure of which is incorporated herein by reference. Nonetheless, it will be recognized by those skilled in the art how these elements and components may be applicable to use in conduction with a variety of other of such moisture extraction systems.
[0193] Table 1 below includes a listing of all special and standard nomenclature used in this specification; the column headed “Indicia” shows the reference number of each feature or element and the column headed “Figure” indicates the figure where the feature or element is first shown. The water collection and treatment processes of the present invention are generally shown in FIGS. 1, 1A , 2 , 5 , and 6 . FIG. 4 is a simplified depiction of a flow rafter expansion valve used for reduction of pressure of refrigerant in the low-pressure side of water-generation system so as to induce freezing of the evaporator. FIG. 7 depicts a water-generating apparatus, capable of intaking external water, integrated into a typical air-conditioning unit, having a membrane filter and Peltier ice finger. FIG. 8 depicts the air-conditioning unit embodiment utilizing solid-core charcoal filters in place of a membrane filter system. FIG. 10 shows a heat exchanger arrangement wherein both the cooled air passing from the refrigerant first evaporator 16 and the low-pressure refrigerant line to second compressor 53 assist in removing heat from the first condenser 4 , and the placement of cooling coils around first compressor within a hermetically sealed cover. FIG. 9 depicts the placement of a water-generating/window air-conditioning unit within a typical window. FIG. 11 portrays the elements of a sink-top sized water-generating apparatus. FIG. 3 demonstrates the position of wheels relative to the housing. FIG. 6 depicts a flow diagram for a membrane filter waste water recycling system.
[0194] As may be seen in FIG. 3 , the working components are enclosed in a housing 1 with a top cover, four vertical side panels and a base. The housing may incorporate a bracketed opening in the front cover panel opening through which is inserted an air filter 119 . The housing may further incorporate a front wall alcove opening and assembly 122 consisting of an alcove shell, grid and waste water receptacle. Above the alcove is a low-light-level lamp 123 , or “night light”. The alcove may also contains a fluid delivery controls 34 & 35 for dispensing water. One panel of the housing has an inlet opening into the air filter 119 . One panel of the housing provides an outlet port 124 for air exhaust. This opening has an insect-resistant screen (not shown) on the interior of the housing outlet port 124 . An ozonator 125 is provided to further remove air-borne particles and treat the air. A keypad 134 located atop the housing provides a user of the present invention operational control over the present invention.
[0195] For added safety, ground fault interruption circuitry is utilized to protect both apparatus users and the high voltage compressors, heaters, and ballast transformers. The remaining components, such as pump, solenoid valves, indicator lights, etc., are low voltage (less than 35 V, and optimally between approximately 12 V and approximately 24 V). Fuses and circuit breakers protect all electrical components.
TABLE 1 Descriptive Nomenclature and Indicia Indicia Description, function FIG. 1 housing, case, cabinet 10 2 fan assembly, multi-speed intake, first evaporator 10 3 fan assembly, multi-speed intake, first condenser 10 4 first condenser, refrigerant, water-generating 10 5 collector, condensate 1 6 tube, condensate collector to UV canister 1 7 canister, UV 1 8 tube, vent 1 9 sensor, UV canister lower 1 10 sensor, UV canister upper 1 11 tube, sealed, UV canister egress, fluid transfer 1 12 tube, sealed, storage tank to UV canister ingress, 1 recirculation 13 bulb, UV 1 14 wire, power transmission, ballast 1 transformer to UV bulb 15 transformer, ballast, UV bulb 1 16 first evaporator, refrigerant, water-generating 1 17 cap, canister 1 18 holder, UV bulb 1 19 surface, mirrored, UV canister 1 20 switch, relay, pump 2 21 wire, power transmission, switch relay 1 pump to upper UV canister sensor 22 wire, power transmission, switch relay 1 pump to lower UV canister sensor 23 solenoid, external water intake, default-closed 1 24 valve, check, external water intake 1 25 tube, sealed, cold water tank 1 to hot water tank 26 tube, sealed, stainless steel, storage tank 1 to cold water tank 27 tank, storage 1 28 gasket, self sealing, hot water 1 29 gasket, self sealing, cold water 1 30 tank, hot water 1 31 element, heating, hot water tank 1 32 tank, cold water 1 33 coil, second evaporator refrigerant, 1 cold water tank chilling 34 spigot, child-proof, hot water dispensing 1 35 spigot, cold water dispensing 1 37 lid, storage tank 1 38 gasket, storage tank 1 39 clasp, locking, storage tank lid 1 40 switch, on/off, hot water tank heating element 1 41 pump, self-priming 1 42 filter, solid-core charcoal 1 43 canister, mineral replacement 1 44 quick-disconnect, female, external water 1 45 tube, external/internal water dual-purpose 1 46 quick-disconnect, male, external water inlet solenoid 1 engaging 46A fitting, typical household faucet 1 47 insulation, tank 1 48 switch, float, storage tank water level 1 49 switch, float, storage tank water level indicator light 1 50 connector, storage tank to fluid transfer tube 1 51 tube, medication/vitamin 1 52 first compressor, water-generating 10 53 second compressor, cold-water chiller 10 55 tube, water system to refrigerator ice-maker 1 55A quick-disconnect, solenoid engaging, 1 external water inlet 55B quick-disconnect, refrigerator ice-maker engaging 1 56 port, tranlucent, UV visual indicator 1 57 line, cold, refrigerant, cold water tank coil entering 1 58 line, cold, refrigerant, cold water tank coil exiting 1 59 solenoid, recirculation, default closed 1 60 valve, manual bleeder, recirculation 1 61 sensor, condensate collector overflow 1 62 screen, sediment 1 63 sensor, storage tank, low water 1 64 pre-filter, external water 5 65 plenum, ambient air 10 66 heat exchanger 10 67 tube, waste water outlet 5 68 pump, booster, membrane filter 5 69 tube, membrane filter to storage tank 5 70 filter, membrane, reverse osmosis 5 71 tube, external water source 1 72 solenoid, waste water outlet, default closed 5 73 tube, external water to membrane filter 5 74 second condenser 10 75 switch, timer, external water intake 5 76 flow restrictor, waste water 5 77 fan, multi-speed, second condenser 10 78 air conditioning unit, typical window-mounted 7 79 quick-disconnect, waste water outlet 5 80 switch, pressure, waste water 5 81 tube, waste water drain quick-disconnect 5 83 coil, cooling, second evaporator 10 84 fitting, tee, water tube 1 85 cover, first compressor, hermetically sealed 10 88 valve, expansion, flow rafter 4 89 cabinet, countertop 11 90 insulation, noise abatement 10 91 spigot, ambient water dispensing 8 92 tube, waste water discharge 11 93 ice finger, Peltier 8 94 tank, ice finger holding 8 95 tube, fluid transfer, storage tank to ice 11 finger holding tank 98 LED 1 102 cover, enlarged platform 7 103 platform, enlarged, typical window 7 air-conditioning system 104 tube, UV canister drain 8 105 valve, UV canister drain 8 107 tank, recycle 6 110 tank, vaporization 12 111 solenoid, recycle 6 112 sensor, upper float 6 113 sensor, lower float 6 114 valve, check 6 115 filter, sand/sediment 6 116 post-filter, membrane filter 6 117 valve, check, post-membrane filter 6 118 canister, water level 1A 119 filter, air 10 122 alcove 3 123 light 3 124 port, outlet, exhaust air 3 125 ozonator 3 126 oxygenator 3 127 pest control device, ultrasonic 3 128 heater, electric 3 129 gold plating 1 130 sensor, upper vaporization tank 12 131 sensor, lower vaporization tank 12 132 tube, external water to vaporization tank 12 133 element, second heating 12 134 keypad 3 136 filter, air 3 138 panel, display 3
[0196] Operation of the present invention, as in FIG. 1 , is initially controlled by a manually operated on/off switch 75 located on the housing. An electronically-operated on/off switch may be utilized in conduction with to turn off visual displays, or utilized alternatively to the manually operated on/off switch A multi-speed fan control switch (not shown) is adjacent to the on/off switch on the housing.
[0197] As may be best seen in FIGS. 1 and 10 , air entering the housing 1 first passes through a replaceable air filter 119 into a plenum 65 and across an optional, self-contained ionizing device (not shown). Air then is drawn across the film-coated, dew-forming surfaces of first evaporator 16 by a multi-speed intake fan assembly 2 , which is controlled by the multi-speed fan control switch Liquid condensate flows by gravity into a condensate collector 5 , and then flows into the first end of a UV canister 7 through a tube 6 . A vent tube 8 permits air in the UV canister 7 to be displaced by the liquid condensate (water). A sensor 61 is provided just below the rim of the condensate collector 5 to disable power to the refrigerant first compressor 52 , thereby preventing first evaporator 16 from cooling the ambient air to its dewpoint to overflow the condensate collector 5 . First condenser 4 is provided to remove heat extracted from the condensing water. Should airflow from first evaporator 16 over first condenser 4 insufficiently remove heat from first condenser 4 , the low-pressure refrigerant line from a second compressor 53 may-be placed in thermally-conductive relationship with first condenser 4 so as to remove additional heat. As may be seen in FIG. 1A , an alternative preferred embodiment provides for the UV canister 7 to be further sealed and disposable, and placed in a location convenient for changing of the UV bulb 13 .
[0198] The UV canister 7 is designed so as to maximize the bacteria-killing effect of an optimal frequency of ultraviolet radiation, as may be seen in FIG. 2 . Accordingly, the interior surfaces 19 of the canister are coated with reflective material, and the UV canister 7 is shaped around a UV bulb 13 so as to direct the liquid condensate into the optimum zone of bacteria destruction. The UV bulb 13 is held by UV bulb holder 18 and is powered by a ballast transformer 15 , to which it is electrically connected by wires 14 . This UV bulb 13 may be changed by removal of the canister cap 17 . A pump 41 may be activated according to the volume of water within the UV canister 7 by means of a lower sensor 9 and an upper sensor 10 . The lower sensor 9 and upper sensor 10 are both electrically connected to a pump relay switch 20 by wires 22 & 21 . The pump relay switch 20 circuit closes and allows power to the pump 41 when both lower sensor 9 and upper sensor 10 are immersed in water. The pump 41 provides extra-gravitational pressure sufficient to pull water from the second end of the UV canister 7 through a sediment screen 62 . The UV canister 7 , sediment screen 62 and pump 41 fluidly communicate via a fluid transfer tube 11 . A check valve 24 is placed serially with respect to the pump 41 and UV canister 7 to prevent reversal of water flow when the pump 41 is deactivated. A transparent port 56 is built into the UV canister 7 to serve as an UV indicator. As shown in FIG. 1A , the alternative preferred embodiment comprising a sealed, disposable UV canister 7 provides a separate water level canister 118 to house the sensors 9 and 10 for activation of the pump 41 .
[0199] The pump 41 is preferably self-priming. The pump 41 forces water through a solid-core charcoal filter 42 , and an mineralizing cartridge 43 into a storage tank 27 . The pump 41 , solid-core charcoal filter 42 , mineralizing cartridge 43 for adding minerals to the purified water, and a storage tank lid 37 fluidly communicate via a fluid transfer tube 11 . The storage tank lid 37 is further attached to the storage tank 27 by releasable, lockable clasps 39 , and is sealed to storage tank 27 by means of a gasket 38 sandwiched between storage tank lid 37 and storage tank 27 . The storage tank lid 37 is provided with an overflow float switch 48 that will disallow power to the refrigerant compressor (not shown) when the level of the water in the storage tank 27 approaches the attached storage tank lid 37 , thereby stopping water condensation on first evaporator 16 . The storage tank lid 37 is further provided with a second overflow float switch 49 that will allow illumination of indicator light 98 located on the display panel 138 in the event that the level of the water in the storage tank 27 approaches the attached storage tank lid 37 .
[0200] Water from the storage tank 27 flows by gravity through a self-sealing gasket 29 and through a stainless steel tube 26 into a cold water tank 32 . The water may then be chilled within the cold water tank 32 to a temperature within a range of approximately 4 C to approximately 12 C by the low-pressure second evaporator refrigerant coil 33 coiled around the cold water tank 32 and fluidly connected to refrigerant second compressor 53 at an cold-water tank 32 refrigerant coil 33 ingress line 57 and an cold water tank 32 refrigerant coil 33 egress line 58 . The water may be further gravity dispensed outside the housing 1 by means of a spigot 35 . Energy dissipation from cold water tank 32 is decreased by insulation 47 . Additionally, a securable tube 51 is sealingly connected to the cold water tank 32 through the surrounding insulation 47 to permit direct introduction of medicines and/or vitamins into the cold water tank 32 . Insulation (not shown) is placed around the secondary cooling device cold refrigerant lines to reduce or eliminate moisture “sweating” and buildup. Such insulation may similarly be placed on both hot and cold refrigerant lines to reduce unwanted heat transfer. Second condenser 74 provides an additional means, air-cooled by fan 77 , for discharging heat from second compressor 53 .
[0201] Water from the cold water tank 32 flows by gravity through a self-sealing gasket 28 and through a tube 25 into a hot water tank 30 . The water may then be heated within the hot water tank 30 to a temperature within a range of approximately 75 C to approximately 91 C by providing electrical power via switch 40 to heating element 31 . The water may be further gravity dispensed outside the housing 1 by means of a child-proof spigot 34 . Energy dissipation from hot water tank 30 is decreased by insulation 47 . The temperature of both hot and cold water is displayed on a display panel 138 .
[0202] As in FIGS. 1 and 3 , for the preferred embodiment, ambient temperature water is dispensed from the hot water tank 30 via the child-proof spigot 34 when the heating element 31 is not provided with electrical power. A display panel 138 connected to temperature sensing means (not shown) is provided to display the temperature of the water in the hot water tank 30 . Enabling the selective powering of the heating element 31 can make maintenance of nearby cold-water tank 32 temperatures more efficient. Disposable liquid containers, e.g., paper cups, suitable for cold water, are provided from attached dispenser (not shown) mounted on the side of the housing.
[0203] The liquid condensate is passed through an oxygenator 126 prior to introduction into the storage tank 27 , in order to healthfully introduce oxygen into the water. A quick-disconnect tube 45 may be attached at quick-disconnect 44 to direct water from a full storage tank 27 into external containers.
[0204] Water in the storage tank 27 is recirculated through the UV canister 7 through connector 50 and a fluid transfer tube 12 . Placed serially in fluid communication via fluid transfer line 12 between the storage tank 27 and the UV canister 7 is a solenoid valve 59 that prevents flow of water from the storage tank 27 to the UV canister 7 unless electrical power is supplied to the solenoid valve 59 . This prevents water in storage tank 27 from draining if electrical power to the apparatus fails. Also placed serially in fluid communication via fluid transfer line 12 between the storage tank 27 and the UV canister 7 is a bleeder valve 60 that may be manually adjusted to regulate the volume of water flowing from storage tank 27 to the UV canister 7 .
[0205] A major improvement in the design of the present invention is the provision of a computer-controlled flow rafter expansion valve 88 , as in FIG. 4 , physically installed in addition to the typically-provided refrigeration expansion valve, but utilized in the alternative to encourage freezing of the condensate on the first evaporator 16 when the ambient air is at a low temperature but is still humid. The present invention is further enabled to reverse the refrigerant flow, thus heating the first evaporator 16 to quickly-thaw the frozen condensate to permit it to drip into the condensate collector 5 . This cycle may be reversed quite rapidly to permit water to be extracted in atmospheric conditions, whereas a non-reversed refrigeration cycle will not function to extract water from ambient air. Devices in the prior art merely shut down the refrigerant cycle to allow the frozen condensate to thaw, rather than actively inducing freezing and thawing by use of a flow rafter expansion valve and reversal the refrigeration cycle. The freezing and thawing cycle is activated by an electronically-timed and activated switch circuitry (not shown), which adjusts the cycle timing to atmospheric conditions. Condensate collection may be increased in a number of ways, including use of an enlarged first evaporator 16 , increased airflow over the first evaporator 16 , and increased temperature of air flowing over the first evaporator 16 . Accordingly, an electrical heater 128 as in FIG. 3 may be placed upstream of first evaporator 16 to heat the low temperature ambient air passing over first evaporator 16 . Heat from first condenser 4 is removed by air passing through the first evaporator 16 surfaces and thence over the first condenser 4 surfaces. For cooling of the first condenser 4 surfaces when the freeze/thaw cycle of the evaporator is active and the first evaporator 16 is clogged with ice, a separate multi-speed fan 3 pulls ambient air through air filter 136 for passage over first condenser 4 , as in FIG. 10 . Further provided for the purpose of cooling first condenser 4 is the low pressure refrigerant line (shown as heat exchanger 66 ) from the second compressor 53 in thermally conductive relationship to first condenser 4 .
[0206] The apparatus is equipped to accept liquid water from an external source, such as a municipal water supply, as in FIG. 5 . Accordingly, fluid transfer tube 11 is fitted with a tee 84 to permit fluid communication of the apparatus with the external water source. A solenoid valve 23 is provided to prevent water flow through the external water source side of the tee 84 absent electrical power by way of low water sensor 63 provided at the inside bottom of the storage tank 27 . At the external water source side of the solenoid valve 23 is a female quick-disconnect fitting 44 to permit easy coupling and uncoupling of external water source tube 71 . A more convenient alternative embodiment provides for a dual-purpose tube 45 adapted with a female faucet fitting 46 A at one end for coupling the tube 45 with a standard household faucet and a male quick-disconnect fitting 46 for coupling the tube 45 with the female quick-disconnect fitting 44 . The externally-supplied water is passed through the tee 84 through the solid core charcoal filter 42 via the fluid transfer tube 11 in the direction of the storage tank. The check valve 24 prevents water from flowing toward the UV canister 7 .
[0207] In an alternative preferred embodiment, the externally-supplied water may be directed through a reverse-osmosis membrane filter 70 , as in FIGS. 5 and 11 , which in turn simultaneously directs filtered water through fluid transfer tube 69 into storage tank 27 and waste water through fluid transfer tube 67 and drain tube 81 connected to the system at quick-disconnect 79 into a drain for disposal. Quick disconnect fitting 79 is provided to permit rapid coupling and uncoupling of the wastewater drain tube 81 . In this membrane filter 70 embodiment, a solenoid valve 23 is provided to prevent water flow through the fluid transfer tube 73 to the membrane filter 70 absent electrical power by way of low water sensor 63 provided at the inside bottom of the storage tank 27 . At the external water source side of the solenoid valve 23 is a female quick-disconnect fitting 44 to permit easy coupling and uncoupling of external water source tube 71 . A fluidly communicating screen 64 is further serially provided between the solenoid valve 23 and a booster pump 68 to remove suspended particulates from the external water. A fluidly communicating sand/sediment filter 115 and pre-filter 64 are further serially provided between the booster pump 68 and membrane filter 70 to remove heavy metals and VOC's from the external water. The waste water from the membrane filter 70 is directed via a fluid transfer tube 67 through a flow restrictor 76 to assist in maintaining a constant pressure within the membrane filter 70 , and thence into the drain.
[0208] Alternatively, the waste water from the membrane filter 70 ray be recycled, as in FIG. 6 . In this embodiment, an additional recycle tank 107 is provided in serial fluid communication with the booster pump 68 , through which external water is directed after passage through a solenoid 23 and a solenoid 111 . Maximum water level in the recyle tank 107 is limited by an upper float sensor 112 to prevent the recycle tank 107 from overfilling, and minimum low water level is sensed by a lower float sensor 113 . When the water level in the storage tank 27 decreases sufficiently to close the circuit of the sensor 63 , the sensor 63 sends an electrical signal to a solenoid 111 to permit water to flow through the solenoid 111 into the recycle tank 107 . Simultaneously, an electrical signal is sent to an external means (not shown) for indicating the status of the sensor 63 . An operator of the present invention may then manually operate the switch 75 to send an electrical signal to the solenoid 23 to permit water to flow through it. When the water level in the recycle tank 107 rises sufficiently to close the sensor 112 circuitry, an electrical signal is sent both to the solenoid 111 to shut off external water flow and to activate the booster pump 68 . The booster pump 68 draws water through the screen 62 and directs water through the sand/sediment filter 115 and pre-filter 64 into the membrane filter 70 . The membrane-filtered water is then directed through tube 69 , post-filter 116 , and post-filter check valve 117 into the storage tank 27 , while the waste water from the membrane filter is simultaneously discharged through wastewater outlet tube 67 through the waste water flow restrictor 76 and check valve 114 back into the recycle tank 107 for re-entry into booster pump 68 for further membrane filtration. The cycle of waste water returning to the recycle tank 107 continues until the water level in the recycle tank decreases sufficiently to close the circuit of the lower float sensor 113 , which sensor 113 in turn de-activates the booster pump 68 . Only when the lower float sensor 113 is closed will the booster pump 68 de-activate; the opening of the upper float sensor 112 by decreasing water level is the means by which the solenoid 111 is re-opened to permit additional external water to flow into the recycle tank 107 , thereby raising the water level to engage the sensor 112 to thus activate the pump 68 . Further manual operation of the switch 75 will close the solenoid 23 , thus preventing additional water from flowing through the solenoid 111 , and the waste-waster recycling process will continue until the water level in the recycle tank 107 decreases sufficiently to shut off the booster pump 68 . The float switch 48 in the Storage tank 27 serves as a master electrical override, shutting down the pump 68 and closing the solenoid 111 when the water level in the storage tank 27 rises sufficiently to engage the float switch 48 .
[0209] A further alternative waste water recycling embodiment provides for automatic introduction of external water into the recycle tank 107 . In this alternative embodiment, the apparatus is semi-permanently connected to an external water source, and the switch 75 is initially operated to open the solenoid 23 . Thereafter, the filling of the recycle tank 107 , recycling of wastewater, and discharge of pure water into the storage tank 27 takes place as described automatically, without any need to further operate the switch 75 .
[0210] In an alternative preferred embodiment not having a membrane filter, impure water is purified by vaporization, as shown in FIG. 12 . It upon inspection, the storage tank 27 is empty, the switch 75 may be operated so as to open the solenoid 23 to permit impure externally-supplied water to be sent from an external water source through a tube 133 directly into a vaporization tank 110 for vaporization by the second heating element 133 . Operation of the switch 75 simultaneously permits electrical power to flow to the second heating element 133 . The vaporization tank- 110 is positioned with respect to the first evaporator 16 such that the steam from the vaporization tank 133 is passed over the dew-forming surfaces of the first evaporator 16 for condensation and passage into the condensate collector 5 . The condensate is then sent through the UV canister 7 and other system components as in the preferred embodiment. An upper sensor 130 and a lower sensor 131 provide a means for controlling the water level within the vaporization tank 110 . When the external water fills the vaporization tank 110 sufficiently to engage the upper sensor 130 , the upper sensor 130 sends an electrical signal to close the solenoid 23 , thus shutting off the external water. When the water level in the vaporization tank 110 decreases sufficiently to engage the lower sensor 131 , the lower sensor 131 sends an electrical signal to open the solenoid 23 , thus permitting water to flow into the vaporization tank. The cycle of filling the hot water tank 30 and vaporizing impure water may be continued until manually shut off by operation of the switch 75 so as to close the solenoid 23 and remove electrical power from the second heating element 133 . If not the solenoid 23 is not closed by manual operation of the switch 75 , the water level in the storage tank 27 will rise to engage the override sensor 48 , thus closing the solenoid 23 and removing power from the second heating element 133 .
[0211] The apparatus is further equipped to supply liquid condensate from the apparatus to a typical refrigerator ice-maker. Accordingly, a tube 55 is adapted with an ice-maker engaging quick-disconnect fitting 55 B to permit coupling of the tube 55 with the refrigerator ice-maker, and a male quick-disconnect fitting 55 A for coupling of the tube 55 with the female quick-disconnect fitting 44 . Solenoid 23 is provided with electrical power from a timer-controlled power switch 75 to permit flow of water through the external water source side of the tee 84 . The pump 41 is activated to push water through the tee 84 into the ice-maker. The water is discouraged from flowing through the fluid transfer tube 11 into, the storage tank 27 by an intervening solid core charcoal filter 42 and an mineralizing cartridge 43 .
[0212] Noise from the present invention is abated primarily by two features: multi-speed squirrel cage fans 2 & 3 and a hermetically sealed compressor cover 85 further insulated by insulation 90 , as may be seen in FIG. 10 . The present invention permits use of such a sealed compressor cover 85 by utilizing the extra cooling capacity of the water chiller second evaporator cod 33 . A section of the refrigerant line coil 83 of second evaporator cod 33 is wrapped around first compressor 52 to absorb heat generated by first compressor 52 , thus permitting a compressor cover 85 to sealingly surround first compressor 52 without causing the first compressor 52 to overheat. In an alternative preferred embodiment, a separate fluid-carrying cod may be wrapped around the first compressor 52 for transportation of heat from the first compressor 52 to an external radiator (not shown), much like that used for an automobile engine.
[0213] As may be seen in FIG. 11 , a smaller, sink-top version of the apparatus generally includes all of the benefits of the larger embodiment inside of a smaller cabinet 89 . A heat exchanger 66 is provided in conjunction with a first evaporator 16 over which air is passed to condense water. The condensate gravity feeds into a condensate collector 5 , and then drains via a fluid transfer tube 6 into the UV canister 7 . When sufficient condensate has entered the UV canister 7 , a pump 41 is activated to direct water through a series of filters 64 & 42 and a mineralization canister 43 into a storage tank 27 . From the storage tank 27 , ambient temperature water may be dispensed through a spigot 91 . For cold water dispensation from a spigot 35 , condensate flows through the tube 95 into a tank 94 containing a Peltier-effect ice finger 93 to chill the water, which ice finger effect and use is described U.S. Pat. No. 6 , 182 , 453 and incorporated herein by reference. The water level in the storage tank is generally controlled by a high water level switch 48 , which removes electrical power from either the first compressor 52 to cease water generation or the booster pump 68 , and a low water level switch 63 , which can open a solenoid 23 to permit external water to flow into the system. External water is introduced into the system through a tube 45 (not shown in FIG. 11 ) attached by mating quick-disconnect fitting 46 to fitting 44 . The other end of tube 45 attaches to a typical household faucet via a fitting 46 A A timing switch 75 may be used to open a solenoid valve 23 and provide power to the booster pump 68 to direct water into the membrane filter 70 . The external water is directed into the storage tank 27 via tube 69 from the membrane filter 70 . Waste water flow through the discharge tube 92 from the membrane filter 70 is controlled by a flow restrictor 76 to maintain water pressure in the membrane filter 70 . When the water flowing from the membrane filter 70 fills up the storage tank 27 , the high-water level switch 48 overrides the switch 75 to cut off electrical power to the solenoid 23 and the booster pump 68 . The solenoid 59 remains open so long as electrical power is supplied to the apparatus; when such power is cut off, it closes, thereby preventing drainage of the storage tank 27 . By opening a flow controller 60 and activating the pump 41 , water can begin circulating from the full storage tank 27 through the UV canister 7 , filter series 64 & 42 , the mineralization canister 43 , and the pump 41 back into the storage tank 27 , all via fluid transfer tubes 11 & 12 . The volume of circulation flow is controlled by a flow controller 60 . A solenoid valve 59 is provided to prevent draining of the storage tank 27 in the event that electrical power to the apparatus is cut off. An alternative sink-top embodiment provides for placement of the UV bulb 13 within the storage tank 27 for space conservation (not shown in Figures).
[0214] The present invention may be further integrated into a window air-conditioning (A/C) system 78 , as in FIGS. 7, 8 and 9 . In this embodiment, the evaporator of the A/C unit coincides with the dew-forming surfaces of the first evaporator 16 of the present invention. The embodiment of FIG. 7 utilizes a membrane filter 70 for filtering the condensate from the A/C evaporator after it passes through the UV canister 7 . This embodiment is also adapted to receive externally-supplied water. The embodiment of FIG. 8 utilizes a solid-core charcoal filter 42 for filtering the condensate from the A/C evaporator after it passes through the UV canister 7 . The condensate in both embodiments is then passed into the storage tank 27 for further external dispensation through a spigot 91 or direction into a tank 94 for chilling by Peltier ice finger for external dispensation through separate spigot 35 . Recirculation as provided in the free-standing apparatus is also provided in the A/C unit embodiments. These air-conditioning unit embodiment may be adapted to fit within an enlarged air conditioning unit platform 102 to be moved with the platform 102 , or may simply be attachable to a window air-conditioning unit 78 and moved to a different such unit 78 as desired. Before movement of the embodiment to a different A/C unit 78 , the UV canister 7 may be drained via drain tube 104 through a drain valve 105 .
[0215] Additional Features. The housing is fitted with an ozone generator 125 adjacent to the departing air stream to further improve air quality. The housing also contains a warbling, ultrasonic pest-control device 127 which operates continuously. To provide for mobility of alternative embodiments of the apparatus, four casters or rollers (not shown) suitable to the weight and size of the present invention may be affixed to the four corners of the lower side of the base of the housing. To further provide for mobility of alternative embodiments of the present invention over uneven surfaces, two enlarged wheels of up to 5 inches diameter may be affixed to two adjacent corners of the lower side of the base of the housing. Carrying handles (not shown), suitable to the weight and size of the present invention, may also be fixed, one on each side of the housing at a height appropriate for transport by two adults.
[0216] For further health benefit, the heat absorption systems of the present invention are assembled by use of lead-free solder to prevent contamination of the condensate with heavy metals.
[0217] As described in U.S. Pat. No. 6,182,453 and incorporated herein by reference, the system of the present invention is provided with various devices for automatically sequencing control operations, including integrated circuits and microprocessors adapted to receive sensor signals and activate operational functions, including safety-interlock functions, and related system components, all operations being activated according to a predetermined, logical control sequence. The present invention is further provided with devices for monitoring and/or visually displaying integrity, including sensors for on/off operation, ambient air humidity, fluid flow rate, fluid level, fluid pressure, head pressure, current flow, radiation intensity, operational frequency, temperature, elapsed time, cumulative flow volume, presence of small quantities of spilled liquid water, open or closed solenoid valve status, open or closed status of external water input ports, open or closed status of external water-delivery ports, status of emergency water-input ports, and status of safety locks.
[0218] The present invention is enabled to operate as an air conditioning apparatus. That is, the fans and electrical heater subsystem of the present invention may be operated independently of the water-generating subsystem to heat the ambient air of a room.
Operation of the Present Invention
[0219] Incoming air is filtered by a known depth-screen filter assembly or an electrostatic filter assembly. If desired for operation in a home or office, an ozone generator can be included; this addition allows the present invention to function as a charged-particle generator and room-air purifier. Additionally, an oxygenator can be included to introduce oxygen into the purified water.
[0220] Condensate collected from the air flow across the first evaporator flows downward by gravity to a collector for condensate and is further conducted by gravity flow into a UV canister. In this UV canister is a set of sensors which actuates the pump when the UV canister is full. The condensate is conducted through the UV canister for exposure to an ultraviolet germicidal light from a UV bulb. Recirculation of the condensate through the UV canister and VOC filter is accomplished by activating the recirculation pump at least once at predetermined time intervals in the range 1-12 hours, for a predefined flow or time duration in the range 1-50 times the tank volume or 1-200 minutes at a specific flow rate. By this repeated process, water is intermittently and continually recirculated across the VOC filter and UV portions of the purification circuit whenever the water generator is in use. The flow duration may be defined by the volume circulated or by time. An indicator port on the exterior of the UV canister visible through the housing confirms proper operation of the UV canister 7 .
[0221] The condensate is pumped under positive pressure through a VOC purification filter assembly capable of NSF-53 purification and then pumped into a storage tank made of plastic or stainless steel as is common for food-service contact. The cold-water tank, into which condensate is directly gravity fed from the storage tank, may be encased by a form-fitted insulation jacket made of a nontoxic material, such as polymer foam. The water from the cold-water tank further flows by gravity into the hot-water tank, which has a child-proof fluid delivery spigot The cold-water tank likewise has a fluid delivery spigot. The storage tank in one embodiment is removable for cleaning. The fluid delivery spigots are at an ergonomically-correct level above the floor, making water easily accessible for children or persons in wheelchairs. An holder (not shown) for disposable cold-liquid containers is shown in close proximity to the fluid delivery controls.
[0222] The storage tank is provided with a storage tank lid which may be attached to the storage tank by means of releasable, lockable clasps. A gasket provides a seal between the storage tank lid and the storage tank. The storage tank is further sealed to the cold-water tank inlet tube by means of a self-sealing gasket. The recirculation fluid transfer tube is attached to the storage tank via a quick-disconnect fitting. These features permit the storage tank to be easily lifted away from the apparatus for cleaning.
[0223] Chilling of the collected purified water in the cold water tank to a nominal temperature of 5 C is accomplished by adding a secondary cooling device, second evaporator. The coil of second evaporator is placed between the exterior of the cold water tank and the surrounding insulation.
[0224] Heating of the water to a nominal temperature of 75 C is accomplished by heating element inside of the hot-water tank. Water is gravity-fed into the hot water tank from the cold-water tank through a tube. Hot water is dispensed through the child-proof fluid delivery spigot, which is connected to the hot water tank.
[0225] In the bottom of the storage tank is a low condensate switch. If there is low water in the storage tank, an electrical signal is either sent to the pump or, if the apparatus is connected to an external water source, sent to the inlet water solenoid which opens, letting water pressurize the system The external water passed through a solid core filter, or alternatively through a reverse-osmosis membrane filter, before introduction into the storage tank. Thereafter, condensate from the storage tank or municipal water can be automatically recirculated through the UV canister, and waste water from the membrane filter is recycled for repeated membrane filtration The water level float switch turns off the water flow when the water level in the storage tank rises sufficiently to trigger it. Remote dispensers as well as municipal water sources are attached by quick-disconnect fittings.
[0226] For purification of water by vaporization, external water is permitted to flow into the vaporization tank until a sensor near the inside-top of the vaporization tank sends a signal to a solenoid to cut off the flow of water. The heating element within the vaporization tank vaporizes the water, which then passes over the dew-forming surfaces. Condensation drips into the condensate collector and into the water treatment stages of the apparatus. When the level of water within the vaporization tank decreases sufficiently to trigger the sensor near the inside bottom of the vaporization tank, the solenoid opens to allow more water into the hot water tank. The cycle of filling the vaporization tank and emptying it by vaporization of the water is continued until either manually ended, or shut off by the storage tank override/overflow switch.
[0227] During unfavorable times for producing condensate, the first compressor is enabled to activate until it frosts over and then deactivate until the frost melts, producing condensate. When there is sufficient humidity as indicated by a humidistat but low temperatures, the first evaporator will freeze. In particular, the typical refrigeration expansion valve is bypassed, and the flow rafter is utilized to further decrease the pressure in the low-pressure cold refrigeration line. Upon freezing of the evaporator and condensate, the refrigerant cycle is reversed, thus rapidly heating the evaporator-turned-condenser so as to melt the condensate. When the thawed condensate has passed into the condensate collector, the refrigeration cycle reverses again to cool the evaporator and freeze condensate collected from passing air. This cycle is computer-controlled for optimal water production. In this way, water may be generated at a higher rate than that produced by use of hot-gas bypass or mere on-off-on action of the compressor. Further, during extended absences, recirculation switch (not shown) activates recirculation of water from the storage tank through the UV canister and the water filter as timed by pump timer (not shown). The present invention is connected to various dispensers remotely located through tee connectors and quick disconnect fittings. An easily cleaned, unitary surface, operation control panel contains various indicator displays electrically or audibly indicating system operation.
[0228] Further, a humidity/temperature water production chart (not shown) showing the expected water production at various combinations of temperature and humidity can be created according to testing conducted in a controlled environmental test chamber. This graph can then be posted on the outside of the housing to show expected water production. Claims:
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A portable, potable-water generator for producing high-purity liquid water by condensation of water vapor from ambient air. The generator ( 125 ) employs an air filter ( 119 ) to remove particulates and aerosols from the incoming air. An enclosed heat absorber cools the filtered air to its dew point and collects droplets of condensate into a condensate collector ( 5 ). Before discharge, the collected dew is treated in a bacteriostat loop to destroy adventitious living organisms and to filter out undesirable and dangerous contaminants. A recirculation loop provides the ability to recirculate stored condensate, including during periods of inactivity. Further, quick disconnect fittings ( 55 b ) and variable length flexible tubing allows use of the invention to serve remote dispensers and/or appliances and allow use of municipal water treated through the apparatus in low condensate situations.
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[0001] This application claims priority from U.S. Provisional Ser. No. 60/773,003 filed on Feb. 14, 2006, the entire contents of which are incorporated herein by reference.
BACKGROUND
[0002] The present application is directed to brake-by-wire braking systems and, more particularly, to full brake-by-wire braking systems with a hydraulic fail-safe.
[0003] Modern vehicles, including electric vehicles, hybrid vehicles and traditional petroleum-powered vehicles, may include numerous electrical and computerized systems, such as brake-by-wire braking systems. Brake-by-wire braking systems typically replace the traditional mechanical and hydraulic fluid connection between the brake pedal and the braking units (e.g., disk or drum brakes) with an electrical connection (i.e., brake-by-wire). The electrical connection typically communicates user input signals from the brake pedal to a control unit and the control unit in turn controls the operation of the brake units to apply or release a braking force.
[0004] A disadvantage associated with brake-by-wire braking systems is the risk that a single failure loss of electrical power will disable the brake system, leaving the vehicle operator with no means for stopping and/or controlling the vehicle. Attempts have been made to reduce the risks associated with an electrical failure by providing redundant or multiple independent electrical systems complete with separate battery reserves to serve as back-up systems in the event of an electrical system failure. However, such redundant electrical systems substantially increase manufacturing and system costs and typically increase the overall complexity of the electrical system.
[0005] Accordingly, there is a need for a brake-by-wire braking system having a hydraulic fail-safe feature that can reduce manufacturing and system costs and electrical system complexity, as well as provide a simple, robust and proven source of braking energy in the event of electrical system malfunction.
SUMMARY
[0006] In one aspect, the disclosed brake-by-wire braking system may include a braking unit, an electro-hydraulic actuator in fluid communication with the braking unit by way of a first fluid path, a master cylinder in fluid communication with the braking unit by way of a second fluid path, a normally open solenoid valve operatively associated with the second fluid path, and a control unit adapted to actuate the normally open solenoid valve, wherein actuation of the normally open solenoid valve generally fluidly isolates the master cylinder from the braking unit.
[0007] In another aspect, the disclosed brake-by-wire braking system may include a control unit, an electro-mechanical brake caliper associated with a first vehicle wheel, the electro-mechanical brake caliper being in communication with and actuateable by the control unit, a hydraulically actuated braking unit associated with a second vehicle wheel, an electro-hydraulic actuator in fluid communication with the hydraulically actuated braking unit by way of a first fluid path, the electro-hydraulic actuator being in communication with and actuateable by the control unit, a master cylinder in fluid communication with the hydraulically actuated braking unit by way of a second fluid path, and a normally open solenoid valve operatively associated with the second fluid path, the normally open solenoid valve being in communication with and actuateable by the control unit, wherein, when the electro-hydraulic actuator is actuated, the normally open solenoid valve is actuated.
[0008] Other aspects of the disclosed braking system will become apparent from the following description, the accompanying drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a schematic view of one aspect of the disclosed brake-by-wire braking system having a hydraulic fail-safe;
[0010] FIG. 2 is a partial schematic and partial sectional view of an electro-hydraulic brake actuator of the system of FIG. 1 ;
[0011] FIG. 3 is a front elevational view, in section, of an electro-mechanical brake caliper of the system of FIG. 1 ;
[0012] FIG. 4 is a front elevational view, in section, of a pedal feel emulator of the system of FIG. 1 ;
[0013] FIG. 5 is a perspective view of a master cylinder assembly of the system of FIG. 1 including the pedal feel emulator of FIG. 4 ; and
[0014] FIG. 6 is a front elevational view, in section of the master cylinder and pedal feel emulator assembly of FIG. 5 .
DETAILED DESCRIPTION
[0015] As shown in FIG. 1 , a first aspect of a brake-by-wire braking system having a hydraulic fail-safe, generally designated 10 , may include a brake pedal 12 , a master cylinder 14 , a pedal feel emulator 16 , a hydraulically actuated bypass valve 18 , a main control unit 20 , a first electro-hydraulic actuator 22 , a second electro-hydraulic actuator 24 , a first electro-mechanical brake caliper 26 , a second electro-mechanical brake caliper 28 , a first normally open solenoid valve 30 and a second normally open solenoid valve 32 . Additionally, the system 10 may include a brake pedal switch 34 , a pedal travel sensor 36 , a hydraulic fluid reservoir 38 , a master cylinder pressure sensor 40 , a front axle control unit 42 , a first wheel pressure sensor 44 and a second wheel pressure sensor 46 .
[0016] As shown in FIG. 1 , the first electro-hydraulic actuator 22 may be in communication with a brake caliper 48 associated with the right front wheel 50 of a vehicle (not shown) by way of fluid line 52 . Fluid line 52 may be in fluid communication with the master cylinder 14 by way of fluid line 54 and the first normally open solenoid valve 30 . Pressure sensor 44 may be positioned on fluid line 52 to monitor the hydraulic fluid pressure and communicate the pressure to the front axle control unit 42 and ultimately to the master control unit 20 .
[0017] As shown in FIG. 1 , the second electro-hydraulic actuator 24 may be in communication with a brake caliper 56 associated with the left front wheel 58 of the vehicle by way of fluid line 60 . Fluid line 60 may be in fluid communication with the master cylinder 14 by way of fluid line 54 and the second normally open solenoid valve 32 . Pressure sensor 46 may be positioned on fluid line 60 to monitor the hydraulic fluid pressure and communicate the pressure to the front axle control unit 42 and ultimately to the master control unit 20 .
[0018] Referring to FIG. 2 , the electro-hydraulic actuators 22 , 24 (only unit 22 is shown in FIG. 2 ) may include a motor 62 (e.g., an electric motor) having a shaft 64 extending therefrom, an actuator housing 66 having a central bore 68 extending therethrough and a piston 70 closely and slidably received within the bore 68 to define a hydraulic fluid chamber 72 within the housing 66 . A gear assembly 74 and a high efficiency screw 76 may be provided to translate rotational torque from the shaft 64 of the motor 62 into axial movement (see arrow A) of the piston 70 within in the bore 68 . In addition, the motor 62 of the electro-hydraulic actuators 22 , 24 may contain a mechanical or electro-mechanical brake mechanism (not shown) that can lock the shaft of the motor and thereby prevent unwanted back-driving of the gear and ball screw mechanisms even when the electrical signal is removed.
[0019] Accordingly, in response to a command from the control unit 42 (or the master control unit 20 ) the piston 70 may advance distally through the hydraulic fluid chamber 72 to urge hydraulic fluid out of the hydraulic fluid chamber 72 and into the fluid line 52 , thereby increasing the fluid pressure in the fluid line 52 and actuating the brake calipers 48 ( FIG. 1 ) to apply a braking force. Similarly, electro-hydraulic actuator 24 may independently actuate brake caliper 56 by increasing fluid pressure in corresponding fluid line 60 . In one aspect, the control unit 42 may actuate (i.e., close) the normally open solenoid valves 30 , 32 when the electro-hydraulic actuators 22 , 24 are actuated to prevent hydraulic fluid from passing to fluid line 54 .
[0020] Once the desired pressure in the fluid lines 52 , 60 is reached, as determined by the wheel pressure sensors 44 , 46 , the control unit 42 may stop each of the motors 62 and corresponding advancement of the pistons 70 . The braking force may be released by retracting the separate pistons 70 and/or opening the solenoid valves 30 , 32 to depressurize the fluid lines 52 , 60 .
[0021] While the two normally open solenoid valves 30 , 32 are actuated (i.e., closed), hydraulic fluid may not pass from the master cylinder 14 to the fluid line 54 (i.e., there is no hydraulic connection between the master cylinder 14 and the brake units at the wheels 50 , 58 , 78 , 80 ). Therefore, to permit rod 13 displacement through the master cylinder 14 (i.e., to simulate a traditional brake pedal movement), the hydraulic fluid may be urged out of the master cylinder, through the normally open hydraulically actuated bypass valve 18 and into the pedal feel emulator 16 , as shown in FIGS. 1 , 5 and 6 .
[0022] Referring to FIG. 4 , the pedal feel emulator 16 may include a channel 96 , a fluid accumulating chamber 98 in communication with the channel 96 , a piston 100 closely and slidably received within the chamber 98 and a spring 102 . The channel 96 may be in fluid communication with the master cylinder 14 by way of the normally open hydraulically actuated bypass valve 18 ( FIG. 1 ). The spring 102 may be coaxially received over the piston 100 to urge the piston in the direction shown by arrow C and resist the introduction of hydraulic fluid into the chamber 98 .
[0023] Referring again to FIG. 1 , the first electro-mechanical brake caliper 26 may be associated with the right rear wheel 78 of the vehicle and the second electro-mechanical brake caliper 28 may be associated with the left rear wheel 80 of the vehicle. Each electro-mechanical brake caliper 26 , 28 may include an electronic control unit 82 , 84 , which in turn may be in communication with the master control unit 20 .
[0024] As shown in FIG. 3 , the electro-mechanical brake calipers 26 , 28 (only caliper 26 is shown in FIG. 3 ) may include a motor 86 , a caliper housing 88 , a piston 90 , two brake pads 92 A, 92 B and a ball screw assembly 94 . The ball screw assembly 94 may be positioned between the motor 86 and the piston 90 to translate rotational torque of the motor 86 into distal advancement of the piston 90 . As the piston 90 advances distally (i.e., in the direction shown by arrow B), the piston may urge the brake pads 92 A, 92 B into engagement with an associated rotor (not shown), thereby clamping the rotor between the brake pads to apply a braking force. In addition, the electro-mechanical brake caliper may include a latching mechanism (not shown) that can be used to function as a parking brake device by prohibiting the motor and geartrain assembly from back-driving and thus maintain the full brake clamping force even when the electrical signal is removed.
[0025] Accordingly, in response to a command from the control units 82 , 84 (or the master control unit 20 ), the motor 86 may be actuated to drive the piston 90 into engagement with the brake pads 92 A, 92 B. The braking force may be released by reversing the rotation of the motor and retracting the piston 90 .
[0026] Thus, the system 10 may allow a user to apply a braking force to the wheels 50 , 58 , 78 , 80 of a vehicle (not shown) by depressing the brake pedal 12 . The movement of the pedal 12 may be detected by any combination of the brake pedal switch 34 , the pedal travel sensor 36 , and the master cylinder pressure sensor 40 and subsequently communicated to the master control unit.
[0027] In normal operation (i.e., not in fail-safe mode), when pedal movement is detected, the master control unit 20 may signal the two normally open solenoid valves 30 , 32 to close, thereby preventing fluid flow in line 54 . The locked fluid condition prevents movement of the master cylinder main piston ( FIG. 6 ), which in turn keeps the seal of the hydraulically actuated bypass valve 18 in its normally open position of the bore undercut and causes trapped fluid in the opposite chamber to flow into the pedal feel emulator 16 through passageway 96 . Then, based upon the inputs received by the master control unit 20 , such as pedal travel (sensor 36 ), master cylinder pressure (sensor 40 ), wheel pressures (sensors 44 , 46 ), vehicle speed, yaw rate, steering angle, lateral acceleration, longitudinal acceleration or any other appropriate signal, the master control unit 20 may actuate one or more of the electro-hydraulic actuators 22 , 24 and/or one or more of the electro-mechanical brake calipers 26 , 28 to generate a desired braking force and/or control the vehicle dynamics.
[0028] Alternatively, in the fail-safe mode (e.g., when an electrical failure has occurred), the two normally open solenoid valves 30 , 32 remain open, thereby allowing hydraulic fluid displaced from the master cylinder 14 to pass directly to the brake calipers 48 , 56 to apply a braking force (i.e., hydraulic braking) to the front wheels 50 , 58 . At the same time, since the master cylinder outlet port is no longer blocked shut, the main master cylinder piston is permitted to displace forward in the bore, allowing the seal of the normally open hydraulically actuated bypass valve 18 to slide past the bore undercut groove. The internal passageway is closed and any additional brake fluid is prevented from entering emulator 16 .
[0029] Accordingly, in normal operation, the system 10 may operate as a full brake-by-wire braking system (i.e., no hydraulic or other mechanical connection between the master cylinder 14 and the brake units). In the fail-safe mode, the system 10 may have a direct hydraulic connection between the master cylinder 14 and at least one brake unit.
[0030] Those skilled in the art will appreciate that various arrangements of electro-hydraulic actuators and electro-mechanical brake calipers may be used. In one alternative aspect, the electro-hydraulic actuators may be positioned at the rear of the vehicle and the electro-mechanical brake calipers may be positioned at the front of the vehicle. In another alternative aspect, an electro-hydraulic actuator is associated with only one wheel of a vehicle. In another alternative aspect, electro-hydraulic actuators are associated with three or more wheels of a vehicle.
[0031] Although various aspects of the disclosed braking system have been shown and described, modifications may occur to those skilled in the art upon reading the specification. The present application includes such modifications and is limited only by the scope of the claims.
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A brake-by-wire braking system including a braking unit, an electro-hydraulic actuator in fluid communication with the braking unit by way of a first fluid path, a master cylinder in fluid communication with the braking unit by way of a second fluid path, a normally open solenoid valve operatively associated with the second fluid path, and a control unit adapted to actuate the normally open solenoid valve, wherein actuation of the normally open solenoid valve generally fluidly isolates the master cylinder from the braking unit.
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BACKGROUND OF THE INVENTION
The invention relates to a process for recovering the alkali metal and alkaline-earth metal chlorides from used salts that accumulate in the course of the heat treatment of steel parts in salt baths, by dissolution of the used salt constituents in water, separation of the insoluble residue, optional eradication of the cyanides and fractional crystallization of the dissolved salts.
For a long time, use has been made of various heat-treatment processes in order to increase the hardness or wear resistance of steel. Amongst these processes, salt-bath technology, in which the work pieces are treated in salt melts, occupies an important position in the anti-wear industry. In a number of salt-bath processes, for example carbonitriding, case hardening, carburizing, annealing and cooling in salt baths, chloridic waste salts, so-called used salts, accumulate. There are several causes for the formation of these used salts--for example, salt melts become contaminated by the work pieces in the course of the steel treatment. For a smooth processing sequence these contaminants have to be removed in the form of sludge, 60to 90% of which also consists of salts. In the course of the reactions with the work pieces the active bath components are additionally consumed, so that they have to be replenished by regenerators or by addition of fresh salt. To this end, a part of the consumed bath, in many cases, has to be ladled out and likewise disposed of as used salt.
The main components of chloridic hardening-shop used salts are the chlorides of alkali and alkaline-earth metals --ie, of sodium, potassium, barium and calcium; a lesser proportion of the used salts also contains potassium cyanide and sodium cyanide.
Hitherto these used salts have been regarded as not economically recoverable, so that efforts to lessen the problem of residual material have concentrated primarily on improving disposability and on partial detoxification. To this end a process for immobilizing a mixture of used salt and gypsum by heating to 850° C. has for example been suggested (DE-OS 21 50 679). Another process for improving the disposability provides for the treatment of the used salt with iron sulphate and sodium sulphate at a temperature between 600° and 900° C. (DE-OS 38 43 285). Various possibilities for detoxification of the cyanide in the used salt have also been published in the past. One way is the injection of oxygen or water vapor into the molten used salt at a temperature between 800° and 1000° C. (DE-OS 23 40 523).
These processes have the serious disadvantage that, on the one hand, they are very energy-intensive and, on the other hand, their aim is not the recovery of the salt constituents but merely simplification of the disposability.
Besides, there have already been attempts to recover the valuable substances from the used salts. For instance, separation of the barium portion by precipitation in the form of barium carbonate or barium sulphate has been described at various times. On the other hand, no particulars are stated with respect to the recovery of other constituents such as sodium chloride and potassium chloride. In addition, the processing of the precipitated barium compounds so as to yield barium chloride is associated with extra process steps and costs.
The partial recovery of salt constituents from hardening shop used salts is described in DE-OS 24 00 318 and DE-OS 24 00 319. After the cyanide detoxification, which is carried out in the melt at 450° to 550° C., the used salt is leached with hot water. The residue, the greater part of which consists of barium carbonate, is separated and supplied to a further processing stage, so as to yield barium chloride for example. The dissolved carbonate is converted into carbon dioxide by addition of nitric acid, and the quantity of chloride is reduced to between 10and 15wt-% by evaporation of the water, whereby sodium chloride is recoverable in the form of crystallization product. The remaining solution is dried at 160° C. and the salt mixture consisting of nitrate and nitrite as well as two per cent sodium chloride and potassium chloride is said to be capable of being used again directly in hardening shops. However, this process also has disadvantages which have prevented conversion on a large scale. For instance, upon addition of nitric acid nitrous gases are released in relatively large amounts and have to be subjected to catalytic incineration. However, avoiding the addition of acid by introduction of barium nitrate into the solution requires in turn an additional process step. In particular, the purities of the salts obtained do not conform to the demands placed on raw materials for the production of hardening salts and are greatly dependent on the composition of the used salts employed, which is subject to considerable fluctuations. By reason of the variable composition the recovered nitrate-nitrite salt is also not capable of being re-used directly, particularly since the specified chloride concentration does not comply with the technical requirements. In addition, through the use of regenerators the composition of the accumulating used salts has in recent years changed in the direction towards lower cyanide and carbonate contents and greater proportions of chloride. The described process is unable to comply with these changed overall conditions without additional process steps.
Processes for the separation of alkali metal and alkaline earth metal chlorides are known per se. One process for the salting-out of barium chloride from solutions is based on the addition of 250 g/l sodium chloride to a heated concentrated solution of barium chloride, as a result of which barium chloride-2-hydrate precipitates out, and after washing with a solution of barium chloride the salt can be obtained with a purity of 99 to 100% (DE-PS-429 716). Another process provides for separation of sodium chloride and potassium chloride (GB-PS-648 903). In this process a mixture of the two salts in a 55% solution of calcium chloride is dissolved at 950° C., whereby sodium chloride precipitates out. To the remaining solution additional solid calcium chloride is added, and this solution is concentrated by evaporation at 95° C. to such an extent that a double salt consisting of calcium chloride and potassium chloride crystallizes out. This double salt is then dissolved with a 27% solution of calcium chloride at 38° C. and this solution is cooled to 15° C., whereby potassium chloride crystallizes out. However, neither process is directly applicable to the hardening-salt problem, since here highly variable compositions of the solution have to be reckoned with, and as a result other process conditions obtain.
OBJECT OF THE INVENTION
The object of the present invention was therefore to develop a process for recovering the alkali metal and alkaline-earth metal chlorides from used salts that accumulate in the course of the heat treatment of steel parts in salt baths, by dissolution of the used-salt constituents in water, separation of the insoluble residue, optional eradication of the cyanides and fractional crystallization of the dissolved salts, whereby said process should be applicable to all used-salt compositions and all used-salt constituents should be recoverable.
In accordance with the invention this object is achieved in that by addition of hydrochloric acid the barium carbonate is separated from the residue in the form of barium chloride and is supplied to the salt solution, in that by addition of sodium chloride and calcium chloride in a ratio of 1:1 to 5:1 at temperatures from -5 to +20° C the barium chloride is crystallized out of the salt solution, whereby for every 300 g/l of used salt in the solution 150 to 350 g sodium chloride and 30 to 150 g calcium chloride are added, in that by addition of calcium chloride until a concentration amounting to between 150 and 400 g/l is attained at a temperature from 40° to 120° C. the sodium chloride is crystallized out, in that by concentrating the solution at 60° to 120° C. to a concentration amounting to between 500 and 900 g calcium chloride per liter remaining sodium chloride and barium chloride are crystallized out, in that by further concentrating the solution at 60° to 120° C. a double salt consisting of potassium chloride and calcium chloride is crystallized out, the double salt is dissolved at 35°-40° C. in a 20to 35% solution of calcium chloride and the potassium chloride is crystallized out at 5° to 20° C., and in that the calcium chloride is recovered from the remaining solution as a result of concentration by evaporation.
In case the used salts contain cyanides, the latter have to be oxidatively eradicated by anodic oxidation or by addition of hydrogen peroxide.
It has been found that after crushing of the solid chioridic hardening-shop used salts to a grain size of, advantageously, less than 2 mm, the soluble salt constituents can be completely removed from the solids by leaching 15 kg to 50 kg of used salt in 100liters of water. Subsequently, complete cyanide detoxification of the suspension is achieved by anodic oxidation or addition of hydrogen peroxide, advantageously with a combination of both processes. By virtue of carbon dioxide and nitrogen being released, at the high salt concentrations a stable foam is formed, the volume of which may amount to a multiple of the solution quantity. It has been found that this foam can be avoided or eradicated by addition of 0.1 to 100 ml of foam-remover solution. The insoluble constituents, consisting of barium carbonate and contaminants arising from the operation of the hardening shop, substantially iron oxides, are separated from the solution by, for example, the addition of flocculating agents with a pH-value of 8.5to 12, whereby the residual concentration of flocculating agents in the solution, also in the case of an overdose of 50per cent, lies below 2 ppm. After conversion of the barium carbonate into barium chloride with hydrochloric acid the iron-oxide sludge can be dehydrated to a residual moisture amounting to 30 to 35 per cent, for example in a filter press. After being washed with water the filter cake no longer contains any salt constituents and, by reason of its low residual moisture, can be disposed of in trouble-free manner.
After neutralization with hydrochloric acid the individual components are selectively separated from the separated salt solutions by selective addition of reagents and a special sequence of crystallization steps. This ensures that for salts of variable composition the process provides invariable products of high purity.
With respect to the recovery of barium chloride it has been found that, contrary to the conventional salting-out with sodium chloride, increases in yield and purity can be achieved by supplementary addition of calcium chloride. At the same time this ensures that defined conditions are established for the next crystallization step, the salting out of sodium chloride. By addition of 150 to 350 g, advantageously 200 to 250 g, of solid sodium chloride and 60 to 300 g of an approximately 50% solution of calcium chloride to one liter of used-salt solution, upon cooling to a temperature between -5° C. and 20° C., preferably 0° C. to 15° C., barium chloride is selectively crystallized out with the exception of a residual content of 1 to 2 wt-%; in addition, the crystallization product has a high degree of purity, generally better than 99%. The weight ratio of the added salts (that is to say, NaCl:CaCl 2 ) amounts to, depending on the content of calcium chloride in the used salt solution, between 1:1 and 5:1, advantageously 3:1, and can be regulated by measurement, for example using ion selective electrodes.
Furthermore it has been found that by subsequent addition of calcium chloride until a concentration of calcium chloride of 150 to 400 g/l is attained at a temperature between 40° C. and 120° C. pure sodium chloride can be crystallized out selectively, whereas the barium chloride remains in the solution.
By concentrating this solution, preferably in a vacuum crystallizer at a temperature between 60° C. and 120° C., in particular at 80° C. to 100° C., the concentration of calcium chloride is increased to between 500 and 900 g/l. It has furthermore been found that the remaining sodium chloride crystallizes out with the exception of less than 0.5 wt-% and the barium chloride crystallizes out almost entirely that is to say, except for traces in the ppm range. This salt mixture can in turn be supplied to the first crystallization stage, so that with this process more than 99.9% of the barium chloride can be recovered.
Potassium chloride can be separated from the remaining solution in known manner by the solution being further concentrated at 60° to 120° C., in particular 80° to 110° C., until calcium-chloride/potassium-chloride crystallizes out in the form of a double salt. The mother liquor is separated and held in intermediate storage. A part of this solution is diluted with water in a ratio of 1:1. In this diluted solution, in which concentrations of 20 to 35 per cent calcium chloride and 0.5 to 1.5 per cent potassium chloride arise, the double salt is 35° to 40° C., preferably at 38° C. By the solution being cooled to between 5° and 20° C., in particular between 10° C. and 15° C., pure potassium chloride crystallizes out. The remaining solution of calcium chloride is partially introduced in preceding process steps, the calcium chloride is recovered from the residual solution as a result of concentration by evaporation, in particular by spray drying.
All the crystallized salts, in particular also the barium chloride-2-hydrate and calcium chloride-2-hydrate salts that contain water of crystallization, are converted by suitable drying into an anhydrous form with a residual moisture amounting to less than 0.1%.
DESCRIPTION OF THE DRAWING
FIG. 1 shows a flow diagram of the process according to the invention in which the sequence of the individual process steps is represented. After crushing (1) of the used salts, leaching (2) with water takes place.
A subsequent cyanide detoxification (3) is the prerequisite for separation of the contaminants by solid/liquid separation, for example filtration (4). From the neutralized solution (5) barium chloride is salted out (6) by addition of sodium chloride. As a result of addition of a hot-saturated solution of calcium chloride, sodium chloride can be crystallized out (7). By concentration of the solution a mixture consisting of sodium chloride and barium chloride (8) is obtained which is used again in step 6. Potassium chloride is separated by concentration of the solution (9), dissolution in a diluted calcium-chloride solution (10) of the CaCl 2 --KCl double salt that has crystallized out in the process, and subsequent cooling of the solution (11). The calcium chloride is obtained after concentration by evaporation of the remaining solution (12).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following Examples are intended to elucidate the process according to the invention in greater detail:
1. 100 kg of a cyanide-free used salt are crushed to a grain size of less than 2 mm and leached in 300 l of water. Carbonate and hydroxide are neutralized by addition of 7.9 kg of 37% hydrochloric acid. Subsequently a pH-value of 9.5 is adjusted with sodium hydroxide. The contaminants are flocculated by addition of 1000 ml of 0.1% polymeric flocculating agent solution, and the used-salt solution is separated from the contaminants by filtration. After this, barium chloride is crystallized out at 0° C. by addition of 39.3 kg of salt mixture arising from the evaporative crystallization, 87% of which consists of sodium chloride and 13% of which consists of barium chloride, and also 0.8 kg sodium chloride and 12.2 kg calcium chloride, and is filtered off. To the solution which has been heated to 50° C. there are added 39 kg calcium chloride, and the crystallized sodium chloride is filtered off. Subsequently the solution is concentrated by evaporation at 90° C. until 175 liters of condensate have accumulated, and the crystallized salt mixture consisting of sodium chloride and barium chloride is separated. The solution with a concentration of calcium chloride amounting to 600 g/l is concentrated at 100° C. until a further 46 liters of condensate have been collected. The crystallized double salt consisting of calcium chloride and potassium chloride is separated. 5 liters of the concentrated solution are diluted with 15 liters of water and the double salt in dissolved therein at 38° C. As a result of cooling this solution to 10° C. the potassium chloride crystallizes out and is filtered off. The solution of calcium chloride is subsequently spray dried.
Quantitative analysis of the processing gives the following result.
______________________________________ Proportion in Product ProductCompound used salt quantity purity______________________________________BaCl.sub.2 56.9% 57.2 kg 99.0%CaCl.sub.2 20.6% 24.5 kg 97.0%NaCl 10.1% 11.8 kg 98.7%KCl 2.6% 2.0 kg 97.7%NaOH 2.0% 0.0 kg --CaCO.sub.3 3.0% 0.0 kg --Fe.sub.3 O.sub.4 4.8% 7.0 kg 32%(Residue) Residual moisture______________________________________
2. The sequence of process steps corresponds to that specified in Example 1, with the difference that conversion of the cyanide by anodic oxidation directly follows the leaching. 100 kg of the cyanide-containing used salt are crushed to a grain size of less than 2 mm and leached in 300 l of water. After this, the cyanide in the used-salt solution with a pH-value of 11 is oxidized to cyanate with the aid of an oxidation electrolysis cell and subsequently, after lowering of the pH-value to 8.5, the cyanate is oxidized further to carbon dioxide and nitrogen. Carbonate and hydroxide are neutralized by addition of 18.2 kg of 37% hydrochloric acid. A pH value of 9.5 is adjusted with sodium hydroxide so that the contaminants are flocculated by addition of 1800 ml of 0.1% polymeric flocculating agent and the contaminants can be separated from the solution by filtration. After this, barium chloride is crystallized out at 0° C. by addition of 38.3 kg of salt mixture arising from the evaporative crystallization, 87% of which consists of sodium chloride and 13% of which consists of barium chloride, 0.8 kg sodium chloride and 25 kg calcium chloride, and is filtered off. To the solution which has been heated to 60° C. there are added 30 kg calcium chloride, and the crystallized sodium chloride is filtered off. Subsequently the solution is condensed by evaporation at 90° C. until 190 liters of condensate have been collected, and the crystallized salt mixture consisting of sodium chloride and barium chloride is separated. The solution, which has a concentration of calcium chloride amounting to 600 g/l, is concentrated at 100° C. until a further 47 liters of condensate have been collected. The crystallized double salt consisting of calcium chloride and potassium chloride is separated. 20 liters of the concentrated solution are diluted with 40 liters of water and the double salt is dissolved therein at 38° C. As a result of cooling the solution to 10° C. the potassium chloride crystallizes out and is filtered off. The solution of calcium chloride is subsequently spray dried.
Quantitative analysis once again shows the high degrees of purity and the complete yield of the salts.
______________________________________ Proportion in Product ProductCompound used salt quantity purity______________________________________BaCl.sub.2 39.9 kg 55.5 kg 98.5%CaCl.sub.2 10.6 kg 11.0 kg 96.1%NaCl 13.1 kg 13.5 kg 99.1%KCl 10.6 kg 13.2 kg 98.6%NaOH 0.9 kg 0.0 kg --BaCO.sub.3 14.0 kg 0.0 kg --KCN 2.1 kg 0.0 kg --Fe.sub.3 O.sub.4 8.8 kg 12.8 kg 31%(Residue) Residual moisture______________________________________
3. 100 kg of a cyanide-containing used salt are crushed to a grain size of less than 2 mm and leached in 300 l of water. After this, the cyanide in the used-salt solution with a pH-value of 11is oxidized to cyanate with the aid of an oxidation electrolysis cell and subsequently, after lowering of the pH-value to 8.5, the cyanate is oxidized further to carbon dioxide and nitrogen. Carbonate and hydroxide are neutralized by addition of 23.8 kg of 37% hydrochloric acid. Subsequently a pH-value of 9.5 is adjusted with sodium hydroxide. The contaminants are flocculated by addition of 950 ml of 0.1% polymeric flocculating agent, and the solution is separated from the contaminants by filtration. After this, barium chloride is crystallized out at 0° C. by addition of 36.2 kg of salt mixture arising from the evaporative crystallization, 87% of which consists of sodium chloride and 13% of which consists of barium chloride, and 28.5 kg calcium chloride, and is filtered off. To the solution which has been heated to 60° C. there are added 39 kg calcium chloride, and the crystallized sodium chloride is filtered off. Subsequently the solution is concentrated by evaporation at 100° C. until 185 liters of condensate have been collected, and the crystallized salt mixture consisting of sodium chloride and barium chloride is separated. The solution, which has a concentration of calcium chloride amounting to 600 g/l, is concentrated at 100° C. until a further 48 liters of condensate have been collected. The crystallized double salt consisting of calcium chloride and potassium chloride is separated. 20 liters of the concentrated solution are diluted with 30 liters of water and the double salt is dissolved therein at 38° C. As a result of cooling the solution to 10° C. the potassium chloride crystallizes out and is filtered off. The solution of calcium chloride is subsequently spray dried.
Quantitative analysis of the processing gave the following result.
______________________________________ Proportion in Product ProductCompound used salt quantity purity______________________________________BaCl.sub.2 26.3% 54.5 kg 99.3%CaCl.sub.2 1.5% 1.3 kg 96.7%NaCl 24.8% 26.5 kg 97.6%KCl 7.3% 17.4 kg 98.0%NaOH 1.1% 0.0 kg --BaCO.sub.3 26.2% 0.0 kg --KCN 8.4% 0.0 kg --Fe.sub.3 O.sub.4 4.4% 7.0 kg 33%(Residue) Residual moisture______________________________________
4. The cyanide-free used salt from Example 1 is processed, with the crystallization temperatures differing from the crystallization temperatures according to the invention. The other crystallization conditions, such as concentration of the added salts and the duration of crystallization, are kept the same as far as possible. 100 kg of the cyanide-free used salt are crushed to a grain size of less than 2 mm and leached in 300 1 of water. Carbonate and hydroxide are neutralized by addition of 7.9 kg of 37% hydrochloric acid. Subsequently a pH-value of 9.5 is adjusted with sodium hydroxide. The contaminants are flocculated by addition of 1000 ml of 0.1% polymeric flocculating-agent solution, and the used-salt solution is separated from the contaminants by filtration. After this, barium chloride is crystallized out at 25° C. by addition of 33.9 kg of salt mixture arising from the evaporative crystallization, 92% of which consists of sodium chloride and 8% of which consists of barium chloride, and also 3.9 kg sodium chloride and 12.2 kg calcium chloride, and is filtered off. To the solution which has been heated to 30° C. there are added 39 kg calcium chloride, and the crystallized sodium chloride is filtered off. Subsequently the solution is concentrated by evaporation at 100° C. until 175 liters of condensate have accumulated, and the crystallized salt mixture consisting of sodium chloride and barium chloride is separated. The solution with a concentration of calcium chloride amounting to 600 g/l is concentrated at 100° C. until a further 46 liters of condensate have been collected. The crystallized double salt consisting of calcium chloride and potassium chloride is separated. 5 liters of the concentrated solution are diluted with 15 liters of water and the double salt is dissolved therein at 38° C. As a result of cooling this solution to 25° C. the potassium chloride crystallizes out and is filtered off. The solution of calcium chloride is subsequently spray dried.
Quantitative analysis of the processing gives the following result, which shows a clearly inferior yield of barium chloride and low degrees of purity, particularly in the case of sodium chloride:
______________________________________ Proportion in Product ProductCompound used salt quantity purity______________________________________BaCl.sub.2 56.9% 51.3 kg 99.1%CaCl.sub.2 20.6% 25.6 kg 93.0%NaCl 10.1% 16.5 kg 73.5%KCL 2.6% 2.1 kg 96.5%NaOH 2.0% 0.0 kg --CaCO.sub.3 3.0% 0.0 kg --Fe.sub.3 O.sub.4 4.8% 7.0 kg 32%(Residue) Residual moisture______________________________________
Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto.
German Priority Application 195 37 198.4 is relied upon and incorporated herein by reference.
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The process for environmentally acceptable and economical recovery of chloride salts from hardening-shop used salts utilizing the steps of leaching of the used salt, detoxification of the cyanide and selective crystallization of the individual chloride salts. The process is characterized in that all the chloride salts that are present in the hardening-shop used salt are recovered in pure form.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/076,740, filed on Jun. 30, 2008 which is incorporated by reference as if fully set forth.
FIELD OF INVENTION
This application is related to wireless communications.
BACKGROUND
The long term evolution-advanced (LTE-A) project of the third generation partnership Project (3GPP) is working towards enhancements of the LTE program. For example, the LTE-A project anticipates the use of peak data rates of 0.5 Gbps in the uplink (UL) direction and 1 Gbps in the downlink (DL) direction. In order to achieve these data rates, UL multiple input/multiple output (MIMO) is being considered for the LTE-A project.
FIG. 1 shows an overview of an Evolved Universal Mobile Telecommunications System (UMTS) Terrestrial Radio Access Network (E-UTRAN) 100 in accordance with the prior art. As shown in FIG. 1 , E-UTRAN 100 includes three eNodeBs (eNBs) 102 , however, any number of eNBs may be included in E-UTRAN 100 . The eNBs 102 are interconnected with each other by means of an X2 interface 108 . The eNBs 102 are also connected by means of an S1 interface 106 to the Evolved Packet Core (EPC) 104 that includes a Mobility Management Entity (MME) 108 and a Serving Gateway (S-GW) 110 .
FIG. 2 shows an LTE user-plane protocol stack 200 in accordance with the prior art. The protocol stack 200 is located in a WTRU 210 and includes the packet data control protocol (PDCP) 202 , the radio link control (RLC) 204 , the medium access control (MAC) 206 and the physical layer (PHY) 208 . The protocol stack 200 may also reside in an eNB (not shown).
FIG. 3 shows an LTE control plane protocol stack 300 of the WTRU 210 of FIG. 2 . The control plane protocol stack 300 includes the non-access stratum (NAS) 302 and a radio resource control (RRC) 304 . Also included are the PDCP 306 , RLC 308 and MAC 310 , which together form the layer 2 sublayer 312 .
Logical channel prioritization is a procedure that is performed for each new transmission by a transmitting entity. The transmitting RRC entity controls the scheduling of UL data by giving each logical channel a priority. A higher priority value indicates a lower actual priority level. Additionally, each logical channel is given a prioritized bit rate (PBR).
The RRC of a wireless transmit receive unit (WTRU) may perform the logical channel prioritization procedure. FIG. 4 shows a logical channel prioritization method 400 in accordance with the prior art. At step 402 the WTRU allocates resources to the logical channels. The WTRU, at step 404 allocates resources to the logical channels in a decreasing priority order up to a value such that on average, the served data rate for radio bearers that have data for transmission equals the configured PBR for the radio bearer. If the PBR of a radio bearer is set to “infinity”, the WTRU allocates resources for all the data that is available for transmission on the radio bearer before meeting the PBR of the lower priority radio bearers. At step 406 the WTRU, if any resources remain, serve all the logical channels in a strict decreasing priority order until either the data for that logical channel or the UL grant is exhausted, whichever comes first.
For the method 400 shown in FIG. 4 , the WTRU may follow certain rules. For example, the WTRU should not segment a radio link control (RLC) service data unit (SDU), or partially transmitted SDU or retransmitted RLC protocol data unit (PDU), if the whole SDU, partially transmitted SDU or retransmitted RLC PDU fits into the remaining resources. Further, if the WTRU segments an RLC SDU from the logical channel, it may maximize the size of the segment to fill the grant as much as possible. Also, the WTRU may use as much data as it can to fill the grant, in general. However, if the remaining resources require the WTRU to segment an RLC SDU with size smaller than a certain number of bytes or smaller than the L2 header size, the WTRU may use padding to fill the remaining resources instead of segmenting the RLC SDU and sending the segment.
Logical channels configured with the same priority are served equally by the WTRU. Medium access control (MAC) control elements for buffer status reporting, with exception of padding BSR, have higher priority than user plane logical channels. At a serving cell change, the first UL dedicated control channel (DCCH) MAC SDU to be transmitted in the new cell has higher priority than MAC control elements for BSR.
With the introduction of UL MIMO in LTE-advanced, enhanced MAC logical channel prioritization and multiplexing mechanisms may be needed to handle multiple transport blocks (TBs) within the same transmission time interval (TTI).
SUMMARY
A method and apparatus for logical channel prioritization in a wireless transmit receive unit (WTRU) is disclosed. This may include the WTRU receiving multiple streams of a multiple input/multiple output (MIMO) signal. This may also include a physical layer (PHY) of the WTRU providing an indicator for each of the multiple streams to a medium access control (MAC) layer of the WTRU and the MAC layer performing logical channel multiplexing based on the indicator for each of the multiple streams.
BRIEF DESCRIPTION OF THE DRAWINGS
A more detailed understanding may be had from the following description, given by way of example in conjunction with the accompanying drawings wherein:
FIG. 1 shows an overview of an Evolved Universal Mobile Telecommunications System (UMTS) Terrestrial Radio Access Network (E-UTRAN) in accordance with the prior art;
FIG. 2 shows an LTE user-plane protocol stack in accordance with the prior art;
FIG. 3 shows an LTE control plane protocol stack of the WTRU 210 of FIG. 2 .
FIG. 4 shows a logical channel prioritization method 400 in accordance with the prior art.
FIG. 5 shows a wireless communication system 200 including a plurality of WTRUs 210 and an e Node B (eNB) 220 ; and
FIG. 6 is a functional block diagram of the WTRU and the eNB of the wireless communication system of FIG. 5 .
DETAILED DESCRIPTION
When referred to hereafter, the terminology “wireless transmit/receive unit (WTRU)” includes but is not limited to a user equipment (UE), a mobile station, a fixed or mobile subscriber unit, a pager, a cellular telephone, a personal digital assistant (PDA), a computer, or any other type of user device capable of operating in a wireless environment. When referred to hereafter, the terminology “base station” includes but is not limited to a Node-B, a site controller, an access point (AP), or any other type of interfacing device capable of operating in a wireless environment.
FIG. 5 shows a wireless communication system 500 including a plurality of WTRUs 510 and an e Node B (eNB) 520 . As shown in FIG. 5 , the WTRUs 510 are in communication with the eNB 520 . Although three WTRUs 510 and one eNB 520 are shown in FIG. 5 , it should be noted that any combination of wireless and wired devices may be included in the wireless communication system 500 .
FIG. 6 is a functional block diagram 600 of a WTRU 510 and the eNB 520 of the wireless communication system 500 of FIG. 5 . As shown in FIG. 5 , the WTRU 510 is in communication with the eNB 520 . The WTRU 510 is configured with a PHY layer, MAC layer, RRC layer and an RLC layer. The WTRU 510 is further configured to perform logical channel prioritization as required.
In addition to the components that may be found in a typical WTRU, the WTRU 510 includes a processor 615 , a receiver 616 , a transmitter 617 , and an antenna 618 . The WTRU 510 may also include a user interface 618 , which may include, but is not limited to, an LCD or LED screen, a touch screen, a keyboard, a stylus, or any other typical input/output device. The WTRU 510 may also include memory 619 , both volatile and non-volatile as well as interfaces 620 to other WTRU's, such as USB ports, serial ports and the like. The receiver 616 and the transmitter 617 are in communication with the processor 615 . The antenna 618 is in communication with both the receiver 616 and the transmitter 617 to facilitate the transmission and reception of wireless data.
In addition to the components that may be found in a typical eNB, the eNB 520 includes a processor 625 , a receiver 626 , a transmitter 627 , and an antenna 628 . The receiver 626 and the transmitter 627 are in communication with the processor 625 . The antenna 628 is in communication with both the receiver 626 and the transmitter 627 to facilitate the transmission and reception of wireless data. The eNB 520 is configured with a PHY layer, a MAC layer and an RRC layer. The eNB 520 is further configured to perform logical channel prioritization upon transmission as required.
The PHY layer within a transmitting entity, for example, a WTRU or an eNB, may provide certain indications to the MAC layer with the transmitting entity. For example, the PHY may indicate to the MAC, for each MIMO stream, channel conditions and/or information on physical allocation so that the modulation and coding scheme (MCS), transmit power, and TB size can be determined for each MIMO stream.
The transmit power and TB size may depend on the MCS and on the particular MAC data flow or combination of data flows assigned to each MIMO stream. For a selected MAC data flow or combination of flows, the choice of MCS, transmit power, and TB size may be dependent on the channel quality of the MIMO stream and channel allocation information of the MIMO stream. The MAC may choose these parameters so that the Quality of Service (QoS) is normalized on each MIMO stream. An intended result is for the residual hybrid retransmission request (HARQ) process error rate to be similar on each MIMO stream when the same data flow or flows are assigned.
The PHY may also indicate to the MAC a ranking of the different TBs, for example, from the most preferred to the least preferred. The ranking may be based on the quality of the TB or underlying MIMO stream. For example, a higher quality TB may be ranked ahead of a lower quality TB. The ranking may also be based on a size of the TB, the MCS, one or more of the link adaptation parameters such as power and/or MCS, the likelihood for correct reception, and/or HARQ acknowledge/non-acknowledge (ACK/NACK) results and statistics. The PHY may indicate the TBs in sequence to the MAC, for example, from the most preferred to the least preferred. Alternatively, PHY can indicate a pointer to a predetermined TB set rather than send a list.
The MAC will may use the indications from the PHY layer to perform logical channel multiplexing on the TBs. Within the transmitting entity, when given multiple TB's within the same TTI, the MAC logical channel prioritization procedure may populate and/or multiplex traffic on a TB according to the MIMO stream quality and physical channel allocation information, or according to the ranking indicated from the PHY layer. For example, if a determination is made that the first TB to be populated is TB 1 and that the second TB to be populated is TB 2 and so on, the MAC will perform the operation. MAC multiplexing/logical channel prioritization on multiple TB's may be according to a certain order. The ranking or ordering criteria can be used to optimize and improve the performance of uplink transmissions in a way that can enhance the quality of service (QoS) and the uplink throughput.
A transmitting entity may receive, for each MIMO stream, an MCS for each of the multiple TBs, size for each of the multiple TBs, transmission power for each of the multiple TBs, UL radio resources, such as frequency and time or space location of radio resource blocks, for example, an UL preceding MIMO index such as a pre0-coding matrix index (PMI) or MIMO channel coefficients, for example, information regarding HARQ processes used for UL transmission and HARQ feedback (ACK/NACK) for each of the multiple TBs. The information may be received in an UL scheduling grant, for example, which is carried on an DL control channel, such as the physical downlink control channel (PDCCH), for example. For each MIMO stream, the information may be signaled explicitly or implicitly. If signaled implicitly, some information may be derived from other signaled parameters. For example, a TB size may be derived from the MCS and allocated resource blocks.
The order or location of the parameters in the control channel may indicate the order of the TB's to be populated by the MAC. For example, the first TB (TB 1 ) may correspond to the first codeword and the second TB (TB 2 ) may correspond to the second codeword, and so on. A MAC multiplexing function may populate TB 1 first, then TB 2 and so on, in accordance with the order implied from or indicated in the signaling channel. Accordingly, the ranking or ordering criteria of populating the TB's by the MAC multiplexing function corresponds to the order that will be implied/derived from the signaling.
When a transmitting entity, such as a WTRU, for example, is processing multiple TBs within the same TTI, the MAC logical channel prioritization procedure may populate or multiplex traffic on the TBs according to a particular order. The population may be performed in a round-robin fashion, for example. The order shifts or circulates in every defined time period, whether the time period is, for example, every TTI, or every TTI allocated. Alternatively, the population may be performed randomly or arbitrarily.
The MAC may perform a logical channel prioritization and multiplexing operation on each of the TB's in the TTI, independent of the other TBs. The MAC may perform logical channel (LC) prioritization and multiplexing, and create a MAC PDU for TB 1 , and perform the same procedure to create a MAC PDU for TB 2 .
This operation is equivalent to running the LC prioritization and multiplexing logic in one TTI, and rerunning the same logic for another TTI. However, the rerunning of the same logic occurs twice in the same TTI. The LC prioritization and multiplexing of different TBs to be transmitted in the same TTI can be operated simultaneously or sequentially.
The MAC evaluates the sizes of all TB's within the TTI, and performs prioritization and multiplexing of LC's on the TBs jointly. Rather than prioritizing logical channels on TB's according to the priority/order of the TBs, the WTRU may map data from different logical channels on any of the TB's in such a way that will minimize the overhead, such as the RLC segmentation overhead, for example. For example, the WTRU may maximize the size of the RLC PDU and minimize the need for segmentation.
If there is sufficient data, the transmitting MAC may multiplex a number of RLC PDUs. The number may be as close as possible to the number of TB's in a TTI. For example, if there are 2 TBs per TTI, 2 RLC data PDUs should be multiplexed, that is, one in each TB. This may prevent excessive segmentation and may maximize the RLC PDU sizes.
If the WTRU is scheduling 2 or more RLC SDUs, the WTRU may compare the size of each of the RLC SDU with the size of each of the TB's. For each of the SDUs, the WTRU multiplexes an RLC SDU on the TB that will not require segmentation of the RLC SDU and/or will lead to minimizing the occurrence of segmentation of the other RLC SDUs that will be multiplexed on the other TBs. The WTRU may not segment an RLC SDU if the whole SDU fits into any of the TBs in the TTI, or if it fits into any of the remaining un-assigned/un-populated TB's of the TTI. If the WTRU segments an RLC SDU from the logical channel, it maximizes the size of the segment to fill the TB as much as possible. If the WTRU has an option to perform segmentation or re-segmentation on at least one RLC SDU, the WTRU may select or segment the RLC PDU that will result in the lowest segmentation overhead. For example, if the WTRU has the option of segmenting an RLC SDU for the first time, or resegmenting an RLC PDU for the first time, then the WTRU may segment the former and retransmit the latter as is, rather than transmitting the former as is and resegmenting the latter, because the overhead due to resegmentation is typically higher.
In another embodiment, the WTRU may select the permutation or mapping that minimizes the occurrence of segmentation and/or resegmentation. For example, assume that the WTRU is scheduling data (Di) from an LC's (LCi) and has 2 TBs of size TBS 1 and TBS 2 . The WTRU may consider the sizes TBS 1 and TBS 2 in order to find the permutation or mapping that minimizes the occurrence of segmentation on all Di. The WTRU may view this in terms of a bin-packing problem, whereby the TBs are the bins, and the MAC SDUs and/or MAC CE's are the objects to be packed in the two bins of sizes TBS 1 and TBS 2 , with the exceptions that the size of one or more of the objects to be packed can be changed and the process is constrained by the goal of minimization of total segmentation overhead and/or padding.
Alternatively the MAC may choose data flows to be multiplexed into TBs based on the quality and/or resource allocation of each MIMO channel. The MAC may chose the data flow or combination of data flows to multiplex for each TB mapped to a MIMO stream based on the data flow quality and/or data rate requirements.
MAC control elements CEs may be transmitted on any of the TBs. However, in order to improve the reception of MAC CEs, the WTRU can transmit then on the TB with the highest quality. The MAC CEs may be handled as the highest priority traffic by the MAC multiplexing logic. However, the MAC CEs may also be distributed among the TBs in such a way that will minimize the occurrence of segmentation for the other MAC PDUs.
In another alternative embodiment, an information element (IE) sent over RRC signaling can include configuration information regarding a mapping of LCs onto TBs. The WTRU may restrict or allow a group of LCs to be multiplexed on a given TB, while allowing another group of LCs to be multiplexed on another TB.
For example, RRC signaling may specify which LCs should be mapped to the first TB, and which LCs should be mapped to the second TB. The first and second TB can be determined by the WTRU. For example, the first TB may be a preferred TB because it is, for example, a high quality TB, and not necessarily the first one available. The WTRU may perform logical channel multiplexing in accordance with the mapping, and if any resources remain, and no more data is available from one of the LC groups, then it may include/multiplex data from the other group onto the TB configured for the other LC group.
By way of example, a WTRU may receive a signal that a first LC group, including, for example, LC 1 , LC 3 , and LC 4 , are to be multiplexed on the first TB, while a second LC group, including, for example, LC 2 and LC 5 are to be multiplexed on the second TB. The WTRU will multiplex the traffic on the TBs in a way that adheres to the signaled mapping. As an optional optimization, if the WTRU does not have sufficient data to transmit from one LC group, then data from the other group may be sent on the other TB. Some LCs may be present in more than one group. As another alternative, L2 signaling can be used to configure the mapping or grouping of LC's onto TBs.
Although features and elements are described above in particular combinations, each feature or element can be used alone without the other features and elements or in various combinations with or without other features and elements. The methods or flow charts provided herein may be implemented in a computer program, software, or firmware incorporated in a computer-readable storage medium for execution by a general purpose computer or a processor. Examples of computer-readable storage mediums include a read only memory (ROM), a random access memory (RAM), a register, cache memory, semiconductor memory devices, magnetic media such as internal hard disks and removable disks, magneto-optical media, and optical media such as CD-ROM disks, and digital versatile disks (DVDs).
Suitable processors include, by way of example, a general purpose processor, a special purpose processor, a conventional processor, a digital signal processor (DSP), a plurality of microprocessors, one or more microprocessors in association with a DSP core, a controller, a microcontroller, Application Specific Integrated Circuits (ASICs), Field Programmable Gate Arrays (FPGAs) circuits, any other type of integrated circuit (IC), and/or a state machine.
A processor in association with software may be used to implement a radio frequency transceiver for use in a wireless transmit receive unit (WTRU), user equipment (UE), terminal, base station, radio network controller (RNC), or any host computer. The WTRU may be used in conjunction with modules, implemented in hardware and/or software, such as a camera, a video camera module, a videophone, a speakerphone, a vibration device, a speaker, a microphone, a television transceiver, a hands free headset, a keyboard, a Bluetooth® module, a frequency modulated (FM) radio unit, a liquid crystal display (LCD) display unit, an organic light-emitting diode (OLED) display unit, a digital music player, a media player, a video game player module, an Internet browser, and/or any wireless local area network (WLAN) or Ultra Wide Band (UWB) module.
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A method and apparatus for logical channel prioritization in a wireless transmit receive unit (WTRU), including the WTRU receiving multiple streams of a multiple input/multiple output (MIMO) signal, a physical layer (PHY) of the WTRU providing an indicator for each of the multiple streams to a medium access control (MAC) layer of the WTRU, and the MAC layer performing logical channel multiplexing based on the indicator for each of the multiple streams.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of and claims the benefit of priority from U.S. application Ser. No. 11/929,894, filed Oct. 30, 2007, which is a divisional of U.S. application Ser. No. 11/188,692, filed Jul. 26, 2005, which is a continuation of U.S. Pat. No. 7,012,894, issued Mar. 14, 2006, which is a continuation of U.S. Pat. No. 6,510,137, issued Jan. 21, 2003 and is based upon and claims the benefit of priority from French Application No. 99 10752, filed Aug. 19, 1999, the entire contents of all of which are incorporated herein by reference.
This invention relates to a method for configuring a telecommunication system comprising at least one sending entity and at least one receiving entity, said sending and receiving entities implementing a step for transmission of data transported on at least one physical channel, said at least one physical channel transmitting a transport channel composite under formation and having its own maximum physical rate, said transport channel composite comprising at least two transport channels, said data transmission step being preceded by a data processing procedure for each of said transport channels, said data processing procedure comprising at least one rate matching step, said rate matching step transforming a number of symbols before rate matching into a number of symbols after rate matching, said number of symbols after rate matching being obtained approximately by multiplying said number of symbols before rate matching by a rate matching ratio specific to each of said at least two transport channels, said transport channel composite having a number of symbols approximately equal to the algebraic sum of the numbers of symbols in the transport channels after the rate matching steps in said processing procedures for a period common to said processing procedures.
The 3GPP (3 rd Generation Partnership Project) Committee is an organization whose members originate from various regional standardization organizations and particularly the ETSI (European Telecommunication Standardization Institute) for Europe and the ARIB (Association of Radio Industries and Businesses) for Japan, and the purpose of which is to standardize a 3 rd generation telecommunication system for mobiles. The CDMA (Code Division Multiple Access) technology has been selected for these systems. One of the fundamental aspects distinguishing 3 rd generation systems from 2 nd generation systems, apart from the fact that they make more efficient use of the radio spectrum, is that they provide very flexible services. 2 nd generation systems offer an optimized radio interface only for some services, for example the GSM (Global System for Mobiles) system is optimized for voice transmission (telephony service). 3 rd generation systems have a radio interface adapted to all types of services and service combinations.
Therefore, one of the benefits of 3 rd generation mobile radio systems is that they can efficiently multiplex services that do not have the same requirements in terms of Quality of Service (QoS), on the radio interface. In particular, these quality of service differences imply that the channel encoding and channel interleaving should be different for each of the corresponding transport channels used, and that the bit error rates (BER) are different for each transport channel. The bit error rate for a given channel encoding is sufficiently small when the Eb/I ratio, which depends on the coding, is sufficiently high for all coded bits. Eb/I is the ratio between the average energy of each coded bit (Eb) and the average energy of the interference (I), and depends on the encoding. The term symbol is used to denote an information element that can be equal to a finite number of values within an alphabet, for example a symbol may be equivalent to a bit when it can only be one of two values.
The result is that since the various services do not have the same quality of service, they do not have the same requirement in terms of the Eb/I ratio. But yet, in a CDMA type system, the capacity of the system is limited by the level of interference. Thus, an increase in the energy of bits coded for a user (Eb) contributes to increasing interference (I) for other users. Therefore, the Eb/I ratio has to be fixed as accurately as possible for each service in order to limit interference produced by this service. An operation to balance the Eb/I ratio between the different services is then necessary. If this operation is not carried out, the Eb/I ratio would be fixed by the service with the highest requirement, and the result will be that the quality of the other services would be “too good”, which would have a direct impact on the system capacity in terms of the number of users. This causes a problem, since rate matching ratios are defined identically at both ends of the radio link.
This invention relates to a method for configuring a telecommunication system to define rate matching ratios identically at both ends of a CDMA type radio link.
In the ISO's (International Standardization Organization) OSI (Open System Interconnection) model, a telecommunication equipment is modeled by a layered model comprising a stack of protocols in which each layer is a protocol that provides a service to the higher level layer. The 3GPP committee calls the service provided by the level 1 layer to the level 2 layer “transport channels”. A transport channel (TrCH for short) enables the higher level layer to transmit data with a given quality of service. The quality of service is characterized in particular by a processing delay, a bit error rate and an error rate per block. A transport channel may be understood as a data flow at the interface between the level 1 layer and the level 2 layer in the same telecommunication equipment. A transport channel may also be understood as a data flow between the two level 2 layers in a mobile station and in a telecommunication network entity connected to each other through a radio link. Thus, the level 1 layer uses suitable channel encoding and channel interleaving, in order to satisfy the quality of service requirement.
Solutions proposed by the 3GPP committee to achieve this balancing are illustrated in FIGS. 1 and 2 . FIG. 1 is a diagrammatic view illustrating multiplexing of transport channels on the downlink according to the current proposal of the 3GPP committee. In the current proposal of this committee, the symbols processed until the last step 130 described below are bits.
With reference to FIG. 1 , a higher level layer 101 periodically supplies transport block sets to the level 1 layer. These sets are supplied in transport channels reference 100 . A periodic time interval with which the transport block set is supplied to the transport channel is called the Transmission Time Interval (TTI) of the transport channel. Each transport channel has its own TTI time interval which may be equal to 10, 20, 40 or 80 ms. FIG. 2 shows examples of transport channels A, B, C and D. In this figure, the transport block set received by each transport channel is represented by a bar in the histogram. The length of the bar in the histogram represents a TTI interval of the associated transport channel and its area corresponds to the useful load in the transport block set . With reference to FIG. 2 , the duration of the TTI intervals associated with transport channels A, B, C and D is equal to 80 ms, 40 ms, 20 ms and 10 ms respectively. Furthermore, the dotted horizontal lines in the histogram bars indicate the number of transport blocks in each transport block set. In FIG. 2 , transport channel A receives a first transport block set A 0 comprising three transport blocks during a first transmission time interval, and a second transport block set A 1 comprising a single transport block during the next TTI interval. Similarly, transport channel B receives transport block sets B 0 , B 1 , B 2 and B 3 during four consecutive TTI intervals, comprising 0, 2, 1 and 3 transport blocks respectively. Transport channel C receives transport block sets C 0 to C 7 during eight successive TTI intervals and finally transport channel D receives transport block sets D 0 to D 15 during sixteen TTI intervals.
Note that a TTI interval for a given transport channel cannot overlap two TTI intervals in another transport channel. This is possible because TTI intervals increase geometrically (10 ms, 20 ms, 40 ms and 80 ms). Note also that two transport channels with the same quality of service necessarily have the same TTI intervals. Furthermore, the term “transport format” is used to describe the information representing the number of transport blocks contained in the transport block set received by a transport channel and the size of each transport block. For a given transport channel, there is a finite set of possible transport formats, one of which is selected at each TTI interval as a function of the needs of higher level layers. In the case of a constant rate transport channel, this set only includes a single element. On the other hand, in the case of a variable rate transport channel, this set comprises several elements and therefore the transport format can vary from one TTI interval to the other when the rate itself varies. In the example shown in FIG. 2 , transport channel A has a first transport format for the set A 0 received during radio frames 0 to 7 , and a second transport format for set A 1 during radio frames 8 to 15 .
According to the assumptions currently made by the 3GPP committee, there are two types of transport channels, namely real time transport channels and non-real time transport channels. No automatic repeat request (ARQ) is used in the case of an error with real time transport channels. The transport block set contains at most one transport block and there is a limited number of possible sizes of this transport block. The expressions “block size” and “number of symbols per block” will be used indifferently in the rest of this description.
For example, the transport formats defined in the following table may be obtained:
Transport
Number of
Corresponding transport
format index
transport blocks
block size
0
0
—
1
1
100
2
1
120
In this table, the minimum rate is zero bit per TTI interval. This rate is obtained for transport format 0. The maximum rate is 120 bits per TTI interval and it is obtained for transport format 2.
Automatic repetition can be used in the case of an error with non-real time transport channels. The transport block set contains a variable number of transport blocks of the same size. For example, the transport formats defined in the following table may be obtained:
Transport format index
Number of transport blocks
Transport block size
0
1
160
1
2
160
2
3
160
In this table, the minimum rate is 160 bits per TTI interval. This rate is obtained for transport format 0. The maximum rate is 480 bits per TTI interval and is obtained for transport format 2.
Thus, considering the example shown in FIG. 2 , the following description is applicable for transport channels A, B, C and D:
Transport channel
A
TTI interval
80 ms
Transport formats
Transport format index
Number of transport blocks
Transport block size
0
1
160
1
2
160
2
3
160
In FIG. 2 , the transport block set A 0 is in transport format 2, whereas A 1 is in transport format 0.
Transport channel
B
TTI interval
40 ms
Transport formats
Transport format index
Number of transport blocks
Transport block size
0
0
—
1
2
80
2
1
80
3
3
80
In FIG. 2 , transport block sets B 0 , B 1 , B 2 and B 3 are in transport formats 0, 1, 2 and 3 respectively.
Transport channel
C
TTI interval
20 ms
Transport formats
Transport format index
Number of transport blocks
Transport block size
0
0
—
1
1
100
2
1
120
In FIG. 2 , transport block sets C 0 , C 1 , C 2 , C 3 , C 4 , C 5 , C 6 and C 7 are in transport formats 2, 2, 1, 2, 2, 0, 0 and 2 respectively.
Transport channel
D
TTI interval
10 ms
Transport formats
Transport format index
Number of transport blocks
Transport block size
0
0
—
1
1
20
2
2
20
3
3
20
In FIG. 2 , transport block sets D 0 to D 15 are in transport formats 1, 2, 2, 3, 1,0, 1, 1, 1, 2, 2, 0, 0, 1, 1 and 1 respectively.
For each radio frame, a transport format combination (TFC) can then be formed starting from the current transport formats for each transport channel. With reference to FIG. 2 , the transport format combination for frame 0 is ((A,2), (B0), (C,2), (D,1)). It indicates that transport formats for transport channels A, B, C and D for frame 0 are 2, 0, 2, and 1 respectively. Index 5 is associated with this transport format combination in the following table that illustrates a possible set of transport format combinations to describe the example in FIG. 2 :
Transport format for
Combination
transport Channels
Frame number with this
index
A
B
C
D
combination
0
0
2
0
0
11
1
0
2
0
2
10
2
0
3
0
0
12
3
0
3
0
1
13
4
0
2
2
1
8
5
2
0
2
1
0
6
0
2
2
2
9
7
2
1
1
0
5
8
2
0
2
2
1 and 2
9
0
3
2
1
14 and 15
10
2
1
1
1
4
11
2
0
2
3
3
12
2
1
2
1
6 and 7
Therefore, with reference once again to FIG. 1 , each transport channel reference 100 receives a transport block set at each associated TTI interval originating from a higher level layer 101 . Transport channels with the same quality of service are processed by the same processing system 102 A, 102 B. A frame checking sequence (FCS) is assigned to each of these blocks during a step 104 . These sequences are used in reception to detect whether or not the received transport block is correct. The next step, reference 106 , consists of multiplexing the various transport channels with the same quality of service (QoS) with each other. Since these transport channels have the same quality of service, they can be coded in the same way. Typically, this multiplexing operation consists of an operation in which transport block sets are concatenated. The next step consists of carrying out a channel encoding operation, 108 , on multiplexed sets of blocks. The result at the end of this step is a set of coded transport blocks. A coded block may correspond to several transport blocks. In the same way as a sequence of transport block sets forms a transport channel, a sequence of sets of coded transport blocks is called a coded transport channel. Channels coded in this way are then rate matched in a step 118 and are then interleaved on their associated TTI intervals in a step 120 and are then segmented in a step 122 . During the segmentation step 122 , the coded transport block sets are segmented such that there is one data segment for each multiplexing frame in a TTI interval in the channel concerned. A multiplexing frame is the smallest time interval for which a demultiplexing operation can be operated in reception. In our case, a multiplexing frame corresponds to a radio frame and lasts for 10 ms.
As already mentioned, the purpose of the rate matching step ( 118 ) is to balance the Eb/I ratio on reception between transport channels with different qualities of service. The bit error rate BER on reception depends on this ratio. In a system using the CDMA multiple access technology, the quality of service that can be obtained is greater when this ratio is greater. Therefore, it is understandable that transport channels with different qualities of service do not have the same needs in terms of the Eb/I ratio, and that if the rate is not matched, the quality of some transport channels would be “too” good since it is fixed by the most demanding channel and would unnecessarily cause interference on adjacent transport channels. Therefore, matching the rate also balances the Eb/I ratio. The rate is matched such that N input symbols give N+ΔN output symbols, which multiplies the Eb/I ratio by the
N + Δ N N
ratio. This
N + Δ N N
ratio is equal to the rate matching ratio RF, except for rounding.
In the downlink, the peak/average ratio of the radio frequency power is not very good, since the network transmits to several users at the same time. Signals sent to these users are combined constructively or destructively, thus inducing large variations in the radio frequency power emitted by the network, and therefore a bad peak/average ratio. Therefore, for the downlink it was decided that the Eb/I ratio will be balanced between the various transport channels by rate matching using a semi-static rate matching ratio.
RF ≈ N + Δ N N ,
and that multiplexing frames would be padded by dummy symbols, in other words non-transmitted symbols (discontinuous transmission). Dummy symbols are also denoted by the abbreviation DTX (Discontinuous Transmission). Semi-static means that this RF ratio can only be modified by a specific transaction implemented by a protocol from a higher level layer. The number of DTX symbols to be inserted is chosen such that the multiplexing frame padded with DTX symbols completely fills in the Dedicated Physical Data Channel(s) (DPDCH).
This discontinuous transmission degrades the peak/average ratio of the radio frequency power, but this degradation is tolerable considering the simplified construction of the receiving mobile station obtained with a semi-static rate matching ratio.
Referring once again to FIG. 1 , the transport channels with different qualities of service after encoding, segmentation, interleaving and rate matching are multiplexed to each other in a step 124 in order to prepare multiplexing frames forming a transport channel composite. This multiplexing is done for each multiplexing frame individually. Since the rate of the multiplexed transport channels may be variable, the composite rate obtained at the end of this step is also variable. The capacity of a physical channel referred to as a DPDCH (Dedicated Physical Data Channel) is limited, consequently it is possible that the number of physical channels necessary to transport this composite may be greater than one. When the required number of physical channels is greater than one, a segmentation step 126 for this composite is included. For example, in the case of two physical channels, this segmentation step 126 may consist of alternately sending one symbol to the first of the two physical channels denoted DPDCH#L, and a symbol to the second physical channel denoted DPDCH# 2 .
The data segments obtained are then interleaved in a step 128 and are then transmitted on the physical channel in a step 130 . This final step 130 consists of modulating the symbols transmitted by spectrum spreading.
DTX symbols are dynamically inserted either for each TTI interval separately in a step 116 , or for each multiplexing frame separately in a step 132 . The rate matching ratios RF i associated with each transport channel i are determined such as to minimize the number of DTX symbols to be inserted when the total transport channel composite rate after the multiplexing step 124 is maximum. The purpose of this technique is to limit degradation of the peak/average ratio of the radio frequency power in the worst case.
The rate is matched by puncturing (RF i <1, ΔN<0) or by repetition (RF i >1, ΔN>0). Puncturing consists of deleting −ΔN symbols, which is tolerable since they are channel encoded symbols, and therefore despite this operation, when the rate matching ratio RF i is not too low, channel decoding in reception (which is the inverse operation of channel encoding) can reproduce data transported by the transport channels without any error (typically when RF i >0.8, in other words when not more than 20% of symbols are punctured).
DTX symbols are inserted during one of the two mutually exclusive techniques. They are inserted either in step 116 using the “fixed service positions” technique, or in step 132 using the “flexible service positions” technique. Fixed service positions are used since they enable to carry out a blind rate detection with acceptable complexity. Flexible service positions are used when there is no blind rate detection. Note that the DTX symbols insertion step 116 is optional.
During step 116 (fixed service positions), the number of DTX symbols inserted is sufficient so that the data flow rate after this step 116 is constant regardless of the transport format of the transport channels before this step 116 . In this way, the transport format of the transport channels may be detected blind with reduced complexity, in other words without transmitting an explicit indication of the current transport format combination on an associated dedicated physical control channel (DPCCH). Blind detection consists of testing all transport formats until the right encoding format is detected, particularly using the frame checking sequence FCS.
If the rate is detected using an explicit indication, the DTX symbols are preferably inserted in step 132 (flexible service positions). This makes it possible to insert a smaller number of DTX symbols when the rates on two composite transport channels are not independent, and particularly in the case in which they are complementary since the two transport channels are then never at their maximum rate simultaneously.
At the present time, the only algorithms that are being defined are the multiplexing, channel encoding, interleaving and rate matching algorithms. A rule needs to be defined to fix a relation in the downlink between the number N of symbols before rate matching and the variation ΔN corresponding to the difference between the number of symbols before rate matching and the number of symbols after rate matching.
Consider the example shown in FIG. 2 . Transport channel B accepts four transport formats indexed from 0 to 3. Assume that the coded transport channel originating from transport channel B produces not more than one coded block for each transport format, as shown in the following table.
Transport channel
B
TTI interval
40 ms
Transport formats
Coded
Transport
Number of
Transport
Number of coded
block
format index
transport blocks
block size
blocks
size (N)
0
0
—
0
—
1
2
80
1
368
2
1
80
1
192
3
3
80
1
544
Assume that RF B =1.3333 is the rate matching ratio, then the variation ΔN generated by rate matching varies with each transport format, for example as in the following table:
Transport channel
B
TTI interval
40 ms
Transport formats
Transport format
Number of
Coded block size
Variation
index
coded blocks
(N)
(ΔN)
0
0
—
—
1
1
368
123
2
1
192
64
3
1
544
181
Thus, the existence of this type of rule to calculate the variation ΔN as a function of the number N of symbols before rate matching could simplify negotiation of the connection. Thus, according to the example in the above table, instead of providing three possible variations ΔN, it would be sufficient to supply a restricted number of parameters to the other end of the link that could be used to calculate them. An additional advantage is that the quantity of information to be supplied when adding, releasing or modifying the rate matching of a transport channel, is very small since parameters related to other transport channels remain unchanged.
A calculation rule was already proposed during meeting No. 6 of the work sub-group WG1 of sub-group 3GPP/TSG/RAN of the 3GPP committee in July 1999 in Espoo (Finland). This rule is described in section 4.2.6.2 of the proposed text presented in document 3GPP/TSG/RAN/WG1/TSGR1#6(99)997 “Text Proposal for rate matching signaling”. However, it introduces a number of problems as we will demonstrate. Note the notation used in this presentation is not exactly the same as the notation in document TSGR1#6(99)997 mentioned above.
In order to clarify the presentation, we will start by describing the notation used in the rest of the description.
Let i denote the index representing the successive values 1, 2, . . . , T of the coded transport channels, then the set of indexes of the transport formats of the coded transport channel i are denoted TFS(i), for all values of i, {1, . . . , T}. If j is the index of a transport format of a coded transport channel i, in other words j , TFS(i), the set of indexes of coded blocks originating from the coded transport channel i for transport format j is denoted CBS(i,j). Each coded block index is assigned uniquely to a coded block, for all transport formats and all coded transport channels. In summary we have:
{ ∀ i ∈ { 1 , … , T } ∀ j ∈ T F S ( i ) ∀ i ′ ∈ { 1 , … , T } ∀ j ′ ∈ T F S ( i ′ )
( i , j ) ≠ ( i ′ , j ′ ) ⇒ C B S ( i , j ) ⋂ C B S ( i ′ , j ′ ) = θ ( 1 )
where θ is an empty set. Note that for the purposes of this presentation, the index of a coded block does not depend on the data contained in this block, but it identifies the coded transport channel that produced this coded block, the transport format of this channel, and the block itself if this transport channel produces several coded blocks for this transport format. This block index is also called the coded block type. Typically, coded transport channel i does not produce more than 1 coded block for a given transport format j, and therefore CBS(i,j) is either an empty set or a singleton. If a coded transport channel i produces n coded blocks for transport format j, then CBS(i,j) comprises n elements.
We will also use TFCS to denote the set of transport format combinations. Each element in this set may be bi-univocally represented by a list of (i,j) pairs associating each coded transport channel indexed i in {1, . . . , T} with a transport format with index j in this coded transport channel (jεTFS(i)). In other words, a transport format combination can determine a transport format j corresponding to each coded transport channel i. In the rest of this presentation, it is assumed that the set TFCS comprises C elements, the transport format combinations for this set then being indexed from 1 to C. If 1 is the index of a transport format combination, then the transport format index corresponding to the coded transport channel indexed i in the transport format combination with index 1 will be denoted TF i (1). In other words, the transport format combination with index 1 is represented by the following list:
((1,TF 1 (l)),(2,TF 2 (l)), . . . , (T,TF T (l)))
The set of block size indexes for any transport format combination 1 is denoted MSB(1). Therefore, we have:
∀
l
∈
{
1
,
…
,
C
}
M
S
B
(
l
)
=
⋃
1
≤
l
≤
T
C
B
S
(
i
,
TF
i
(
l
)
)
(
2
)
Furthermore, the number of multiplexing frames in each transmission time interval on the coded transport channel i is denoted F i . Thus, in the sending system shown in FIG. 1 , any block originating from the coded transport channel i is segmented into F i blocks or segments. Based on the current assumptions made by the 3GPP committee, the sizes of these blocks are approximately equal. For example, if F i =4 and the block on which segmentation step 122 is applied comprises 100 symbols, then the segments obtained at the end of this step 122 comprise 25 symbols. On the other hand, if the segmented block comprises only 99 symbols, since 99 is not a multiple of 4, then after segmentation there will be either 3 blocks of 25 symbols with 1 block of 24 symbols, or 4 blocks of 25 symbols with a padding symbol being added during the segmentation step 122 . However, if X is the number of symbols in the block before segmentation step 122 , it can be written that
⌈ X F 1 ⌉
is the maximum number of symbols per segment, the notation ┌x┐ denoting the smallest integer greater than or equal to x.
Finally, for a coded block with type or index k, the number of symbols in this coded block before rate matching is denoted N k , and the variation between the number of symbols after rate matching and the number of symbols before rate matching is denoted ΔN k . Furthermore, note that in the rest of this text, the expressions “rate” and “number of symbols per multiplexing frame” are used indifferently. For a multiplexing frame with a given duration, the number of symbols expresses a rate as a number of symbols per multiplexing frame interval.
Now that the notation has been defined, we can describe the calculation rule described in document 3GPP/TSG/RAN/WG1/TSGR1#6(99)997 “Text proposal for rate matching signaling”.
A prerequisite for this rule is to determine a transport format combination l o for which the composite rate is maximum. For this transport format combination l o , the variations ΔN k MF for blocks with N k MF symbols before rate matching will be determined. This is done only for transport format combination l o , in other words only for all values kεMBS(1 0 ). The upper index MF in the ΔN k MF and N k MF notations means that these parameters are calculated for a multiplexing frame and not for a TTI interval. By definition:
{
∀
i
∈
{
1
,
…
,
T
}
∀
j
∈
T
F
S
(
i
)
∀
k
∈
C
B
S
(
i
,
j
)
N
k
MF
=
⌈
N
k
F
i
⌉
(
3
)
The next step is to proceed as if the rate matching 118 was carried out after segmentation per multiplexing frame step 122 to define the variations ΔN k MF . For flexible service positions, the variations ΔN k MF for k∉MBS(1 0 ) are calculated using the following equation:
{ ∀ l ∈ { 1 , … , C } ∀ k ∈ M S B ( l ) and k ∉ M S B ( l 0 )
Δ N k MF = ⌊ Δ N K ( k ) MF N K ( k ) MF · N k MF ⌋ ( 4 )
where, for any coded block with index k, κ(k) is the element of MSB(1 0 ) such that coded blocks with index k and κ(k) originate from the same coded transport channel and where └x┘ denotes the largest integer less than or equal to x.
For fixed service positions, the variations ΔN k MF for k∉MSB(1 0 ) are calculated using the following equation:
{
∀
l
∈
{
1
,
…
,
C
}
∀
k
∈
M
S
B
(
l
)
and
k
∉
M
S
B
(
l
0
)
Δ
N
k
MF
=
Δ
N
K
(
k
)
MF
(
4
bis
)
Note that the definition of κ(k) does not create any problem with this method since, for any value of (i,j), CBS(i,j) comprises a single element and therefore if i is the index of the coded transport channel that produces the coded block with indexed size k, then κ(k) is defined as being the single element of CBS(i,1 0 ).
With this rule, it is guaranteed that CBS(i,j) is a singleton since, firstly the number of coded blocks per TTI interval is not more than one (basic assumption), and secondly when this number is zero it is considered that the block size is zero and CBS(i,j) then contains a single element k with N k =0.
Finally, the set of variations ΔN k is calculated using the following equation:
{ ∀ i ∈ { 1 , … , T } ∀ j ∈ T F S ( i ) ∀ k ∈ C B S ( i , j )
Δ N k = F i · Δ N k MF
which, in terms of variation, corresponds to the inverse operation of equation (3), by reducing the considered multiplexing frame period to a TTI interval.
The following problems arise with this calculation rule:
1) nothing is written to say what is meant by the composite rate (the exact rate can only be determined when the variations ΔN have been calculated; therefore, it cannot be used in the calculation rule);
2) even if this concept were defined, it is probable that there are some cases in which the transport format combination that gives the maximum composite rate is not unique; the result is that the definition of the combination lo is incomplete;
3) equation (4) introduces a major problem. The transport format combination for which the composite rate is maximum is not necessarily such that all transport channels are simultaneously at their maximum rates. In the following, the number of symbols available per multiplexing frame for the CCTrCH composite will be called the maximum physical rate N data . The maximum physical rate depends on the resources in allocated physical channels DPDCH. Therefore, it is possible that the maximum physical rate N data of the physical channel(s) carrying the composite is insufficient for all transport channels to be at their maximum respective rates simultaneously. Therefore in this case, there is no transport format combination in which all transport channels are at their maximum rates simultaneously. Thus, transport channel rates are not independent of each other. Some transport channels have a lower priority than others such that when the maximum physical rate N data is insufficient, only the highest priority transport channels are able to transmit, and transmission for the others is delayed. Typically, this type of arbitration is carried out in the medium access control (MAC) sublevel of the level 2 layer in the OSI model. Since transport channels are not necessarily at their maximum rates simultaneously when the composite is at its maximum rate in transport format combination l o , in particular it is possible that one of them is at zero rate; therefore, it is possible to find a value k 0 εMBS(1 0 ) such that N k 0 MF =0, and consequently ΔN k 0 MF =0. If k 1 εMBS(1 0 ) is such that k 0 =κ(k 1 ), equation (4) then becomes as follows for k=k 1 :
Δ
N
k
1
MF
=
⌊
Δ
N
k
0
MF
N
k
0
MF
·
N
k
1
MF
⌋
=
⌊
0
0
·
N
k
1
MF
⌋
It then includes a 0/0 type of indeterminate value. In the same way, it is possible that N k 0 MF is very small compared with N k 1 MF , even if it is not 0. Thus, whereas the composite is in the transport format combination l o at its maximum rate, the transport channel corresponding to coded block indexes k 0 and k 1 is at a very low rate N k 0 MF compared with another possible rate N k 0 MF for the same transport channel. The result is that equation (4) giving ΔN k 1 MF as a function of ΔN k 0 MF amplifies the rounding error made during determination of ΔN k 0 MF by a factor
N k 1 MF N k 0 MF
which is very large compared with one. However, such amplification of the rounding error in this way is not desirable.
One purpose of the invention is to suggest a rule for overcoming the disadvantages described above.
Another purpose of the invention is to provide this type of method that can define rate matching for the downlink for all possible situations, and particularly for at least one of the following cases:
when ΔN k 0 MF and N k 0 MF are zero simultaneously;
the
N k 1 MF N k 0 MF
ratio is very large compared with 1;
the rate of at least some transport channels of a transport channel composite
depends on at least some other transport channels in the same transport channel composite.
Another purpose of the invention is to provide a method for minimizing the number of dummy symbols (DTX) to be inserted when the rate of the coded transport channel composite is maximum.
BACKGROUND OF INVENTION
Consequently, the subject of the invention is a method for configuring a telecommunication system comprising at least one sending entity and at least one receiving entity, said sending and receiving entities implementing a step for transmission of data transported on at least one physical channel, said at least one physical channel transmitting a transport channel composite under formation and having its own maximum physical rate offered by said at least one physical channel, said transport channel composite comprising at least two transport channels, said data transmission step being preceded by a data processing procedure for each of said transport channels, said data processing procedure comprising at least one rate matching step, said rate matching step transforming a number of symbols before said rate matching step into a number of symbols after said rate matching step, said number of symbols after said rate matching step being obtained approximately by multiplying said number of symbols before said rate matching step by a rate matching ratio specific to each of said at least two transport channels, said transport channel composite having a number of symbols approximately equal to the algebraic sum of the numbers of symbols in the transport channels after the corresponding rate matching steps in said processing procedures for a period common to said processing procedures,
characterized in that it comprises the following successive steps:
a step for determining, from at least one of said entities,
for each of said processing procedures, a first parameter related to the rate matching, said first parameter being proportional to said rate matching ratio, and
for all said processing procedures, a second parameter representing said maximum physical rate;
a transmission step for said first and second parameters determined from at least one of said entities, called the first entity, to another of said entities, called the second entity; and
a step in which at least said second entity determines the variation between the number of symbols after said rate matching step and the number of symbols before said rate matching step, for each of said processing procedures, starting from one of said first and second transmitted parameters, such that the maximum rate of said transport channel composite obtained does not cause an overshoot of said maximum physical rate of said at least one physical channel.
Note that data blocks to which the rate matching step 118 is applicable are the coded blocks originating from the channel encoding step 108 (see FIG. 1 ).
According to one important characteristic of the invention, said step in which the variation between the number of symbols after said rate matching step and the number of symbols before said rate matching step is determined starting from one of said first and second transmitted parameters includes at least some of the following steps:
a step in which a temporary variation is calculated for each of said data block types starting from said first and second parameters and said number of symbols before said rate matching step;
a correction step of said temporary variations for all said transport format combinations, such that a temporary rate of the composite, said temporary rate resulting from said temporary variations, does not cause an overshoot of said maximum physical rate for the all said transport format combinations, said correction step being called the global correction step;
a step in which final variations are determined.
Another subject of the invention is a configuration apparatus of the type comprising at least means of transmitting data transported on at least one physical channel, said at least one physical channel transmitting a transport channel composite under formation and with a maximum physical rate offered by said at least one physical channel, said transport channel composite comprising at least two transport channels, said apparatus comprising a data processing module comprising at least rate matching means for each of said transport channels, said rate matching means transforming a number of input symbols to said rate matching means into a number of output symbols from said rate matching means obtained approximately by multiplying said number of input symbols by a rate matching ratio specific to said at least one transport channel concerned, said transport channel composite having a number of symbols approximately equal to the algebraic sum of the numbers of transport channel symbols originating from the corresponding rate matching means in said processing modules for a period common to said processing,
characterized in that it comprises:
means of determining a first parameter related to the rate matching proportional to said rate matching ratio for each of said processing modules, and a second parameter representative of said maximum physical rate for the set of said processing modules, from at least one of said entities;
means of transmitting said first and second determined parameters from at least one of said entities called the first entity, to another of said entities called the second entity; and
means by which at least said second entity determines the variations between the number of output symbols from and the number of input symbols to said rate matching means starting from said first and second transmitted parameters, for each of said processing modules, such that the maximum rate obtained for said transport channel composite does not cause an overshoot of said maximum physical rate of said at least one physical channel.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow diagram for downlink rate matching according to the prior art;
FIG. 2 is an example of variable channel rates according to the prior art;
FIG. 3 is a flow diagram for downlink rate matching according to the present invention;
FIG. 4 is a first alternative flow chart for downlink rate matching according to the present invention;
FIG. 5 is a second alternative flow chart for downlink rate matching according to the present invention;
FIG. 6 is a flow chart for downlink rate matching corrections according to the present invention.
The invention will be better understood after reading the following description which is given solely as an example and which is given with reference to the attached drawings including FIGS. 3 to 5 which represent the different methods of calculating the variations ΔN k according to the invention, and FIG. 6 represents a step in which the temporary variations are partially corrected.
DETAILED DESCRIPTION
The following description applies to the case of flexible service positions, unless specifically mentioned otherwise.
According to the invention, each coded transport channel i is characterized by two parameters RM i and P i . The first parameter RM i represents a rate matching attribute for coded transport channel i. This attribute is proportional to the Eb/I ratio expected in reception, in other words if several coded transport channels denoted 1, 2, . . . , T, are considered with attributes denoted RM 1 , RM 2 , . . . RM T respectively, then the expected Eb/I ratios for each coded transport channel will be in the same proportions as the RM i parameters. The second parameter P i is a coefficient corresponding to the maximum allowable puncturing ratio for a given coded transport channel i. Thus, a maximum puncturing ratio denoted P 1 , P 2 , . . . P T is associated with each coded transport channel 1, 2, . . . , T. The maximum puncturing ratio is imposed by the channel coding used in the processing system specific to the coded transport channel considered. Puncturing consists of eliminating coded symbols. This elimination is tolerable since channel encoding introduces a redundancy. However, the number of punctured symbols cannot be too large compared with the total number of coded symbols, therefore there is a maximum puncturing ratio that depends on the channel coding and the decoder used in reception.
Furthermore, note that the maximum physical rate N data is the maximum number of symbols that can be transmitted in a multiplexing frame, allowing for the allocation of one or several physical channels DPDCH.
According to the invention, only the set of parameters {RM 1 } where iε[1,T] , and N data are transmitted on a logical control channel associated with a previously existing coded transport channel composite, in order to enable each telecommunication system entity to know the set of correspondences between the numbers of symbols after rate matching N+ΔN and the numbers of symbols before rate matching N, for each coded transport channel. A logical channel denotes a channel that can connect two level 3 layer protocols, typically two Radio Resource Control (RRC) protocols. This type of logical channel is carried by one of the transport channels within a previously existing coded transport channel composite.
These parameters {RM i } iε[1,T] and N data may be determined by one of the entities, or they may be “negotiated” between several entities. Note that N data is a positive non-null integer and the {RM i } iε[1,T] parameters are also positive and non-null, and may also typically be expressed simply as binary numbers.
At the end of the negotiation, the {RM i } iε[1,T] and N data parameters come into force at a moment determined by the negotiation to define the (N, ΔN) pairs for each coded transport channel and for each of their respective transport formats within a new transport channel composite. Note that this new composite is the result of the composite under formation before the instant at which the RM i and N data parameters came into force. This new composite typically replaces the previously existing composite on which the negotiation took place. It is impossible to make any negotiation when there is no previously existing transport channel composite on the dedicated physical channels DPDCH in duplex at the time that a transport channel composite is set up. Under these conditions, the number of coded transport channels T and the {RM i } iε[1,T] and N data parameters of the new coded transport channel composite are either predefined for the system, or are determined in a simplified negotiation for which dedicated physical data channels do not have to exist in advance. Typically, this type of negotiation may take place on common physical channels such as the Physical Random Access Channel (PRACH) for the uplink, and the Forward Access Channel (FACH) for the downlink. This simplified negotiation could also relate to a context including the {RM i } iε[1,T] and N data information, this context having been set up during a previous connection of dedicated physical data channels.
The RM i parameters are such that the rate matching ratios RF i associated with the same coded transport channel are proportional to the parameters, factored by a semi-static factor L independent of the coded transport channel i. Therefore, we have:
∀ iRF i =L·RM i (5)
Furthermore, the following must be satisfied in order to respect the constraint on the maximum puncturing ratio:
∀ iRF i ≧1 −P i (6)
Note that according to the invention, there is no need to know the value of each parameter P i to calculate the set of, correspondences (N, ΔN). The system of equations (5) and (6) is equivalent to the system of equations (5), (7) and (8) with respect to the factor L:
L≧L MIN (7)
where
L
MIN
=
max
i
1
-
P
i
RM
i
(
8
)
Therefore, all that has to be known is LMIN or any other proportional value determined using a factor dependent on known data, for example
PL = L MIN · min i RM i ,
to have the same information on all possible values of the rate matching ratios {RF i }. However, this is not necessary. In fact, the factor L is maximized as a function of N data such that the number of inserted DTX symbols is minimum when the transport channel composite rate is maximum. Consequently, since N data is sufficiently large so that equation (7) is satisfied when the L factor is at a maximum, there is no need to know the P i parameters or any other parameter (for example LMIN) giving a puncturing limit to determine the variations ΔN. All that is necessary is that the method used to calculate the correspondences (N, ΔN) maximizes the L factor, in other words minimizes the number of inserted DTX symbols for the maximum rate of the transport channel composite. However, this does not mean that the values of the P i , PL or LMIN parameters are not negotiated. It simply means that all that is necessary to calculate correspondences (N, ΔN) according to the invention is to know the value of the maximum physical rate N data in addition to the value of the parameters {RM i }.
Thus, if 1 is the index of a transport formats combination, and if the coded transport channel i is in transport format index j in this transport formats combination (in other words j=TF i (1)), then for each coded block with index k in coded transport channel i with format j ( in other words kεCBS(i,j)), if N k +ΔN k is the number of symbols before segmentation step 122 , the segments will have not more than
⌈ N k + Δ N k F i ⌉
symbols at the end of this step. The result is that when considering all k type coded blocks, where kεCBS(i,TF i (1)) on the coded transport channel i for the transport formats combination with index 1 and all coded transport channels iε{1, . . . , T}, it is deduced that the total number of symbols D(1) in a multiplexing frame of the transport format combination, 1 is equal to not more than the following sum:
D
(
l
)
=
∑
i
=
1
i
=
T
∑
k
∈
CBS
(
i
,
TF
i
(
1
)
)
⌈
N
k
+
Δ
N
k
F
i
⌉
(
9
)
Furthermore, given the rate limits of the dedicated physical data channels, we have:
∀ l ε{1, . . . , C}D ( l )≦N data (10)
Note that N data −D(l) is the number of DTX symbols inserted during step 132 for the transport formats combination 1.
Since it is required to minimize the number of DTX symbols inserted during step 132 when the transport channel composite rate is maximum, we need:
max D (1)≈ N data 1≦1≦ C (11)
Also, according to the invention, the calculation of the variation ΔN k for any value of k includes mainly three phases. In the first phase, temporary variations denoted ΔN k temp are calculated so as to satisfy equation (11). In the second phase, these temporary variations are corrected by a “global” correction step in order to satisfy the relation (10), and in the third phase the final variations are generated by assigning the most recent temporary variations obtained to them. These three phases are illustrated in FIGS. 3 , 4 and 5 which show three different methods of calculating the variations ΔN k . Identical steps are referenced by the same number in each of these figures.
Phase 1: Calculation of Temporary Variations
Note that N K +ΔN k ≈4RF i ·N k is true for all values of kεCBS(i,j). According to equation (5), we can then write:
D
(
l
)
=
∑
i
=
1
i
=
T
∑
k
∈
CBS
(
i
,
TF
i
(
1
)
)
RM
i
·
N
k
F
i
(
12
)
The member at the right of this equation is a rate estimator of the composite CCTrCH for the transport formats combination 1. This equation (12) can then be used to find an approximate value of the factor L maximized under the constraint represented by equation (10) to satisfy equation (11). According to a first embodiment illustrated in FIG. 3 , this value is given by the following equation:
L
=
N
data
max
1
≤
1
≤
C
∑
i
=
1
i
=
T
∑
k
∈
CBS
(
i
,
TF
i
(
1
)
)
RM
i
·
N
k
F
i
(
13
)
Note that the denominator in the member at the right of equation (13) is the maximum value of the rate estimator of the composite CCTrCH for the transport format combinations and calculated assuming L=1 (which is equivalent to assume fictitiously that RF 1 =RM i ).
This calculation step is denoted 301 in FIG. 3 . Note that transmission of the N data parameter is referenced 300 A in FIG. 3 . Similarly, the transmission of parameters {RM i } 1≦i≦T and the transmission of the numbers of symbols {N k } kε,CBS(I,F i (1)) are denoted 300 B and 300 C respectively.
We then determine the values of the various rate matching ratios RFi, making use of equations (5) and (13), in a step 302 .
The temporary variation ΔN k temp for each type k is then determined in a step 303 , for example using the following equation:
{
∀
i
∈
{
1
,
…
,
T
}
∀
j
∈
TFS
(
i
)
∀
k
∈
CBS
(
i
,
j
)
Δ
N
k
temp
=
⌈
RF
i
·
N
k
⌉
-
N
k
(
14
)
As a variant, equation (14) could be replaced by equation (14bis) given below. This equation has the advantage that the number of symbols after rate matching N k +ΔN k provided (assuming)N k =ΔN k temp ) at the beginning of the segmentation step 122 ( FIG. 1 ) is a multiple of the number F i of segments to be produced. Thus, all segments originating from the same block have the same number of symbols, which simplifies the receiver since the number of symbols does not vary during the TTI interval.
{
∀
i
∈
{
1
,
…
,
U
}
∀
j
∈
TFS
(
i
)
∀
k
∈
CBS
(
i
,
j
)
Δ
N
k
temp
=
F
i
⌈
RF
i
·
N
k
⌉
-
N
k
(
14
bis
)
As a variant, it would be possible to use a rounding function other than the x ┌x┐ function in equation (14) or (14bis). For example, it would be possible to use the x └x┘ where └x┘ is the largest integer less than or equal to x.
It would also be possible to consider calculating the factor L and the rate matching ratio RF i by making approximations, for example by expressing L and/or RF i as a fixed decimal number with a limited number of digits after the decimal point. This embodiment is illustrated in FIG. 4 .
Thus as a variant, the factor L is calculated using the following equation, in a step 401 :
L = 1 LBASE · ⌊ LBASE · N data max 1 ≤ 1 ≤ C ∑ i = 1 i = T ∑ k ∈ CBS ( i , TF i ( 1 ) ) RM i · N k F i ⌋ ( 13 bis )
where LBASE is an integer constant, for example a power of 2 such as 2 n , where n is the number of bits in the L factor after the decimal point.
The rate matching ratios RF i are then calculated in a next step 402 using the following equation:
∀ i RF i = 1 RFBASE · ⌊ RFBASE · L · RM i ⌋ ( 5 bis )
where RFBASE is an integer constant, for example a power of 2 such as 2 n , where n is the number of bits after the decimal point in RF i .
In the same way as for equations (5) and (14), the x └x┘ function in equations (5bis) and (14bis) can be replaced by any other rounding function.
According to a third embodiment illustrated in FIG. 5 , the expression of the factor L is modified by using a coefficient that depends on known data (for example {RM i } or N data ), in the numerator and in the denominator. This could have an impact on the calculated values to the extent that the expression of the factor L uses an approximation. For example, the following equation could be used:
L
=
1
LBASE
·
min
RM
i
1
≤
i
≤
T
·
⌊
LBASE
·
(
min
1
≤
i
≤
T
RM
i
)
N
data
max
1
≤
1
≤
C
∑
i
=
1
T
∑
k
∈
CBS
(
i
,
TF
i
(
1
)
)
RM
i
·
N
k
F
i
⌋
(
13
ter
)
The rate matching ratios RF i are then calculated using equation (5) or (5bis).
In summary, the phase in which the temporary variations ΔN k temp are calculated comprises the following steps:
1. Calculate the factor L as a function of the maximum physical rate N data and the RM i parameters (step 301 , 401 or 501 ).
2. Calculate the rate matching ratio RF i for each coded transport channel i, as a function of the RM i parameters and the factor L (step 302 , 402 or 502 ).
For each k type coded block in a coded transport channel i, calculate the temporary variation ΔN k temp as a function of the number of symbols N k before rate matching and the rate matching ratio RF i (step 303 ).
Phase 2: Global Correction of Temporary Variations
In this second phase, an iterative check is carried out to verify that the number of symbols D temp (1) per multiplexing frame for the CCTrCH composite is less than or equal to the maximum physical rate N data , for each transport format combination with index 1, where D temp (1) is determined using current values of temporary variations ΔN k temp , in other words initially with variations determined during the first phase and then with the most recent temporary variations calculated during the second phase. If necessary, the value of the temporary variations ΔN k temp is corrected. This step is also called the. global temporary variations correction step for all transport format combinations 1. This step is marked as reference 308 in FIGS. 3 , 4 and 5 .
If equation (9) is rewritten with temporary variations ΔN k temp , the following expression of the temporary rate D temp (1) of the composite is obtained:
D
temp
=
∑
i
=
1
T
∑
k
∈
CBS
(
i
,
TF
i
(
1
)
)
⌈
N
k
+
Δ
N
k
temp
F
i
⌉
(
9
bis
)
This calculation is carried out in step 304 in FIGS. 3 , 4 and 5 . As described previously, this second phase implies that D temp (1)≦N data for each transport format combination with index 1.
Every time that a transport format combination 1 is detected such that D temp (1)>N data , then the values of some temporary variations ΔN k temp are corrected by a “partial correction” step. Thus, the values of some temporary variations ΔN k temp reduced in this step so that the temporary rate D temp (1) of the composite is less than the maximum physical rate N data after correction.
Considering that the temporary rate D temp (1) of the composite is an increasing function that depends on temporary variations ΔN k temp , a partial correction applied to the transport format combination with index 1 does not change the result of verifications already made for previous transport format combinations. Therefore, there is no point of rechecking that D temp (1)≦N data for previously verified combinations.
The second phase is summarized by the following algorithm:
for all values of 1 from 1 to C, do
if D temp (1) ≦ N data then
partial correction of ΔN k temp values
end if
end do.
The step in which the maximum physical rate N data is compared with the temporary rate D temp (1) of the composite and the step in which temporary variations ΔN k temp are partially corrected, are denoted 305 and 306 , respectively, in FIGS. 3 , 4 and 5 . The final variations ΔNk are the temporary variations ΔN k temp obtained at the end of the second phase. This assignment step forms the third phase.
We will now describe the partial correction step of the temporary variations ΔN k temp mentioned in line 3 of the previous algorithm. In the remainder of the description of the partial correction, all notation used is applicable for a current index 1 of the transport format combination 1 is not always given in the new expressions, in order to simplify the notation.
Remember that MBS(1) is the set of coded block indexes for the transport format combination 1. In other words, we have:
MSB
(
1
)
=
⋃
1
≤
i
≤
T
CBS
(
i
,
TF
i
(
1
)
)
Let U be the number of elements of MBS(1). Since MBS(1) is a set of integer numbers, it is ordered into the canonical order of integer numbers. Therefore, it is possible to define a strictly increasing monotonic bijection K from {1, . . . , U} to MBS(1). We then have:
MBS (1)={ K (1), K (2), . . . , K ( U )}
where
K (1)< K (2)<. . . < K ( U )
Note that any other ordering rule can be used as a variant, for example another bijection of (1, . . . , U) to MBS(1). (K(1), . . . , K(U)) defines an ordered list. Similarly, for every coded block with index k in MBS(1), there is a single coded transport channel i producing this coded block for the transport format combination with index 1 such that kεCBS(i,TF i (1)). Therefore, it is possible to univocally define an application I from {1, . . . , U} to {1, . . . , T}, which identifies the single transport channel with index i=I(x) such that kεCBS(I,TF(1)) for each coded block with index k=K(x).
Thus, a partial sum S m can be defined for all values of mε{1, . . . , U}, for m equal to U, a total sum S U , and an coefficient Z m increasing as a function of m such that:
S
m
=
∑
x
=
1
x
=
m
RM
I
(
x
)
·
N
K
(
x
)
F
I
(
x
)
(
16
)
Z
m
=
⌊
S
m
S
U
·
N
data
⌋
(
17
)
Note that, like for any coded transport channel i, 8 is a multiple of the duration F i expressed as a number of multiplexing frames in the TTI interval in the coded transport channel i, then the partial sum S m can be coded without approximation as a fixed decimal number with 3 bits after the decimal point.
As a variant, the x └x┘ rounding function in equation (17) may be replaced by any other increasing monotonic rounding function.
Assuming Z 0 =0, new variations called the intermediate variations ΔN k new can then be defined and can replace the temporary variations ΔN k temp used for the transport format combination 1. These intermediate variations ΔN K(x) new are given by the following equation:
∀ x , {1, . . . , U}ΔN K(x) new =( Z x −Z x−1 )· F 1(x) −N K(x) (18)
In summary, temporary variations ΔN k temp are partially corrected using the following algorithm:
for all x from 1 to U, do
if ΔN K(−x) temp > ΔN K(x) new then
ΔN K(x) temp ← ΔN K(x) new
end if
end do.
Note that the ← symbol in the third line of the algorithm means that the value of ΔN K(x) temp is changed, and that it is replaced by the value of ΔN K(x) new .
This partial correction step is illustrated in FIG. 6 . In a first step 601 , the intermediate variation ΔN K(x) new is calculated and is then compared with the value of the corresponding temporary variation ΔN K(x) temp in a step 602 . If ΔN K(x) temp >ΔN K(x) new , the value of the intermediate variation ΔN K(x) temp is assigned to the temporary variation ΔN K(x) temp in a step 603 , and then the next step 604 is executed. If ΔN K(x) temp <ΔN K(x) new , the next step 604 is executed directly. In this step 604 , it is checked whether x is equal to the value U. If it is not, x is incremented in a step 605 , and then step 601 is carried out again with this new value of x. If x is equal to U, the partial correction step is terminated.
Phase 3: Determination of Final Variations
Remember that during this third phase, the value of the final variations ΔN k are the values of the temporary variations ΔN k temp originating from the second phase. This phase corresponds to step 307 in FIGS. 3 , 4 and 5 . Consequently, the value of the final rate D(1) of the composite is equal to the value given by equation (9), for a given transport formats combination 1.
In order to enable blind rate detection, a “fixed service positions” technique comprises the step in which DTX symbols are inserted in step 116 such that the rate (including DTX symbols) at the end of this step 116 is constant.
Consequently, all steps following encoding of the channel are carried out independently of the current rate. Thus in reception, demultiplexing, de-interleaving steps, etc., can be carried out in advance without knowing the current rate. The current rate is then detected by the channel decoder (performing the reverse of the operation done by the channel encoder 108 ).
In order for the step inverse to step 118 of rate matching to be independent of the current rate, the puncturing pattern or repetition pattern should be independent of the rate, in other words the number of coded blocks and the numbers of symbols N in each.
Thus firstly, in the case of fixed service positions there is never more, than one coded block per TTI interval, and in fact it is considered that there is always one if it is assumed that the lack of a coded block is equivalent to the presence of a coded block without a symbol. Consequently, the number of blocks does not vary as a function of the rate.
The optimum puncturing/repetition pattern depends on the N and ΔN parameters giving the number of symbols before rate matching and the variation due to rate matching, respectively. Therefore, these two parameters need to be constant to obtain a pattern independent of the rate, in other words the rate matching step 118 should be placed after step 122 in which DTX symbols are inserted. However, since all DTX symbols are identical, puncturing them or repeating them at predetermined positions induces unnecessary complexity (the same result can be achieved by puncturing or repeating the last DTX symbols in the block, and this is easier to implement). Therefore, it was decided that the rate matching step 118 and the DTX symbol insertion step 122 would be carried out in this order as shown in FIG. 1 , but that the repetition/puncturing pattern would be determined only for the case in which the composite is at its maximum rate. The pattern thus obtained is truncated for lower rates.
Note that in prior art, the fixed service positions and flexible service positions are two mutually exclusive techniques. In the invention, it is possible to have some transport channels in fixed service positions, and other channels in flexible service positions. This makes it possible to carry out blind rate detection only for transport channels in fixed service positions, and a rate detection using an explicit rate information for the other transport channels. Thus, the explicit rate information, TFCI, only indicates current transport formats for transport channels in flexible service positions. The result is that a lower capacity is necessary for TCFI transmission.
In the case of combined fixed and flexible service positions, some composite transport channels are in fixed service positions and others are in flexible service positions. Step 116 in which DTX symbols are inserted is only present for coded transport channels in fixed service positions, and it is missing for other transport channels that are in flexible service positions. Furthermore, the DTX symbol insertion step 132 is present if there is at least one coded transport channel in fixed service positions, and otherwise it is missing.
During reception of a multiplexing frame and the associated TFCI, the receiver may implement all steps inverse to those following the channel encoding. The TFCI information gives it the encoding format of coded transport channels in flexible service positions, and for transport channels in fixed service positions, the receiver acts as if they were in the highest rate transport format.
In the invention, the repetition/puncturing pattern depends on the two parameters N and ΔN, regardless of whether the coded transport channel is in the fixed service positions or flexible service positions, however in the flexible service position N and ΔN correspond to the number of symbols before rate matching and to the variation of this number during the rate matching step 118 , respectively, while in fixed service positions they are only two “fictitious” parameters used to determine the puncturing pattern when the coded transport channel rate is not maximum. In other words, these two parameters correspond to the size of the block for which the rate is to be matched, and its variation after rate matching when the rate of the coded transport channel is maximum.
When the rate of the coded transport channel is not maximum, the puncturing/repetition pattern is truncated. This pattern is actually a list of symbol positions that are to be punctured/repeated. Truncating consists of considering only the first elements in this list, which are real positions in the block for which the rate is to be matched.
Thus according to the invention, when there is at least one coded channel in the fixed service positions, rate matching parameters are determined in the same way as when all coded transport channels are in the flexible service positions, except that coded transport channels in fixed service positions are considered fictitiously to be at their maximum rate.
Consider the example in FIG. 2 , and assume that coded transport channel D is in the fixed service position, whereas transport channels A, B and C are in flexible service positions. The table below shows the list of transport format combinations for this example.
Transport format for
Combination
transport channels
Example frame
index
A
B
C
D
with this combination
0
0
2
0
0
11
1
0
2
0
2
10
2
0
3
0
0
12
3
0
3
0
1
13
4
0
2
2
1
8
5
2
0
2
1
0
6
0
2
2
2
9
7
2
1
1
0
5
8
2
0
2
2
1 and 2
9
0
3
2
1
14 and 15
10
2
1
1
1
4
11
2
0
2
3
3
12
2
1
2
1
6 and 7
The rate matching configuration parameters are calculated in the same way as for flexible service positions, except that it includes the additional prior step of fictitiously replacing the column in this table corresponding to coded transport channel D, by setting all elements to the transport format for the highest rate, in other words the transport format with index 3. This gives the following “fictitious” table in which the boxes that have been modified and which correspond to “fictitious” transport formats are shown in grey:
Transport format for
Combination
transport channels
Example frame
index
A
B
C
D
with this combination
0
0
2
0
3
11
1
0
2
0
3
10
2
0
3
0
3
12
3
0
3
0
3
13
4
0
2
2
3
8
5
2
0
2
3
0
6
0
2
2
3
9
7
2
1
1
3
5
8
2
0
2
3
1 and 2
9
0
3
2
3
14 and 15
10
2
1
1
3
4
11
2
0
2
3
3
12
2
1
2
3
6 and 7
By definition, coded transport channels i in the fixed services positions, have not more than one coded block per TTI interval (∀jεTFS(i) CBS(ij) has not more than one element).
Furthermore, in the invention it is assumed that coded block sizes are indexed such that the absence of a coded block for coded transport channels in fixed service positions leads to indexing with the convention that the absence of a block is equivalent to the presence of a zero size block (i.e., an index k is assigned with N k =0, and therefore ∀j εTFS(i) CBS(ij) has at least one element).
With the previous assumptions, the first phase in the calculation of the temporary variations ΔN k temp , which has already been described, must be preceded by the following step when there is at least one coded transport channel in the fixed service positions.
For all i from 1 to T do
if the coded transport channel with index i is
in the fixed service positions then
for all values of j in TFS(i), do
let k be the single element of CBS(I, j)
N
k
←
max
j
′
∈
TFS
(
i
)
k
′
∈
CBS
(
k
,
j
′
)
N
k
′
end do
end if
end do
The fifth instruction means that the coded transport channel i is fictitiously considered to be at its maximum rate; its actual rate (N k ) is replaced (←) by its maximum rate
(
max
j
′
∈
TFS
(
i
)
k
′
∈
CBS
(
k
,
j
′
)
N
k
′
)
.
|
The invention relates to a method for configuring a telecommunication system comprising at least one sending entity and one receiving entity between which the same link transmits several transport channels with different qualities of service. The sending entity matches the rate between the different coded transport channels with separate qualities of service, and the different coded transport channels are then multiplexed. The matching rate specific to each coded transport channel is determined from at least one first parameter representative of the expected Eb/I ratio and a second parameter representative of the capacity of the physical channel.
| 7
|
FIELD OF THE INVENTION
[0001] The invention relates to oncology and methods of cancer diagnosis, stratification, disease staging and treatment. The field of the invention therefore concerns markers of predictive or clinical value in cancer diagnosis and treatment and the use of medicaments for the treatment of cancer. The invention also concerns screening assays for identifying active anti-cancer agents.
BACKGROUND TO THE INVENTION
[0002] Chemokine receptors and their ligands direct the trafficking of cells in normal tissue homeostasis and in disease, influencing cell motility, invasiveness and survival [1]. In inflammation and in cancer, chemokines in the diseased tissues contribute to the rolling, tethering and invasion of leucocytes from the blood vessels through the endothelial cell basement membrane and into the parenchyma [2].
[0003] CCR4 is one of 18 known chemokine receptors. Chemokine receptors are generally expressed on immune cells and in the tumour microenvironment a number of receptors and their ligands are present in the immune cell infiltrate.
[0004] In many cancers, malignant cells also express certain chemokine receptors, receptors that are not usually found on their normal counterparts. Metastatic cancer cells are thought to gain characteristics of chemokine receptor-expressing leucocytes, using chemokines to aid their migration to, and survival at, sites distant to the original tumour [3, 4, 5]. Inappropriate presence on cancer cells of chemokine receptors that usually have a highly restricted pattern of expression further supports the hypothesis that specific chemokine receptors may help cells spread to, and/or survive in, different metastatic sites [8]. In carcinomas, melanomas and haematological malignancies, expression of chemokine receptors, especially CXCR4 and CCR7, on malignant cells in advanced disease, correlates with increased lymph node metastasis, greater dissemination of disease, lower disease-free survival and/or overall survival [6,7,8]. CXCR5 is normally restricted to B cells and some T cell subtypes, but is also expressed by pancreatic cancer cells where it is implicated in the establishment of liver metastases; the liver being a site of production of the CXCR5 ligand, CXCL13 [9]. Melanoma cells that have metastasised to the intestine express CCR9 [10]. In homeostasis, the CCR9 ligand CCL25 recruits rare T cell subsets to the intestine. In pancreatic cancer, expression of CCR6 has been observed [38][39]. CCR6 expression has also been reported in human renal carcinoma, together with CCR3 and CXCR2 [40].
[0005] This demonstrates that a few chemokine receptors are known to be upregulated in tumour epithelial cells in late stage carcinogenesis, including CXCR4, and are thought to play a role in invasion and metastasis. In contrast, CCR4 has only previously been reported to be upregulated in some blood cancers, particularly T cell lymphomas.
[0006] As described above, CXCR4 is commonly found on malignant cells in many advanced human cancers. In addition, Woerner et al found that CXCR4 was also present in the early stages of disease in glioblastoma [20]. However, using a phospho-specific anti-CXCR4 antibody, they found that in the less malignant Grade 1 lesions, the level of receptor activation was much lower.
[0007] Although it is generally reported that malignant cell chemokine receptor expression is associated with advanced disease, there are also a few other reports in the art of expression of a chemokine receptor on malignant cells at early and pre-invasive stages of cancer, but all of these concern CXCR4. In a large tissue array study (over 2000 samples) of breast cancer, cytoplasmic/membrane expression of CXCR4 expression was reported in 67% of ductal carcinomas in situ, DCIS [21]. This was confirmed in a study from Schmid et al who showed that both CXCR4 and its ligand CXCL12 were expressed in DCIS [22]. The inventors have also found CXCR4 on the epithelial cells of borderline non-invasive ovarian cancer tumours (Kulbe et al., manuscript in preparation) and this has also been reported by Pils et al [23].
[0008] No data on expression of other chemokine receptors on epithelial cells in early cancers is available, but there is evidence that oncogenic pathways can induce chemokine receptor expression on epithelial cells. The RET/PTC1 oncogene is necessary and sufficient for malignant transformation of primary thyrocytes [24]. This oncogene induces a pro-inflammatory programme in the thyrocytes that includes induction of functional CXCR4. Alveolar rhabdomyosarcoma is a highly aggressive tumour characterised by recurrent PAX3 and PAX7-FKHR gene fusions. Transfer of PAX3-FKHR into embryonal rhabdomyosarcoma cells also activates CXCR4 expression [Libura, 2002 #9346].
[0009] In all these studies a conclusion is that acquisition of certain chemokine receptors by malignant cells appears to be, a relatively late event in malignant progression, and in the case of CCR4, expression has not been reported at any stage of solid tumour development
[0010] CCR4 expression is generally restricted to the immune system, and is known as a marker of Th2 and regulatory T cells. In the tumour environment, these cells act to suppress cytotoxic T cells and dendritic cell maturation, hence suppressing anti-tumour immune responses. In addition, CCR4 has been shown to be expressed in haematological malignancies, including by a high proportion of adult T cell lymphomas (ATL), and was a significant prognostic factor associated with metastasis to skin [35], [41]. As such, CCR4 is of interest as a therapeutic target in ATL [37], [42]. CCR4 expression by adult T cell leukaemia is associated with skin metastases; its ligands CCL17 and CCL22 are produced by both malignant cells and the skin tumor microenvironment [36]. Ishida et al have developed an anti-CCR4 monoclonal antibody therapeutic for the treatment of adult T cell lymphoma that induces ADCC activity against the tumor cells and may also act on immunosuppressive malignant Treg cells found in this disease [37].
[0011] The only report in the academic literature of a CCR4 positive solid tumor cell line is the human lung cancer cell line SBC-5 [34]. These cells migrated towards CCL22 gradients and in bone metastatic SBC-5 xenografts there was close co-localisation of osteoclasts expressing CCL22 and SBC-5 cells expressing CCR4. There are no reports of CCR4 expression in primary human tumour cells.
[0012] WO05106471 (BAYER HEALTHCARE AG) discloses screening methods for agents of potential use in treating a wide range of diseases; specifically consisting of cardiovascular disorders, gastrointestinal and liver diseases, inflammatory diseases, metabolic diseases, haematological disorders, cancer disorders, neurological disorders, respiratory diseases and reproduction disorders in a mammal. The screening method determines the degree of binding or otherwise of candidate agents to CCR4. There is also a description of the screening of a wide range of human cells and tissues for their expression level of CCR4 relative to housekeeping gene expression. The cells and tissues were obtained from disparate sources and just an isolated few were cancerous cells/tissues; e.g. thyroid, ileum, HeLa, Jurkat, lung and breast cancer cells. The results for the relative expression of CCR4 show no distinguishable pattern associated with any particular disease. Indeed amongst tumour cells tested, e.g. thyroid and ileum, there were low levels of relative expression of CCR4 and other non-tumour cells showed higher levels of relative expression of CCR4.
[0013] WO9623068 (GLAXO GROUP LIMITED) discloses a chemokine receptor able to bind to Monocyte Chemotactic Protein-1 (MCP-1/CCL2), Macrophage Inflammatory Protein 1α (MIP1α/CCL3) and/or ‘RANTES’ (Regulated upon Activation, Normal T-cell Expressed, and Secreted/CCL5). A nucleotide and an amino-acid sequence for CCR4 are disclosed (CC-CKR-4/K5.5. K5.5 and CC-CKR-4 are alternative names for CCR4.) The expression of CCR4 is discovered in a relatively limited range of normal human tissues and in a range of T-cell samples. There is also general disclosure of screening assays for agents capable of activating T-lymphocytes or blocking binding of ligands MCP-1, MIP-1α and/or RANTES to the chemokine receptor. There is some suggestion that active agents obtained via screening may be useful in the treatment of allergies, for example.
[0014] WO0041724A1 (LELAND STANFORD/LEUKOSITE) proposes the modulation of systemic memory T cell trafficking by administration of CCR4 modulating agents. This is intended as a treatment for inflammatory skin disease. Substances capable of modulating CCR4 binding to its ligands are used in in vitro tests to show how T-cell migration is affected.
[0015] Antibodies reactive against CCR4 are known. WO0164754 (Kyowa Hakko Kogyo) discloses a recombinant antibody or fragment thereof allegedly reactive specifically with the extracellular domain of CCR4. Also disclosed is a polypeptide sequence of such an antibody. There is also disclosed an antibody which reacts with a CCR4 positive cell and is cytotoxic or causes antibody-dependent cell-mediated cytotoxicity (ADCC.) These antibodies are proposed for the use in the treatment of Th2-mediated immune diseases or blood cancer, specifically leukaemia.
[0016] WO05035582 (Kyowa Hakko Kogyo) discloses an antibody capable of specifically binding CCR4 and also discloses a CCR4 antibody which has a complex N-linked glycosylation in the Fc region. Also disclosed are antibodies to the extracellular domains of CCR4.
[0017] WO03018635 (Kyowa Hakko Kogyo) discloses ‘Human CDR-grafted antibodies and fragments’. A specific CDR (complementarity determining region) which binds specifically to CCR4 is disclosed. The antibodies are proposed for use in the diagnosis or treatment of Th2-mediated immune diseases or cancers such as blood cancers.
[0018] WO05053741 (Kyowa Hakko Kogyo) discloses a medicament comprising a recombinant antibody, which specifically binds CCR4, in combination with at least one other agent. The antibody is proposed for the treatment of tumours, specifically haematopoietic organ tumours.
[0019] WO0042074 (MILLENIUM PHARMACEUTICALS) discloses antibodies to CCR4 and antibodies that can compete with their binding. No specific diagnostic applications are disclosed. Therapy of inflammatory disorders is proposed.
[0020] Also known in the art are a variety of small molecules that bind to the CCR4 receptor.
[0021] WO04007472 (ONO PHARMACEUTICAL CO.) discloses a small molecule tricyclic compound with anti-CCR4 activity.
[0022] WO05023771 (ONO PHARMACEUTICAL CO.) discloses small molecule nitrogen-containing heterocyclic compounds with anti-CCR4 activity.
[0023] WO02094264 (TULARIK INC.) discloses specific compounds with CCR4 inhibitory activities.
[0024] WO0230358 (TULARIK/CHEMOCENTRYX) discloses various CCR4-binding compounds and uses for treatment of various diseases, but not including cancer.
[0025] WO0230357 (CHEMOCENTRYX) discloses compounds that are antagonists of CCR4. This application describes uses for the treatment of inflammatory diseases and conditions.
[0026] WO051236976 (ASTELLAS PHARMA INC.) discloses quinazoline derivatives as CCR4 regulators.
[0027] WO05085212 (YAMANOUCHI PHARMACEUTICAL CO., LTD.) discloses pyrimidine derivatives as CCR4 modulators.
[0028] WO05082865 (YAMANOUCHI PHARMACEUTICAL CO., LTD.) discloses fused bicyclic pyrimidine derivatives as CCR4 function-controlling agents.
[0029] WO04108717 (ASTRAZENECA AB) discloses sulphonamide compounds that modulate chemokine (specifically CCR4) receptor activity.
[0030] EP1633729 (ASTRAZENECA AB) discloses sulphonamide compounds that modulate chemokine (specifically CCR4) receptor activity.
[0031] WO03014153 (TOPIGEN PHARMACEUTIQUE INC.) discloses another technology in the art, a method of modulating viral infection of a cell by modulating the interaction between chemokine receptors (including CCR4) and a virus.
[0032] WO2004/045526 (Morehouse School of Medicine) discloses antibodies to particular chemokines and chemokine receptors and their use in inhibiting the growth and metastasis of cancer cells. Antibodies were raised against the particular chemokine receptors and their ligands, which does not include CCR4. Also described are methods of testing for over-expression of particular chemokines in a tumour and the suggestion that such tumours can be treated by administering antibodies against the particular over-expressed chemokine or chemokine receptor.
[0033] WO99/15666 (Icos Corporation) discloses nucleotide sequences and polypeptide sequences of a macrophage-derived C-C chemokine designated ‘Macrophage Derived Chemokine’ (MDC). MDC appears synonymous with CCL22. TARC appears synonymous with CCL17. Methods for the recombinant or synthetic production of MDC protein or polypeptide fragments are described. Also disclosed are antibodies reactive with MDC as well as assays for identifying modulators of MDC and TARC chemokine activity.
[0034] Cervical cancer is the second most common type of cancer in women worldwide. Symptoms are often absent until the cancer is at a late stage and hence cervical cancer has been the subject of an intense population screening program using the Pap smear, which can detect pre-malignant changes by histopathology. Although an abnormal Pap smear indicates possible cervical neoplasia, it is insufficient for diagnosis, which is subsequently carried out by biopsy and additional invasive procedures (‘colposcopy’). In total, 24,000 women are referred in the UK each year with abnormal Pap smears. The Pap smear has only 70% sensitivity, hence a significant proportion of women with cervical cancer or pre-invasive lesions remain undiagnosed. Therefore, more accurate screening methods are required to i) allow screening to be more automated and less subjective ii) to improve the sensitivity of screening.
[0035] HPV (Human Papilloma Virus) infection is found in the majority of invasive cervical carcinomas, one strategy is to screen for the presence of HPV markers such as E6 and E7 in concert with the Pap smear. However, due to the high level of HPV infection in the sexually active population (up to 80% infection history), this also results in the identification of a large number of false positives and makes the accuracy of the test dependent on HPV prevalence. As such, identifying new biomarkers for cervical cancer remains an area of active interest.
[0036] Furthermore new or alternative biomarkers are required for other forms of cancer including, but not limited to, the following cancer types: bronchial, nasopharyngeal, laryngeal, small cell and non-small cell lung, skin (e.g. melanoma or basal cell carcinoma), brain, pancreatic, neck, lung, kidney, liver, breast, colon, bladder, oesophagus, stomach, cervical, ovarian, germ cell and prostate. A biomarker characteristic of one cancer type may be shared with other cancer types thus the use of a biomarker may extend beyond the original cancer type it was found to be associated with.
[0037] There is a need for improved biomarkers for a range of cancers which allow for stratification of patients in need of anti-cancer treatment.
[0038] The stage of a cancer is a descriptor (usually numbers I to IV) of how much the cancer has spread. The stage often takes into account the size of a tumour, how deep it has penetrated, whether it has invaded adjacent organs, if and how many lymph nodes it has metastasized to, and whether it has spread to distant organs. Staging of cancer is important because the stage at diagnosis is the most powerful predictor of survival, and treatments are often changed based on the stage
[0039] Correct staging is critical because treatment is directly related to disease stage. Thus, incorrect staging would lead to improper treatment, and material diminution of patient survivability. Correct staging, however, can be difficult to achieve. Pathologic staging, where a pathologist examines sections of tissue, can be particularly problematic for two specific reasons: visual discretion and random sampling of tissue. “Visual discretion” means being able to identify single cancerous cells intermixed with healthy cells on a slide. Oversight of one cell can mean mis-staging and lead to serious, unexpected spread of cancer. “Random sampling” refers to the fact that samples are chosen at random from patients' lymph nodes and are examined. If cancerous cells present in the lymph node happen not to be present in the slices of tissue viewed, incorrect staging and improper treatment can result.
[0040] There is an ongoing need for new treatments against cancer, whether these involve improved ways of administering existing anti-cancer agents, or whether these involve identifying, testing and verifying effective new anti-cancer agents. There is also an ongoing need for improved methods of monitoring the efficacy of existing and any new anti-cancer agents in the course of a given treatment regime. Improved methods of generating data of predictive value are needed. The dosage and frequency of treatments using anti-cancer agents is an important factor. Also, the timing of the start of an anti-cancer treatment relative to the stage of progression of a cancer, or relative to a patient group, are important factors. Improved methods of monitoring are required in order to seek optimal treatments for patients, whether as individuals or classified into groups by virtue of genetic, phenotypic or other characteristics.
[0041] An example of the prognostic function of a biomarker in the choice of treatment for a patient is the use of the anti-cancer drug Herceptin (Trastumuzab). The HER2/neu gene is a proto-oncogene located at the long arm of human chromosome 17(17q11.2-q12) and amplification of HER2/neu occurs in 25-30% of early-stage breast cancers. In cancer the growth promoting signals from HER2/neu are constitutively transmitted, promoting invasion, survival and angiogenesis of cells. Furthermore overexpression can also confer therapeutic resistance to cancer therapies. Herceptin (Trastumuzab) is a humanised monoclonal antibody which binds to the extracellular segment of the receptor HER2/neu, (also known as ErbB-2) and is only effective in treating breast cancer where the HER2/neu receptor is overexpressed. Because of its prognostic role as well as its ability to predict a patient's response to Herceptin breast tumors are routinely checked for overexpression of HER2/neu by a variety of techniques including immunohistochemistry (IHC) Chromogenic and fluorescence in situ hybridisation (CISH and FISH respectively).
[0042] There also exists the need for more accurate and reliable methods of diagnosing/staging of cancers and a need for new methods for screening anti-cancer agents.
SUMMARY OF THE INVENTION
[0043] The inventors have surprisingly discovered that in certain solid tumours, chemokine receptor CCR4 expression is an early event in carcinogenesis. In addition the inventors have discovered that the expression of two ligands of CCR4, CCL17 and CCL22, increases during tumour progression.
[0044] The present invention provides a method of obtaining information of predictive or diagnostic character for a cancer patient, comprising the step of measuring the amount and/or activity of chemokine receptor CCR4 expressed by tumour cells in a solid tumour sample or in a non-haematological cell tumour sample taken from the patient, the amount and/or activity of CCR4 providing the information of predictive or diagnostic character.
[0045] Haematological tumours are derived from blood cells, including immune cells and include leukaemias and lymphomas of various types. The invention does not therefore concern haematological tumours.
[0046] In the solid or non-haematological tumours which the invention is concerned with, CCR4 is expressed by cells of the tumour. The methods of the invention therefore concern the CCR4 expressed by samples of patient tumour cells (or reference cells) and substantially not by cells of the immune system. To the extent that CCR4 arises in any patent tumour samples from an undesired source, such as infiltrating immune cells, the amount and/or activity of CCR4 being measured in accordance with the invention is either not significant or it is controlled for in any measurements being made.
[0047] In preferred embodiments, the reference amount and/or level of activity of CCR4 may be measured in one or more non-tumour samples. The, or at least one non-tumour sample may be taken from the patient. When a reference amount and/or level of activity of CCR4 is determined from non-tumour cells of the patient, a single sample of non-tumour tissue may be taken from the patient. If desired, a multiplicity of non-tumour samples can be taken from different locations of the same patient. The reference amount may therefore be a mean figure determined from a number of samples taken from the patient.
[0048] In other embodiments, the one or more non-tumour samples are optionally not taken from the patient. Such samples may be taken from other patients and may include cultured tumour cell lines.
[0049] The information may be used to predict whether the solid tumour or the non-haematological cell tumour of the patient will be susceptible to an anti-cancer treatment. This aspect of the invention advantageously permits stratification of cancer patients. This allows an optimal anti-cancer treatment or regime to be identified for a given individual patient.
[0050] In preferred embodiments, the patient will have received an anti-cancer treatment and measurements of the amount and/or activity of CCR4 in the solid tumour sample or the non-haematological tumour sample of the patient may be made before and after the start of treatment, and the information obtained is then used to determine whether the solid tumour or the non-haematological cell tumour of the patient has responded to the anti-cancer treatment. This aspect of the invention advantageously permits monitoring of cancer patients to determine how their individual treatment is progressing. Adjustments to the treatment regime may be made in light of the progress being made.
[0051] The information may be used in diagnosis of a solid tumour or a non-haematological cell tumour.
[0052] The information may be used to stage a solid tumour or a non-haematological cell tumour.
[0053] The invention also provides a method of obtaining information of predictive or diagnostic character for a cancer patient whose tumour cells express chemokine receptor CCR4, comprising the step of measuring the amount and/or activity of CCR4 ligand CCL17 and/or CCL22 in a solid tumour sample or in a non-haematological cell tumour sample taken from the patient, the amount and/or activity of CCL17 and/or CCL22 providing the information of predictive or diagnostic character.
[0054] The information of predictive or diagnostic character may be obtained by comparing the amount and/or activity of CCL17 and/or CCL22 in the solid tumour sample or in the non-haematological cell tumour sample with a reference amount and/or level of activity of CCL17 and/or CCL22.
[0055] The reference amount and/or level of activity of CCL17 and/or CCL22 may be measured in one or more non-tumour samples. As in the previous aspect of the invention, non-tumour samples may be taken from the patient or from a different patient or source, including cultured cell lines.
[0056] The information may be used to predict whether the solid tumour or the non-haematological cell tumour of the patient will be susceptible to an anti-cancer treatment.
[0057] In further optional embodiments, the patient has received an anti-cancer treatment and measurements of the amount and/or activity of CCL17 and or CCL22 are made before and after the start of treatment and the information obtained is used to determine whether the solid tumour or the non-haematological cell tumour of the patient has responded to the anti-cancer treatment.
[0058] In all aspects of the invention, a particular anti-cancer treatment may comprise an agent which modulates or inhibits CCR4 expression or activity.
[0059] The invention also provides the use of an antibody reactive against chemokine receptor CCR4 for detecting the presence or measuring the amount of CCR4 expressed by a solid tumour or a non-haematological tumour in a cancer patient, the presence or amount of CCR4 expressed by the tumour and when detected or measured providing the information of diagnostic character.
[0060] The invention further provides the use of an oligonucleotide primer or probe capable of hybridizing under stringent conditions to a nucleic acid of SEQ ID NO:1 for detecting or measuring the amount of expression of CCR4 by cells of a solid tumour or a non-haematological tumour, the presence or amount of CCR4 expressed by the tumour when detected or measured providing the information of diagnostic character.
[0061] The aforementioned uses to which the information may be put are as hereinbefore defined in relation to the method aspects of the invention.
[0062] The nucleic acid of SEQ ID NO:1 is not limited to the specific sequence, but includes variants which still encode biologically active CCR4 protein. Such variants may include nucleotide sequences having at least 99% identity with SEQ ID NO:1. Other variants may have at least 95%, optionally at least 90% identity. The range of identities of from at least 65% to at least 99% identity with SEQ ID NO:1 is disclosed herein.
[0063] A variety of stringent hybridisation conditions will be familiar to the skilled reader in the field. Hybridization of a nucleic acid molecule occurs when two complementary nucleic acid molecules undergo an amount of hydrogen bonding to each other. The stringency of hybridization can vary according to the environmental conditions surrounding the nucleic acids, the nature of the hybridization method, and the composition and length of the nucleic acid molecules used. Calculations regarding hybridization conditions required for attaining particular degrees of stringency are discussed in Sambrook et al., Molecular Cloning: A Laboratory Manual (Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., 2001); and Tijssen, Laboratory Techniques in Biochemistry and Molecular Biology—Hybridization with Nucleic Acid Probes Part I, Chapter 2 (Elsevier, New York, 1993). The T m is the temperature at which 50% of a given strand of a nucleic acid molecule is hybridized to its complementary strand. The following is an exemplary set of hybridization conditions and is not limiting:
[0000] Very High Stringency (Allows Sequences that Share at Least 90% Identity to Hybridize)
[0000] Hybridization: 5x SSC at 65° C. for 16 hours Wash twice: 2x SSC at room temperature (RT) for 15 minutes each Wash twice: 0.5x SSC at 65° C. for 20 minutes each
High Stringency (Allows Sequences that Share at Least 80% Hybridize)
[0000] Hybridization: 5x-6x SSC at 65° C.-70° C. for 16-20 hours Wash twice: 2x SSC at RT for 5-20 minutes each Wash twice: 1x SSC at 55° C.-70° C. for 30 minutes each
Low Stringency (Allows Sequences that Share at Least 50% Identity to Hybridize)
[0000]
Hybridization:
6x SSC at RT to 55° C. for 16-20 hours
Wash at least twice:
2x-3x SSC at RT to 55° C. for 20-30 minutes each.
[0064] The invention includes a method of treating a cancer patient having a solid tumour or a non-haematological tumour expressing CCR4, comprising administering an effective amount of an agent which modulates or inhibits CCR4 expression or activity.
[0065] The agent may be administered in the form of a pharmaceutical formulation. Suitable formulations include sterile aqueous or non-aqueous solutions, suspensions, and emulsions. The compositions may further comprise auxiliary agents or excipients, as known in the art, see, e.g., Berkow et al., The Merck Manual, 16 th edition Merck & Co., Rahman, N.J. (1992), Avery's Drug_Treatment: Principles and Practice of Clinical Pharmacology and Therapeutics, 3 rd edition, ADIS Press, Ltd., Williams and Wilkins, Baltimore, Md. (1987) & Osol (ed.), Remington's Pharmaceutical Sciences, Mack Publishing Co., Easton, Pa. 1324-1341 (1980). The pharmaceutical compositions administered in accordance with the invention are preferably presented in the form of individual doses (unit doses).
[0066] A composition or medicament employed in the methods and uses of the invention may further comprise salts, buffers, or other substances which are desirable for improving the efficacy of the composition. The administration of composition or medicament in accordance with the invention may be local or systemic.
[0067] The invention also includes the use of a chemokine receptor CCR4 modulating or inhibiting agent for the treatment or prevention of solid tumours or non-haematological tumours.
[0068] In all of the aforementioned method and use aspects of the invention, the agent which modulates or inhibits CCR4 expression or activity may be:
(i) an antibody which binds to CCR4; optionally an anti-CCR4 antibody as disclosed in any of WO0041724, WO0164754, WO05035582, WO03018635, WO05053741, WO0042074; or (ii) an antibody which binds to CCR4 ligands CCL17 or CCL22; optionally anti-CCL17 or anti-CCL22 antibodies as disclosed in WO99/15666 or Ishida, T., et al (2004) Clin Cancer Res 10:7529-7539. (iii) a CCR4 antagonist; optionally a CCR4 antagonist as disclosed in any of WO04007472, WO05023771, WO02094264, WO0230358, WO0230357, WO051236976, WO05085212, WO05082865, WO04108717, EP1633729, WO03014153.
[0072] Appropriate compositions and formulations of active agents include those described in the aforementioned publications.
[0073] The invention further provides a kit for obtaining information of predictive or diagnostic character for a cancer patient from a solid tumour or a non-haematological tumour sample from the patient, wherein the kit comprises:
at least one reagent selected from an antibody reactive with CCR4, an antibody reactive with CCL17, an antibody reactive with CCL22, and an oligonucleotide probe or primer capable of hybridizing with SEQ ID NO:1 under stringent conditions; and indicia directing a user of the kit to apply the reagent to a sample of a solid tumour or a non-haematological tumour from a patient so as to measure the amount and/or activity of one or more of CCR4, CCL17 and CCL22 in the sample.
[0076] In certain embodiments, the kit may comprise a reference sample of one or more non-tumour cells and the indicia are a set of instructions and direct the user of the kit to measure the amount and/or level of activity of one or more of CCR4, CCL17 and CCL22 in both the patient sample and the reference sample. The reference sample(s) may comprise cultured tumour cell or cell extracts.
[0077] In other embodiments, the indicia may be a set of instructions and include reference values for the reference amount and/or level of activity of one or more of CCR4, CCL17 and CCL22. The reference values are preferably obtained by previous work carried out by making measurements of amounts and/or activity of CCR4, CCL17 or CCL22 in selected non-tumour samples from individuals or patients, whether or not they have or have had a cancerous condition. Such previous measurements may have been carried out on cultured non-tumour human cell lines.
[0078] The invention also includes a method of screening for an anti-cancer agent active against a solid tumour or a non-hematological tumour which expresses chemokine receptor CCR4 comprising the steps of:
i) providing test cells that express CCR4 and are capable of, or are in the process of exhibiting a biological activity selected from (a) proliferation, (b) migration, (c) secretion of a protein or a signalling molecule, or (d) cell survival when cultured under specified conditions; ii) exposing the test cells to a candidate agent for a period of time, iii) measuring the biological activity of the test cells, whereby no biological activity or biological activity which is less than the expected activity of such test cells in the absence of candidate agent identifies an anti-cancer agent.
[0082] In preferred methods, a control aliquot of test cells is not exposed to the candidate agent and the biological activity of the control cells is measured so that the expected biological activity is determined.
[0083] The biological activity of the test cells and any control cells may be induced by the addition of a ligand of the CCR4 receptor, preferably CCL17 and/or CCL22.
[0084] In all aspects of the invention, the solid tumour or non-haematological tumour may be a cancer selected from cancer of the cervix, oesophagus, kidney, brain, breast, ovary, prostate, stomach or pancreas. The invention may be of particular advantage in relation to cancers of the cervix, oesophagus, kidney, brain, breast and ovary.
[0085] The invention therefore provides a method for determining whether a cancer patient is suitable for treatment with an agent that modulates CCR4 expression and/or CCR4 activity, comprising determining the amount or activity of CCR4 in a sample of patient tumour cells.
[0086] The invention further provides a method for determining whether a cancer patient is suitable for treatment with an agent that modulates the levels or activity of CCL17 and/or CCL22, comprising determining the amount or activity of CCL17 and/or CCL22 in a sample of patient tumour cells.
[0087] The invention therefore provides for the use CCR4, CCL17, and/or CCL22 as a biomarker for stratification of cancer patients according to their suitability for treatment with CCR4, CCL17 and/or CCL22 modulating or inhibiting agents, including the agents disclosed herein.
[0088] The suitability of a cancer patient for treatment with a particular therapeutic agent is governed by a multiplicity of factors, some inter-related. Patient age, sex, stage of the cancer, type of cancer, genetic make up of patient, lifestyle factors, such at diet or smoking, may all impact on the potential outcome of a given treatment regime. Stratification is usually undertaken in order to group patients on the basis of a multiplicity of selected parameters that can allow predictions to be made in terms of clinical outcome for a group of patients or an individual patient falling within a group.
[0089] Generally, an increased level or activity of one or more of CCR4, CCL17 and/or CCL22 in a patient tumour sample is indicative of a patient for whom treatment with the anti-cancer agents disclosed herein is beneficial.
[0090] The invention also includes a method of monitoring the efficiency of an anti-cancer treatment in a patient comprising determining the amount or activity of CCR4 in a sample of tumour cells from the patient,
[0091] The invention further includes a method of monitoring the efficiency of an anti-cancer treatment in a patient comprising determining the amount or activity of CCL17 and/or CCL22 in a sample of tumour cells from the patient.
[0092] In the aforementioned methods, the sampling of tumour cells may take place before, during and/or subsequent to the anti-cancer agent being administered.
[0093] The invention also provides methods for prevention or treatment of certain solid tumours as described herein comprising administration of an agent selected from:
(a) CCR4 modulating agents e.g. as disclosed in WO0041724A1 (LELAND STANFORD/LEUKOSITE); (b) anti-CCR4 antibodies, e.g. as disclosed in WO0164754 (Kyowa Hakko Kogyo), WO05035582 (Kyowa Hakko Kogyo), WO03018635 (Kyowa Hakko Kogyo), WO05053741 (Kyowa Hakko Kogyo) or WO0042074 (MILLENIUM PHARMACEUTICALS); or (c) CCR4 antagonists, e.g. as disclosed in WO04007472 (ONO PHARMACEUTICAL CO.), WO05023771 (ONO PHARMACEUTICAL CO.), WO02094264 (TULARIK INC.), WO0230358 (TULARIK/CHEMOCENTRYX), WO0230357 (CHEMOCENTRYX), WO051236976 (ASTELLAS PHARMA INC.), WO05085212 (YAMANOUCHI PHARMACEUTICAL CO., LTD.), WO05082865 (YAMANOUCHI PHARMACEUTICAL CO., LTD.), WO04108717 (ASTRAZENECA AB), EP1633729 (ASTRAZENECA AB) or WO03014153 (TOPIGEN PHARMACEUTIQUE INC.)
[0097] The invention therefore also provides a method for diagnosing a solid tumour in an individual susceptible to treatment with CCR4 modulating agents, anti-CCR4 antibodies or CCR4 antagonists, comprising determining the level of activity and/or expression of CCR4, CCL17 and/or CCL22 in a tumour sample from the patient. Increased levels of activity and/or expression, whether in absolute terms on a standardized basis having regard to reference values, or whether on a relative (standardized) basis as between (a) tumour/non-tumour cells or (b) tumour cells over time, is generally indicative of a tumour susceptible to treatment with the anti-CCR4 agents disclosed herein.
[0098] The invention includes a method of providing information of diagnostic relevance to the diagnosis or treatment of solid tumours, wherein the method comprises determining the amount or activity of CCR4, CCL17 and/or CCL22 in a sample of cells from a patient suspected of having cancer.
[0099] The present invention also provides a method of identifying or staging a cancer in an individual comprising determining the level of one or more of the chemokine receptor CCR4, or its ligands CCL22 or CCL17, in a sample of tumour cells obtained from the individual, wherein the cancer is a solid tumour.
[0100] Advantageously, the methods of the invention provide a more reliable and more accurate way of identifying, or staging cancer in an individual, or for stratifying individuals for selection of appropriate treatments, particularly in relation to solid tumours, more particularly cervical and oesophageal cancers, but also including cancers selected from the group consisting of bronchial, nasopharyngeal, laryngeal, small cell and non-small cell lung, skin (e.g. melanoma or basal cell carcinoma), brain, pancreatic, neck, lung, kidney, liver, breast, colon, bladder, oesophagus, stomach, cervical, ovarian, germ cell and prostate.
[0101] Samples obtained from patients are preferably biopsy samples. A biopsy is a medical test involving the removal of cells or tissues for examination. The tissue is generally examined under a microscope by a pathologist and/or may be analyzed chemically using techniques well known in the art to assess protein or RNA levels. When a smaller sample of tissue is removed, the procedure is called an incisional biopsy or core biopsy. When an entire lump or suspicious area is removed, the procedure is called an excisional biopsy. When a sample of tissue or fluid is removed with a needle, the procedure is called a needle aspiration biopsy.
[0102] In alternative embodiments samples may be obtained from patients by other methods well known in the art, including but not limited to, samples of blood, serum, urine, sputum, ascites, intraperitoneal fluids and samples of cells taken by a ‘smear’ test. Blood samples may be taken via venipuncture, (e.g. by vacuum collection tube or syringe,) catheter, cannula, or by finger prick or heel prick as appropriate to the needs of the patient and the amount of blood required. Once a blood sample has been taken it may be treated prior to analysis (e.g. with sodium citrate, EDTA, ethanol or Heparin) for the purposes of preservation or in order to maximise the accuracy and/or reliability of the signal obtained by analysis of the sample.
[0103] Methods of processing (e.g. centrifugation and/or filtration) may be used to separate a blood sample into fractions each of which may be tested independently. For example, a blood serum sample is produced by allowing a whole-blood sample to clot on contact with air where the clotted fraction is removed by centrifugation to leave the serum as the supernatant.
[0104] Urine samples are preferably collected by urination or catheterisation.
[0105] Sputum samples may be collected from the patient by coughing and/or expectoration, or by extracting a sample with a suction tube or needle inserted in the airway. Preferably sputum samples should have minimal contact with saliva to avoid contamination.
[0106] A smear test (for example a Papancolaou test, also called a Pap smear or cervical smear test) may be used to sample cells from a patient. In the case of a cervical smear test cells are collected and removed from the surface of the tissue being tested by means of physical contact with an Aylesbury spatula, plastic fronded ‘broom’ or other instrument.
[0107] The cells and/or liquid collected in a sample taken from a patient may be processed immediately or preserved in a suitable storage medium for later processing. For example, in the case of a cervical smear test the cells are often preserved in an ethanol based storage medium for later processing and analysis. The sample may be treated for the purposes of preservation or for maximising the accuracy and/or reliability of the signal obtained by analysis of the sample. Methods of processing (e.g. centrifugation and/or filtration) may be used to separate a sample into fractions each of which may be tested independently.
[0108] In all of the methods and uses of the invention whether hereinbefore or hereinafter defined or described, the cancers are those that give rise to solid humours. The cancer is also preferably one selected from the group consisting of bronchial, nasopharyngeal, laryngeal, small cell and non-small cell lung, skin (e.g. melanoma or basal cell carcinoma), brain, pancreatic, neck, lung, kidney, liver, breast, colon, bladder, oesophagus, stomach, cervical, ovarian, germ cell and prostate. More preferably the cancers are cancers of the cervix, oesophagus, kidney, brain, breast and ovary.
[0109] In other embodiments the cancer may be a carcinoma, preferably a squamous cell carcinoma (SCC) or adenocarcinoma, preferably selected from cancers of the cervix, oesophagus, kidney, brain, breast and ovary.
[0110] In preferred embodiments, an increased level of CCR4 and/or CCL17 and/or CCL22 produced by the tumour cells identifies a malignant cancer or a prospectively malignant cancer.
[0111] The level of one or more of CCR4 and/or CCL17 and/or CCL22 produced in non-tumour cells may be determined and the level in tumour and non-tumour cells compared.
[0112] In preferred embodiments the level of CCR4 alone is determined. In other embodiments the level of CCL17 or CCL22 alone is determined.
[0113] The level of CCR4 and/or CCL17 and/or CCL22 in tumour cells may be compared with pre-determined levels. Pre-determined levels may be derived from normal non-cancerous tissue, earlier stage cancerous tissue, data obtained from databases or directly from available biological material or samples.
[0114] Various ways of determining the level of CCR4 and/or CCL17 and/or CCL22 may be employed in methods of the invention. Preferably the protein level and/or activity of CCR4 and/or CCL17 and/or CCL22 may be used as a measure of the gene products of CCR4 and/or CCL17 and/or CCL22 in the sample.
[0115] In a further preferred embodiment, the protein level of CCR4 and/or CCL17 and/or CCL22 is measured using an antibody reactive against CCR4, CCL17 and CCL22 respectively, preferably a specific antibody, e.g. a monoclonal antibody.
[0116] The location and amount of specific proteins can be detected by microscopy and histological techniques. Using sample preparation, staining and probing techniques well known in the art, the structure of cells can be shown and specific proteins associated with them can be detected and their location within the sample found.
[0117] Histochemical stains are well known in the art and may be used to show cell morphology and/or more specific cellular components. Commonly used stains include hematoxylin (which stains nucleic acids and ergastoplasm, blue) and eosin (which stains elastic and reticular fibres, pink)
[0118] Immunohistochemistry is a technique whereby antibodies to specific proteins are used for detection of said proteins in samples. Their binding of antibody to antigen in the sample can be detected in a number of ways.
[0119] The most standard method is to conjugate an enzyme that catalyses a colour changing reaction (e.g. alkaline phosphatase, horseradish peroxidase) to the antibody, thus the use of a suitable chromogenic substrate allows visualisation of the location of the antigen under the light microscope. A variation upon this method is immunofluorescence whereby the antibody is conjugated to a fluorophore (e.g. FITC, rhodamine, Texas Red) that emits a detectable signal when excited by a suitable source of energy. Normally this is light of a specific wavelength. Immunofluorescence is advantageous because the use of multiple fluorophores attached to different antibodies allows detection of multiple targets within a sample and is particularly suitable for confocal laser scanning microscopy, which is highly sensitive and can also be used to visualise interactions between multiple proteins. Often detection of the specific antigen is done by a, multiply staged, indirect method. An unlabelled or unconjugated ‘primary’ antibody, raised against the antigen being tested for is used to bind said antigen. This ‘primary’ antibody may then be detected by a ‘secondary’ antibody conjugated to a detectable marker and raised such that it will react with the immunoglobulin of the species that the ‘primary’ antibody was raised in.
[0120] Measurement of protein levels using antibodies may use techniques such as ELISA (Enzyme-linked Immunosorbent Assay), RIA (Radioimmunoassay), EMIT (Enzyme Multiplied Immunoassay Technique), protein microarray analysis, flow cytometry, western blotting, dot blotting or slot blotting, preferably the methodology is quantitative.
[0121] Flow cytometry is a technique for counting, examining, and sorting microscopic particles suspended in a stream of fluid. It allows simultaneous multiparametric analysis of the physical and/or chemical characteristics of single cells flowing through an optical and/or electronic detection apparatus.
[0122] Fluorescence-activated cell-sorting (FACS) is a specialised type of flow cytometry. It provides a method for sorting a heterogeneous mixture of biological cells into two or more containers, one cell at a time, based upon the specific light scattering and fluorescent characteristics of each cell. It is a useful scientific instrument as it provides fast, objective and quantitative recording of fluorescent signals from individual cells as well as physical separation of cells of particular interest.
[0123] The population of cells in a sample is normally heterogeneous. In order to detect the differences between cells, they are treated with chemical and immunochemical techniques similar to those of histochemistry. Immunochemical detection of antigens may be done using antibodies labeled with fluorophores such as FITC, Cy5 and GFP. Staining the cells with dyes (such the DNA binding dyes SYBR-Green and DAPI) may be used to detect differences such as cell size or cell cycle stage within and between samples. Using these techniques in combination allows different cells within the heterogeneous to be given specific fluorescence profiles that are distinguishable by the flow cytometer. In this way cells expressing particular antigens or associated with particular light scattering profiles may be detected and their prevalence, within the sample population, measured.
[0124] Alternatively, the level of CCR4 and/or CCL17 and/or CCL22 may be determined by measuring the level of mRNA encoding CCR4 and/or CCL17 and/or CCL22 as a measure of the level of the gene products of CCR4 and/or CCL17 and/or CCL22 in the sample
[0125] In further preferred embodiments of the invention the mRNA level is measured by a quantitative polymerase chain reaction (qPCR) method, preferably a qPCR method where the template is the product of a reverse transcriptase reaction (RT-qPCR.)
[0126] In preferred embodiments mRNA is extracted from the sample and reverse transcribed to produce cDNA prior to qPCR.
[0127] In other preferred embodiments the level of transcription of CCR4 and/or CCL17 and/or CCL22 is measured using a nuclease protection assay, preferably the probe used is specific for CCR4 and/or CCL17 and/or CCL22.
[0128] In other preferred embodiments of the invention the mRNA level is measured using a DNA microarray.
[0129] A DNA microarray (also known as gene or genome chip, DNA chip, or gene array) is a collection of microscopic DNA spots, commonly representing single genes, arrayed on a solid surface by covalent attachment to chemically suitable matrices. Qualitative or quantitative measurements with DNA microarrays utilize the selective nature of DNA-DNA or DNA-RNA hybridization under high-stringency conditions. Fluorophore-based detection may be used to determine the degree of hybridisation from which a quantitative measurement may be calculated.
[0130] In preferred embodiments, the cancer is a malignant cancer. Alternatively, the cancer may be a pre-malignant cancer. The method of the invention can advantageously identify the stage to which cancer in a patient has progressed, thereby permitting identification of the most appropriate course of treatment. Consistent with the method of the invention herein before described, including all subsidiary aspects, the invention also provides for the use of CCR4 receptor as a marker for the identification and/or staging of cancer. The CCR4 receptor may be detected by means of an antibody, preferably a specific antibody, e.g. a monoclonal antibody.
[0131] Similarly, the invention also provides for the use of CCL17 ligand as a marker for the identification and/or staging of cancer. The CCL17 ligand may be detected by means of an antibody, preferably a specific antibody, e.g. a monoclonal antibody.
[0132] The invention also provides for the use of CCL22 ligand as a marker for the identification and/or staging of cancer. The CCL22 ligand may be detected by means of an antibody, preferably a specific antibody, e.g. a monoclonal antibody.
[0133] The invention includes a method of treating or preventing malignant disease in an individual suffering from cancer comprising treating the individual with an effective amount of antibodies reactive against reactive against CCR4 and/or CCL17 and/or CCL22. The invention therefore provides the use of antibodies reactive against CCR4 and/or CCL17 and/or CCL22 for the manufacture of a medicament for the treatment or prevention of cancer in an individual suffering from cancer.
[0134] In a further embodiment of the invention antibodies reactive against CCR4 and/or CCL17 and/or CCL22 may be used in the manufacture of a medicament for the treatment or prevention of cancer.
[0135] In a preferred embodiment, the medicament comprises an antibody specific for CCR4, and may be a monoclonal antibody.
[0136] Embodiments of this aspect of the invention are, for example, the antibodies disclosed in WO0164754 (Kyowa Hakko Kogyo), WO05035582 (Kyowa Hakko Kogyo), WO03018635 (Kyowa Hakko Kogyo), WO05053741 (Kyowa Hakko Kogyo) or WO0042074 (MILLENIUM PHARMACEUTICALS);
[0137] In an additional preferred embodiment, the medicament comprises an antibody specific for CCL17, and may be a monoclonal antibody.
[0138] In an additional preferred embodiment, the medicament comprises an antibody specific for CCL22, and may be a monoclonal antibody.
[0139] In another embodiment, the medicament comprises an antibody which may be a Fab fragment wherein said Fab fragment may be selected from the group consisting of: scFv, F(ab′) 2 , Fab, Fv and Fd fragments; or CDR3 regions.
[0140] The fragment antigen binding (Fab fragment) is a region on an antibody which binds to antigens. It is composed of one constant and one variable domain of each of the heavy and the light chain. These domains shape the paratope—the antigen binding site—at the amino terminal end of the monomer. The two variable domains bind the epitope on their specific antigens.
[0141] Fc and Fab fragments can be generated. The enzyme papain can be used to cleave an immunoglobulin monomer into two Fab fragments and an Fc fragment. The enzyme pepsin cleaves below the hinge region, so a F(ab′)2 fragment and a Fe fragment may be formed. The variable regions of the heavy and light chains can be fused together to form a single chain variable fragment (scFv), which is only half the size of the Fab fragment yet retains the original specificity of the parent immunoglobulin.
[0142] A complementarity determining region (CDR) is a short amino acid sequence found in the variable domains of antigen receptor (e.g. immunoglobulin and T cell receptor) proteins that complements an antigen and therefore provides the receptor with its specificity for that particular antigen. Most of the sequence variation associated with immunoglobulins and T cell receptors are found in the CDR regions, these regions are sometimes referred to as hypervariable domains. Among these, CDR3 shows the greatest variability as it is encoded by a recombination of the VJ regions.
[0143] In another embodiment, the medicament comprises antibodies that may be humanised or chimeric antibodies.
[0144] Humanized antibodies or chimeric antibodies are a type of monoclonal antibody that are synthesized using recombinant DNA technology to circumvent the clinical problem of immune response to foreign antigens. The standard procedure of producing monoclonal antibodies yields mouse antibodies. Although murine antibodies are very similar to human antibodies the differences are significant enough that the human immune system recognizes mouse antibodies as foreign, rapidly removing them from circulation and causing systemic inflammatory effects. Humanized antibodies may be produced by merging the DNA that encodes the binding portion of a monoclonal mouse antibody with human antibody-producing DNA. Mammalian cell cultures are then used to express this DNA and produce these part-mouse and part-human antibodies that are not as immunogenic as the purely murine variety.
[0145] Modifications may be made to monoclonal antibodies that bind only to cell-specific antigens and preferably induce an immunological response against the target cancer cell. Such monoclonal antibodies are preferably modified for delivery of a toxin, radioisotope, cytokine or other active conjugate.
[0146] In another aspect of antibody technology, bispecific antibodies may be designed that can bind with their Fab regions both to target antigen and to a conjugate or effector cell. Also, all intact antibodies can bind to cell receptors or other proteins with their Fc region.
[0147] The production of recombinant monoclonal antibodies may also involve technologies, referred to as repertoire cloning or phage display/yeast display. These may involve the use of viruses or yeast to create antibodies, rather than mice. These techniques rely on rapid cloning of immunoglobulin gene segments to create libraries of antibodies with slightly different amino acid sequences from which antibodies with desired specificities can be selected. This process can be used to enhance the specificity with which antibodies recognize antigens, alter their stability in various environmental conditions, increase their therapeutic efficacy, and modulate their detectability in diagnostic applications.
[0148] The invention includes a method of treating or preventing malignant disease in an individual suffering from cancer comprising treating the individual with an effective amount of a small molecule inhibitor of CCR4 and/or CCL17 and/or CCL22. The invention therefore provides the use of small molecule inhibitor of CCR4 and/or CCL17 and/or CCL22 for the manufacture of a medicament for the treatment or prevention of cancer in an individual suffering from cancer.
[0149] Embodiments of this aspect of the invention are, for example, the small molecule inhibitors disclosed in WO04007472 (ONO PHARMACEUTICAL CO.), WO05023771 (ONO PHARMACEUTICAL CO.), WO02094264 (TULARIK INC.), WO0230358 (TULARIK/CHEMOCENTRYX), WO0230357 (CHEMOCENTRYX), WO051236976 (ASTELLAS PHARMA INC.), WO05085212 (YAMANOUCHI PHARMACEUTICAL CO., LTD.), WO05082865 (YAMANOUCHI PHARMACEUTICAL CO., LTD.), WO04108717 (ASTRAZENECA AB), EP1633729 (ASTRAZENECA AB) or WO03014153 (TOPIGEN PHARMACEUTIQUE INC.)
[0150] The invention also includes a method of treating or preventing malignant disease in an individual suffering from cancer comprising treating the individual with an effective amount of an agent that modulates the activity of CCR4 and/or CCL17 and/or CCL22. The invention therefore provides the use of an agent that modulates the activity of CCR4 and/or CCL17 and/or CCL22 for the manufacture of a medicament for the treatment or prevention of cancer in an individual suffering from cancer.
[0151] Embodiments of this aspect of the invention are, for example, the CCR4 modulating agents as disclosed in WO0041724A1 (LELAND STANFORD/LEUKOSITE);
[0152] In preferred aspects, the method and use of the invention are for the treatment of cancer, preferably selected from the group consisting of bronchial, nasopharyngeal, laryngeal, small cell and non-small cell lung, skin (e.g. melanoma or basal cell carcinoma), brain, pancreatic, neck, lung, kidney, liver, breast, colon, bladder, oesophagus, stomach, cervical, ovarian, germ cell and prostate. More preferably the cancers are cancers of the cervix, oesophagus, kidney, brain, breast and ovary.
[0153] In particularly preferred treatments the cancer is cervical cancer, preferably squamous cell carcinoma (SCC).
[0154] In particularly preferred treatments the cancer is oesophageal cancer, preferably squamous oesophageal carcinoma.
[0155] In another aspect, the invention provides a method of screening for anti-cancer agents comprising the steps of:
a) providing test cells that express the CCR4 receptor and that are capable of, or are in the process of, proliferation, b) exposing the test cells to a candidate agent for a period of time, c) measuring proliferation of the test cells, whereby a decrease in any proliferation in the test cells identifies an anti-cancer agent and/or increased or continued proliferation of the test cells identifies a poor or inactive anti-cancer agent.
[0159] In other aspects, the invention provides a method of screening for anti-cancer agents comprising the steps of:
a) providing test cells expressing the CCR4 receptor and that are capable of, or are in the process of, proliferation, b) providing at least first and second aliquots of said cells, c) exposing said first aliquot to a candidate agent for a period of time, d) not exposing said second aliquot to the candidate agent for the period of time, e) measuring the degree of proliferation of the cells in the first and second aliquots, whereby a decrease in any proliferation of the cell(s) in the first aliquot relative to the cell(s) in the second aliquot identifies an anti-cancer agent and/or increased or continued proliferation of the cell(s) in the first aliquot relative to the cell(s) in the second aliquot identifies a poor or inactive anti-cancer agent.
[0165] In certain preferred embodiments, the test cells are induced to proliferate, preferably prior to exposure to the candidate agent.
[0166] In other preferred embodiments, the test cells are induced to proliferate by the addition of a ligand of the CCR4 receptor.
[0167] In another aspect, the invention provides a method of screening for anti-cancer agents comprising the steps of:
a) providing test cells that express the CCR4, b) exposing the test cells to a candidate agent for a period of time, c) measuring the level of a secreted protein or signalling molecule of the test cells, whereby a decreased level of the secreted protein or signalling molecule identifies an anti-cancer agent and/or no decrease or an increased level of secreted molecule or signalling molecule identifies a poor or inactive anti-cancer agent.
[0171] In other aspects, the invention provides a method of screening for anti-cancer agents comprising the steps of
a) providing test cells expressing the CCR4, b) providing at least first and second aliquots of said cells, c) exposing said first aliquot to a candidate agent for a period of time, d) not exposing said second aliquot to the candidate agent for the period of time, e) measuring the level of a secreted protein or signalling molecule of the test cells in the first and second aliquots, whereby a decreased level of the secreted protein or signalling molecule by the cell(s) in the first aliquot relative to the cell(s) in the second aliquot identifies an anti-cancer agent and/or no decrease or an increased level of secreted molecule or signalling molecule from the cell(s) in the first aliquot relative to the cell(s) in the second aliquot identifies a poor or inactive anti-cancer agent.
[0177] In preferred embodiments, the secreted protein or signalling molecule is a cytokine or chemokine.
[0178] In other preferred embodiments, the level of the secreted protein or signalling molecule is measured at any time before, during or after exposure of the test cells to the candidate agent.
[0179] In certain preferred embodiments, test cells are induced to secrete a particular protein, or other signalling molecule, preferably a chemokine or cytokine, preferably prior to exposure to the candidate agent.
[0180] In other preferred embodiments, test cells are induced to secrete a particular protein, or other signalling molecule, preferably a chemokine or cytokine, by the addition of a ligand of the CCR4 receptor.
[0181] In another aspect, the invention provides a method of screening for anti-cancer agents comprising the steps of
a) providing test cells that are expressing the CCR4 receptor and that are capable of, or are in the process of, migration. b) exposing the test cells to a candidate agent for a period of time. c) simultaneously or subsequent to the period of exposure, providing conditions suitable for cell migration, and measuring any migration of exposed cells, whereby reduced or absent migration in the exposed cells identifies an anti-cancer agent and/or increased or continued migration of the test cells identifies a poor or inactive anti-cancer agent.
[0185] A method of screening for anti-cancer agents comprising the steps of:
a) providing test cells expressing the CCR4 receptor and that are capable of, or are in the process of migration, b) providing at least first and second aliquots of said cells, c) exposing said first aliquot to a candidate agent for a period of time, d) not exposing said second aliquot to the candidate agent for the period of time, e) simultaneously or subsequent to the period of exposure, providing conditions suitable for cell migration, and measuring the degree of migration of the cell(s) in the first aliquot relative to the cell(s) in the second aliquot, whereby reduced or absent migration identifies an anti-cancer agent and/or increased or continued proliferation of the cell(s) in the first aliquot relative to the cell(s) in the second aliquot identifies a poor or inactive anti-cancer agent.
[0191] Chemotaxis, is the phenomenon in which bodily cells, bacteria, and other single-cell or multicellular organisms direct their movements according to certain chemicals in their environment. This is important for bacteria to find food (e.g. glucose) by swimming towards the highest concentration of food molecules, or to flee from poisons (e.g. phenol). In multicellular organisms, chemotaxis and cell migration are critical to development as well as normal function. In addition, it is known in the art that mechanisms that allow chemotaxis and cell migration in animals can be subverted during cancer metastasis.
[0192] Chemotaxis is called positive if movement is in the direction of a higher concentration of the chemical in question, and negative if the direction is opposite.
[0193] In haptotaxis the gradient of the chemoattractant is expressed or bound on a surface, in contrast to the classical way of chemotaxis when the gradient develops in a soluble space.
[0194] Necrotaxis embodies a type of chemotaxis when the chemoattractant molecules are released from necrotic or apoptotic cells. Depending on the chemical character of released substances necrotaxis can accumulate or repel cells, which underlines the pathophysiological significance of this phenomenon.
[0195] In certain preferred embodiments, the test cells are induced to migrate, preferably prior to exposure to the candidate agent.
[0196] In other preferred embodiments, the test cells are been induced to migrate by the addition of a ligand of the CCR4 receptor.
[0197] Cell migration and cell invasion assays measure the ability of certain cell types to move through a porous membrane or matrix toward a chemoattractant or growth factor. Cell migration and invasion may be critical processes in angiogenesis and tumour metastasis. Cell invasion may be measured in one or more dimensions by using suitable culture conditions and a suitable porous matrix for the cells to move through.
[0198] In accordance with preferred screening methods, cell invasion may be measured preferably using a matrigel Boyden chamber.
[0199] In the method aspects of the invention defined herein the ligand may be CCL17 and/or the ligand may be CCL22.
[0200] In another aspect, the invention provides a method of screening for anti-cancer agents comprising the steps of:
a) providing cancer cells that express the CCR4 receptor, b) culturing the cancer cells under conditions that result in at least some cancer cell death, c) exposing the test cells to a candidate agent for a period of time, d) measuring death of cancer test cells, whereby no or no significant increase in cell death in the test cells identifies a poor or inactive anti-cancer agent and/or increased cell death identifies an anti-cancer agent.
[0205] In other aspects, the invention provides a method of screening for anti-cancer agents comprising the steps of:
a) providing cancer cells that express the CCR4 receptor, b) providing at least first and second aliquots of said cells, c) culturing the cancer cells under conditions that result in at least some cancer cell death, d) exposing said first aliquot to a candidate agent for a period of time, e) not exposing said second aliquot to the candidate agent for the period of time, f) measuring death of cancer test cells in the first and second aliquots, whereby no or no significant increase in cell death in the first aliquot relative to the cell(s) in the second aliquot identifies a poor or inactive anti-cancer agent and/or increased cell death in the first aliquot relative to the cell(s) in the second aliquot identifies an anti-cancer agent.
[0212] In other preferred embodiments the exposure of the test cells or cancer cells to candidate agent may be before or after the change in culture conditions.
[0213] In preferred embodiments or methods of screening for anti-cancer agents, the test cells or cancer cells are capable of, or are in the process of, proliferation.
[0214] In methods of screening for anti-cancer agents, the cell or cells may be from a tumour biopsy sample or may be cervical cancer cell(s), e.g. C-41 (ATCC, Rockville Md., USA) or another cell line endogenously expressing CCR4.
[0215] The invention will now be described in detail, including by way of experimental examples and with reference to the drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0216] FIG. 1 —Expression of CCR4 mRNA is increased in malignant cervical biopsies compared with normal tissues.
[0217] (A) Summary of the percentage of samples expressing CC and CXC chemokine receptor mRNA in non-neoplastic (white bars) and malignant (black bars) cervical tissue after ribonuclease protection assay (RPA) for mRNA expression.
[0218] (B) RPA of non-neoplastic tissue samples 1 to 14 and malignant tissues: Adenocarcinoma biopsies, samples 1 to 4 and squamous cell carcinoma (SCC) biopsies, samples 1 to 11. Stages of adenocarcinoma tissues were: 1 to 3, 1B1; 4, 1B2. Stages of SCC were: 1, 1A2; 2 to 8-11, 1B1; 9, 1B2 and 10, 2A.
[0219] (C) Up-regulation of CCR4 gene expression in epithelial and stromal compartments when compared to their non-neoplastic counterparts. mRNA expression in non-neoplastic cervical tissue was used as a baseline to compare malignant tissue mRNA and is represented as value “1”.
[0220] FIG. 2-Immunohistochemistry for CCR4 during malignant progression of the cervix
[0221] CCR4 protein expression in the stroma of (A) non-neoplastic cervical tissue, 200×; (B) CIN 200×; (C) invasive cervical tissue, 200×. CD68+ protein expression in (D) normal, 400×: (E) CIN, 200×: and (F) invasive cervical cancer, 400×. FoxP3+ protein
[0222] staining in (G) non-neoplastic cervical tissue, 200×; (H) CIN, 400×; and (I) invasive cervical cancer, 400×. Epithelial CCR4 protein expression in (J) non-neoplastic, 200×; (K) CIN, 400× and (L) invasive cervical cancer, 400×.
[0223] FIG. 3 —Immunohistochemistry score for CCR4, CD68 and FoxP3 positive cells during malignant progression of the cervix
[0224] (A) Total score for epithelial cell (black bars) and stromal cell (white bars) staining for CCR4, calculated by ‘positivity’בintensity” in normal (n=23), CIN (n=63) and SCC (n=45), recurrent cancer (n=15), lymph node metastasis (n=10) and adenocarcinoma (n=10). (B) Mean CD68+ score (+SE) of intra- and peritumoral macrophage infiltration in normal (n=11), CIN (n=16), adenocarcinomas (n=16), recurrent cancer (n=24) and metastatic deposits in lymph nodes (n=11); ** p<0.001; p<0.005. (C) Mean FoxP3+ score (+SE) of intra and peritumoral Treg cell infiltration in normal (n=11), CIN (n=16), SCC (n=44), adenocarcinomas (n=16) recurrent cancers (n=24) and metastatic deposits in the lymph node (n=11), * p<0.01. (D) Total CCR4 score on epithelial cells (black bars) and stromal cells (white bars) calculated by ‘positivity’בintensity’ in CIN I (n=26), CIN II (n=19) and CIN III (n=17).
[0225] FIG. 4 —mRNA and protein expression of the CCR4 ligand CCL22 in normal, CIN and SCC cervix
[0226] (A) CCL22 mRNA expression levels as assessed by quantitative Real Time RT-PCR in normal (n=14) and SCC (n=11) cervical biopsies (P=0.43). CCL22 protein expression in (B) non-neoplastic, 200×; (C) CIN, 200× and (D) SCC, 200× cervical tissues. (E) Total CCL22 score of epithelial cells (black bars) and stromal cells (white bars) calculated by ‘Positivity×Intensity’ in normal (n=16), CIN (n=17), SCC (n=19) and adenocarcinomas (n=5) samples of the cervix.
[0227] FIG. 5 —mRNA and protein expression of the CCR4 ligand CCL17 in normal, CIN and SCC cervix
[0228] (A) CCL17 mRNA expression levels as assessed by quantitative Real Time RT-PCR in normal (n=7) compared with SCC (n=11) cervical biopsies (P=0.02). CCL17 protein expression in (B) non-neoplastic, 200×; (C) CIN, 200× and (D) SCC, 200×. (E) Total CCL17 score of epithelial cells (black bars) and stromal cells (white bars) calculated by ‘positivity×intensity’ in normal (n=21), CIN (n=33), SCC (n=20) and adenocarcinomas (n=4) samples of the cervix.
[0229] FIG. 6 —CCR4 is functional on the cervical cancer cell line C-41
[0230] (A) CCR4, CCL17 and CCL22 protein expression (blue lines) was measured in the C-41 cervical cancer cell line by using flow cytometry. Expression/internalization of CCR4 by C-41 was examined after 100 ng/ml (B) of CCL17 and (C) CCL22 stimulation (blue line represents CCR4 control at 0 minutes; orange line indicates CCR4 protein expression after stimulation with the appropriate ligand). (D) Migration of the C-41 cervical cancer cell in response to CCL17 and CCL22. Values are the mean±SD of 10 determinations, * P<0.05, ** P<0.01. (E and F) C-41 growth under suboptimal conditions after stimulation of 1 ng/ml, 10 ng/ml and 100 ng/ml of CCL17 and CCL22 for 2, 4 and 6 days. After 6 days C-41 showed in significant growth increase after stimulation with 10 ng/ml CCL17; (P=0.017) and 100 ng/ml CCL17 (P=0.044), but not with 1 ng/ml CCL17 (P=0.383). Stimulation of 1 ng/ml CCL22 and 100 ng/ml CCL22 also showed significant increased growth: 1 ng/ml CCL22; (P=0.026) and 100 ng/ml CCL22 (P=0.043), but not with 10 ng/ml CCL22 (P=0.195).
[0231] FIG. 7 —CCR4 expression in carcinogenesis of oesophagus CCR4 expression in normal (A, ×40; D, ×40), hyperplastic (B, ×100), dysplastic (C, ×40; D, ×40) epithelial cells of oesophagus and invasive cancer cells (H, ×200). CCR4 expression in the stroma during carcinogenesis of oesophagus: E, normal oesophagus (×200); F, dysplasia I (×200); G, dysplasia III (×200); H, invasive cancer (×200).
[0232] FIG. 8 —Immunohistochemistry scoring results of CCR4 positive stromal cells during malignant progression of the cervix
[0233] Scoring was assessed by number of cells positive for CCR4 and by intensity of CCR4 staining. Number of cells was measured as average of 15 HPF: 0=no CCR4 protein expression; +1=1-10 CCR4 positive cells per HPF; +2=10-20 positive cells per HPF; +3 (21-30 cells per HPF); +4 (>30 cells). Intensity was measured as: 0=no expression; 1+=mild expression; 2++=moderate expression; 3+++=strong expression.
[0234] FIG. 9 —Immunohistochemistry scoring results of CCR4 positive epithelial cells during malignant progression of the cervix
[0235] Scoring was assessed by number of cells positive for CCR4 and by intensity of CCR4 staining. 0=no CCR4 protein expression on epithelial cells; +1=less than 25% of the section has CCR4 expression; +2=26-50% cells positive; +3=51-75% cells positive; +4 more than 76% cells CCR4 positive. Intensity was measured as: 0=no expression; 1+=mild expression; 2++=moderate expression; 3+++=strong expression
[0236] FIG. 10 —The results of a screen for CCR4 expression in a wider range of tumours using a human tissue-derived cDNA library (Cancer Research UK). The library contains cDNA generated from RNA isolated from 5-10 tumour samples and 2-5 normal samples for 11 different tumour types: lung, colon, bladder, stomach, pancreas, skin, breast, brain, oesophagus, ovary and prostate. The CCR4 mRNA expression levels were measured using quantitative Real Time RT-PCR.
[0237] FIG. 11 shows the results of FACS analysis for CCR4 expression on cervical cell lines (C41, C33A) and renal cancer cell lines (786, A498, CAKI). Dashed line: isotype-matched control antibody; grey line CCR4 expression
[0238] FIG. 12 shows the results of FACS analysis of CCR4 expression on C41 cells after 24 h stimulation with IL-10, TGF-β and FGF. Dashed line: isotype control; grey line CCR4 expression; bold line; CCR4 expression after cytokine stimulation.
[0239] FIG. 13 shows a cDNA sequence of CCR4. This is SEQ ID NO:1 referred to herein.
DETAILED DESCRIPTION OF THE INVENTION
[0240] The inventors have discovered that chemokine receptor CCR4 expression is an early event in carcinogenesis in certain tumour types. Epithelial expression of a receptor for homeostatic chemokines usually present in a tissue may confer a survival advantage on the initiated cell.
[0241] The chemokine receptor CCR4 was present on dysplastic non-invasive lesions of the cervix and oesophagus. This was particularly striking in some of the oesophageal cancer samples where CCR4 positive dysplastic areas were clearly seen adjacent to normal epithelial areas in the same section (e.g. FIGS. 7 C and D).
[0242] The chemokine receptor CCR4 increased with malignant progression of the cervix. This was not only due to increased infiltration of CCR4-positive macrophages and Treg cells, but also to acquisition of CCR4 expression by epithelial cells. An unexpected finding was that CCR4 was strongly expressed on non-invasive epithelial cells in intraepithelial (CIN) lesions as well as invasive cancer cells. Progression from CIN to invasive disease was associated with increased stromal cell expression of CCR4 ligands CCL17 and 22 and these chemokines stimulated growth and migration of a CCR4-positive cervical cancer cell line (e.g. FIG. 4 and FIG. 6 ). CCR4 was also detected on dysplastic as well as invasive epithelial cells in oesophageal cancer, again with CCL17 and CCL22 levels increasing during malignant progression. Changes in CCL17 and 22 gradients aid transition from pre-invasive to invasive disease and attract tumour-promoting leucocytes that help initiated cells evade immune surveillance.
[0243] The two CCR4-binding chemokines, CCL17 and CCL22, were also found on the surface of blood and lymphatic vessels in the tumour biopsies. It was not possible to quantify this but preliminary observations indicate an increase in the intensity of staining with malignant progression.
[0244] Another element of the CCR4 system is the non-signalling chemokine receptor D6 that has a high affinity for CCL17 and CCL22 [18]; its presence in the tissues would be expected to influence gradients of these chemokines [19].
[0245] FIG. 6 shows that the CCR4 receptor is functional on the cervical cancer cell line C-41. CCR4 can be up-regulated by the microenvironment. CCR4 positive and negative cells were exposed to a number of cytokines (TNF-α, IFN-γ, IL-4 and IL-10) known to be present in the cervical microenvironment and for which receptors were likely to be present on the tumour cells. None of these influenced CCR4 expression. However, CCR4 mRNA levels, but not protein levels, were up-regulated by co-culture of C-41 cells with macrophages.
[0246] CCR4 and D6 are located on chromosome 3p close to where critical cervical cancer tumour suppressor genes are thought to be located with complex aberrations (loss of heterozygosity, homozygosity and gene amplification) reported [25, 26, 27]. While neither CCR4 nor D6 are directly implicated in these changes [26], genetic alterations nearby may have an impact on their regulation.
[0247] EBV-immortalised B cells secrete CCL22 as well as CCL3 and CCL4 [28]. Stable expression of the EBV oncogene LMP1 also induced CCL17 and CCL22 in a B cell line and LMP1-induced CCL17 and CCL22 expression was regulated by NF-kB. It was suggested that induction of these two chemokines by EBV helps malignant cells evade immune surveillance by attracting Th2 and Treg cells. Other oncogenic changes may induce CCL17 and CCL22 production by epithelial cells.
[0248] The inventors undertook the detailed quantitation of two components of the mononuclear infiltrate in cervical cancer, specifically CD68+ macrophages and FoxP3+ Tregs. The density of CCR4-positive infiltrating cells increases in CIN compared with normal cervix and increases further in both SCC and adenocarcinomas. CD68+ macrophages follow the same pattern and we found that these were CCR4 positive. Cross talk between macrophages and malignant cells is critical at all stages of cancer progression, influencing malignant cell survival, aiding the angiogenic switch, polarizing leucocytes and aiding malignant cell invasion [29,30,31]. In cancers of the cervix and oesophagus, the chemokines CCL17 and CCL22 play a role in macrophage recruitment whereas in other cancers e.g. ovarian cancer, chemokines such as CCL2 are critical [32].
[0249] CCL17 and CCL22 are also important in the recruitment of Tregs that increase in a manner parallel to the CD68+ cells in the cervical biopsies. The recruitment of Treg cells to the pre-malignant and malignant lesions fosters immune privilege. For instance, in Hodgkin's Lymphoma, HL, the malignant cells are surrounded by a large number of CCR4+ FoxP3+ lymphocytes [33]. These cells, recruited by the malignant HL cells, create a favourable environment for malignant cells to escape the host immune system. The inventors think that this is also the case for cervical and oesophageal cancer. Hence not only do the changes in CCL17 and CLL22 gradients directly encourage tumor cell survival and spread but they attract in leucocytes that may also provide survival factors for the tumor cells and contribute to immune privilege/immunosuppression that prevents effective host responses against the tumor.
[0250] These data demonstrate that the presence of epithelial CCR4 is both a highly sensitive and highly specific biomarker for both pre-malignant and malignant cervical neoplasia. The role of CCR4 expression in cervical cancer progression is, as yet, unclear though the inventors' data suggests that CCR4 may offer cells protection from apoptotic stimuli within the tumour environment as well as being necessary for tumour cell invasion of the basement membrane. Due to its high sensitivity and selectivity, there is the potential for CCR4 to be used as a diagnostic biomarker for all stages of cervical cancer.
[0251] Subsequently the inventors also tested for the expression of CCR4 in 31 samples of oesophageal tumours, another tumour type that has a strong link with inflammation. By IHC they found that CCR4 was not detectable in any normal epithelial oesophageal tissue, but was present in epithelial cells of all pre-invasive and invasive lesions. Due to its high sensitivity and selectivity, there is the potential for CCR4 to be used as a diagnostic biomarker for all stages of oesophageal cancer.
[0252] In summary, the chemokine receptor CCR4 and its ligands increase during malignant progression of cervical, oesophageal, kidney, brain, ovarian or breast cancers. Changes in CCR4 and gradients of its ligand have several pro-tumor implications. First CCR4 stimulation increases the growth and survival of the initiated and invasive cancer cells; second, changes in chemokine gradients assists in invasion of the basement membrane and subsequent movement of the malignant cells into the blood vessels or lymphatic system. Finally CCL17 and CLL22 attract the types of cells, including M2 macrophages and FoxP3 Tregs that encourage tumor growth and allow the initiated cells to escape immune surveillance. CCR4 and its ligands may be useful diagnostic markers and therapeutic targets in epithelial neoplasia.
[0253] The invention is in part described by way of experimental work and examples, in which the following materials and methods were employed:
EXAMPLES
Cervical Tissue Samples and Oesophageal Specimens
[0254] For the mRNA studies, fifteen tumour biopsies from patients with cervical cancer (11 squamous cell carcinoma, S1-S11, and 4 adenocarcinomas, A1-A4) and 14 samples of non-neoplastic cervical tissue (N1-N14) were obtained during surgery and snap-frozen in liquid nitrogen. Diagnosis was made by the pathology department of Barts and The London NHS Trust. Patient samples were divided according to the FIGO classification (stage I, II, III, IV) and tumour biopsies were classified according to increasing grade of nuclear atypia (1, 2, 3) or as well, moderately, or poor differentiation.
[0255] For immunohistochemistry, paraffin embedded samples (n=166) from 150 different patients were obtained from Barts and The London NHS Trust and the Clinical Centre of Serbia, Belgrade. Access to fresh and paraffin-embedded human samples satisfied the requirements of the East London and City Health Authority Research Ethics Subcommittee (LREC no. T/02/046).
[0256] Resected specimens from thirty-one patients with primary squamous oesophageal carcinoma were also included in this paper. These patients were from a high-risk area for oesophageal carcinoma in Anyang City, Henan Province, China. All patients received surgical treatment at the Department of Surgery of the Central Hospital of Anyang. None of these patients had undergone chemotherapy, radiotherapy or immunomodulatory therapy before surgery. Samples were taken from macroscopically cancerous and the corresponding normal areas of the same cancer patient. The tissues were fixed in PBS containing 10% neutral-buffered formalin.
RNA Extraction and RNase Protection Assay (RPA)
[0257] Cervical tissue biopsies were homogenised using a liquid nitrogen-cooled mill 6750 (Glen Creston Ltd, Stanmore) and then solubilised in Tri Reagent™ (Sigma, Poole, UK). Extracted RNA was treated with 10 units DNase (Pharmacia, St Albans, UK) following the manufacturers instructions. RPA was performed using Riboquant® hCR5 and hCR6 template sets (BD Pharmingen, Oxford, UK) and [α 32 P] UTP (Amersham International plc, Aylesbury, UK). RNase-protected fragments were run on an acrylamide-urea sequencing gel (BioRad Laboratories Ltd, Hemel Hempstead, UK), adsorbed to filter paper and dried under vacuum. Autoradiography was performed using Kodak Biomax MS film with a Transcreen LE intensifying screen (Sigma).
Microdissection and Gene Array
[0258] Paraffin-embedded cervical tissues were cut under RNase-free conditions and mounted onto UV-treated PALM® membrane slides (PALM, Microlaser Technologies, Germany). These were then deparaffinised in xylene and rehydrated through graded alcohols. Samples were stained for 1 min with Mayer's haematoxylin solution, dehydrated and air-dried before processing. Sections were laser-microdissected following the manufacturer's protocol. Briefly, areas of interest were laser microdissected and catapulted into a microfuge cap containing Protein Kinase (PK) buffer. Approximately 500-5000 cells were captured in each session. Laser microdissected cells were dissolved in 100 μl PK Buffer mixed with 5 μl PK. Total RNA was then extracted using the Paraffin block RNA isolation kit (1902, Ambion, USA) according to the manufacturer's instructions. cDNA was amplified as described above and analysed using custom-made microfluidic gene array cards (PE Applied Biosystems) according to the manufacturer's instructions.
[0259] The gene expression profile of individual genes in seven cervical tumour samples was compared to five normal cervical samples. The gene expression levels in the normal epithelial or stromal cells samples was used as a baseline value of “1” and was compared with the average value of either tumour epithelial cells or tumour stromal cells respectively. The laser microdissected tumour samples comprised of one sample from stage 1A2 and 2B, and five of stage 1B1.
Immunohistochemistry
[0260] Paraffin-embedded sections (4 μm) were stained for CCR4, CCL17 and CCL22. Briefly, sections were dewaxed in xylene and dehydrated through an ethanol gradient. Following PBS washing the antigen was exposed using Target Retrieval Solution (S1700, DAKO) at 95° C. for 20 min or Antigen Unmasking Solution (H-3300, Vector) for 9 min in a microwave. Sections were blocked with normal rabbit or goat serum for 30 min and incubated overnight at 4° C. with the primary antibody: CCR4 (1:300, ab1669, AbCam, Cambridge), CCL17 (1:50, ab9816-50, AbCam, Cambridge) and CCL22 (1:20, 500-P107, Peprotech). Following incubation with a biotinylated secondary antibody (anti-goat or anti-rabbit IgG, 1:200, Vector) for 30 min at room temperature, antigens were revealed with 3,3′-diaminobenzidine (DAB; Sigma). Slides were then counterstained with haematoxylin, dehydrated and mounted. Omission of the primary antibody was used as a negative control. To check specificity of the CCR4 antibody, some CCR4-negative cells were transfected with cDNA for this chemokine receptor. The CCR4 antibody detected surface protein only on the successfully transfected cells.
Double Staining, CD68, FoxP3, SR-A: Scoring Methods and Categories
[0261] For assessment of CCR4, CCL17 and CCL22 expression on non-malignant and malignant epithelial cells, each sample was assessed semi-quantitatively with the following scoring system: 0 (no positive protein expression), +1 (<25% of the cross-section on average has positive expression), +2 (26-50%), +3 (51-75%), +4 (>76%).
[0262] The intensity of positive cells was analysed as follows: 0 (no expression), 1 (mild expression), 2 (moderate expression), 3 (strong expression). Scoring of CCR4, CCL17 and CCL22 expression in tumour stroma (intratumoral infiltrating cells) and the invasive border of the tumour (peritumoral infiltrating cells) was performed based on the ‘running mean’ method [43]. Necrotic areas were avoided. A total of 15 high-power fields (×400 magnification) were counted. Five scales were set up as follows: 0=no CCR4 protein expression; +1=1-10 CCR4 positive cells per HPF; +2 =10-20 positive cells per HPF; +3 (21-30 cells per HPF); +4 (>30 cells). The overall staining result was obtained by calculating ‘percentage’בintensity’. The IHC scoring on tumour and infiltrating cells was performed by a board-certified pathologist (YW).
Cervical Cancer Cell Line Culture
[0263] The cervical cancer cell line C-41 (ATCC, Rockville, Md., USA) was cultured in DMEM medium supplemented with 10% FCS. In some experiments cells were stimulated with 1, 10, 100, or 1000 ng/ml of CCL17 or CCL22 (PeproTech, London, UK). Proliferation and migration were assessed using methods described previously [11].
Statistical Analysis
[0264] Statistical significance was evaluated using unpaired t-test with Welch's correction (Instat software, San Diego, Calif.). A P value of <0.05 was considered significant.
Experiment 1—Ribonuclease Protection Assay for Chemokine Receptors
[0265] Ribonuclease protection assays (RPA) were used to screen for 13 chemokine receptor mRNAs in fresh-frozen biopsies of human cervical tissue. As can be seen from the summary graph in FIG. 1A , a range of chemokine receptor mRNAs was found in cervical tissue extracts with some discrete differences between the non-neoplastic and the malignant biopsies. Of particular interest was the chemokine receptor CCR4, which was present in the malignant cervix but not in extracts from non-neoplastic cervical biopsies ( FIG. 1B ).
[0266] As chemokine receptor expression was examined on whole tissue extracts containing a mixed population of stromal cells and epithelial cells, we next investigated the cellular source of the CCR4 mRNA. mRNA was extracted from laser microdissected stromal and epithelial cell areas of normal and malignant cervical biopsies, and semi-quantitative Real Time RT-PCR was used to analyse CCR4 expression with 18S rRNA as a control. As shown in FIG. 1C , CCR4 mRNA was up-regulated in stromal areas from malignant tissues when these were compared to their non-neoplastic counterparts. In addition, and unexpectedly, CCR4 mRNA was also up-regulated in extracts from the malignant epithelial cell areas compared to normal epithelium.
[0267] To investigate further these observations relating to CCR4 mRNA, we stained a cohort of biopsies for CCR4 using immunohistochemistry, IHC. We assessed CCR4 protein expression in 166 samples of paraffin embedded cervical tissues from 150 different patients: nonneoplastic, n=23; CIN I, n=30; CIN II, n=17; CIN III, n=16; SCC, n=45; recurrent tumour, n=15; lymph node metastasis (LN mets), n=10; adenocarcinoma, n=10. Both leucocytes and epithelial cells expressed CCR4 protein. To quantify our results, an IHC score was calculated by multiplying the ‘positivity’ and ‘intensity’ (see the description of methods and FIGS. 8 and 9 for a more details).
Experiment 2—CCR4 Protein is Found on Infiltrating Leucocytes in Human Cervical Biopsies.
[0268] As shown in FIG. 2 (A-C), leucocytes in the stromal areas of the biopsies stained positive for CCR4. The IHC score for CCR4 positivity in the stromal areas is summarised in FIG. 3A (white bars). The non-neoplastic tissues were negative for CCR4 leucocytes ( FIGS. 2A , 3 A). There were more CCR4 expressing stromal cells in the CIN samples ( FIG. 2 B, 3 A) and this increased further in the invasive neoplastic cervical samples ( FIG. 2 C, 3 A). The intensity of CCR4 expression on the infiltrating leucocytes also increased with malignant progression. In non-neoplastic tissues this was mild; intensity was moderate to strong in CIN and adenocarcinomas, and intensity was strong in invasive SCC, recurrent tumours and lymph node metastases ( FIG. 8 ).
[0269] The stroma consists of various cell types, and tests were carried out to ascertain which of the infiltrating cells contributed to CCR4 expression. As macrophages and Treg cells express CCR4, CCR4 protein expression was examined in these two cell types and also counted the number of CD68+ macrophages and FoxP3+ Treg cells in the tissue biopsies were counted.
[0000] Experiment 3—CCR4 Positive Macrophages Treg Cells Increase with Malignant Progression.
[0270] The number of CD68+ macrophages and FoxP3+ Tregs increased with malignant progression of the cervix. As shown in FIG. 2 D-I there were few CD68 and FoxP3 cells in biopsies of normal cervix, but the numbers increased in CIN and both cell types were prominent in invasive cancers.
[0271] The numbers of CD68+ and FoxP3+ cells were then counted in the 122 and 33 biopsies respectively. As shown in FIG. 3B there was a significant (p<0.001) increase in CD68+ cells in CIN lesions compared to normal cervix. The number of 13 CD68+ cells further increased in SCC, adenocarcinoma, recurrent cancers and lymph node metastases (P<0.001, and for LN mets P<0.05, compared to normal cervix). A similar increase in FoxP3+ cells occurred with malignant progression with SCC, adenocarcinomas and lymph node metastases all showing significant increases in the FoxP3+ infiltrate compared to normal cervix (p<0.01).
[0272] To study the phenotype of infiltrating CCR4 expressing cells, an assessment was made of cell surface expression of CCR4 by macrophages and Tregs using double immunohistochemical staining for CD68 and FoxP3. This confirmed that CD68+ and FoxP3+ cells also express CCR4 protein (data not shown). A subset of 33 paraffin embedded tissues were also stained for scavenger receptor-A (SR-A) protein (non-neoplastic=10, CIN=10, SCC=10, adenocarcinoma=3). SR-A is a cell surface marker for M2 alternatively activated macrophages [12]. SR-A could not be detected on stromal cells in normeoplastic lesions but in CIN and invasive cancer, a proportion of the CD-68+ cells expressed SR-A (data not shown).
[0273] These studies show, firstly, that malignant progression of the cervix is associated with an increase in the numbers of CD68+ macrophages and FoxP3+ Treg cells. These cells could provide pro-tumour growth factors for the malignant cells and also help create an immunosuppressive microenvironment that would help transformed cells evade immune surveillance. Secondly, these results showed that the original observation of an increase in CCR4 mRNA in malignant compared to normal cervical cancer was due, at least in part, to an increased infiltrate of CCR4 expressing leucocytes, including macrophages and Treg cells.
[0274] However, the laser microdissection result showed that CCR4 mRNA was also increased in epithelial areas of the tumours, and when assessing CCR4 protein on infiltrating leukocytes, it was clear that the chemokine receptor was also present on some epithelial cells (see FIGS. 2B and C). This was unexpected and warranted further investigation.
Experiment 4—Epithelial Cells in Cervical Biopsies Also Express CCR4
[0275] In the non-neoplastic cervical biopsies, normal epithelial cells did not express CCR4 ( FIG. 2A ). However epithelial cells in over 90% of the CIN cases expressed CCR4 ( FIGS. 2B and 2E ). 96% of the SCC samples had CCR4-positive epithelial cells ( FIGS. 2C and 2F ) and epithelial cells 90% of adenocarcinoma samples were positive for CCR4 ( FIG. 2G ). Malignant epithelial cells in all recurrent tumours and lymph node metastases expressed CCR4 protein. Full details of the IHC results for CCR4 protein on epithelial cells are shown in FIG. 9 and summarised in FIG. 2D (black bars). CCR4 expression was not restricted to a minority of epithelial cells. FIGS. 2E-G and 9 show that the majority of malignant epithelial cells in cervical biopsies of CIN and invasive cancer were CCR4 positive.
[0276] More detail relating to the IHC score for different stages of CIN is shown in FIG. 2 H. This shows that epithelial CCR4 expression was essentially unchanged through progression from CINI to III but that stromal levels of CCR4 increased from CIN I-III
Experiment 5—Statistical Analysis of CCR4 Expression During Cervical Cancer Progression
[0277] Statistical analysis of the data in FIGS. 8 and 9 showed that CIN lesions showed a significant up-regulation of CCR4 protein in both epithelial (P=0.0001) and stromal (P=0.0001) compartments when compared to non-neoplastic cervical tissues. CCR4 expression in invasive SCC was also significantly increased in both the epithelial (P=0.0001) and stromal compartments (P=0.0001) when compared to non-neoplastic tissues. Also in adenocarcinoma samples, CCR4 was up-regulated 15 on epithelial (P=0.0006) and stromal cells (P=0.0050) when compared to non-neoplastic cervical tissue.
[0000] Experiment 6—CCL22 mRNA and Protein Levels Change with Malignant Expression
[0278] In normal tissues, CCL22 is a product of macrophages, monocytes, DC, B and T cells [13, 14]. It is also found in epithelial tissues; for instance intestinal epithelium constitutively produces CCL22 that can be further up-regulated by inflammatory cytokines such as TNF- [15]. mRNA was isolated from 14 biopsies of normal cervix, 11 SCC and 4 adenocarcinomas and CCL22 levels assessed by real time RT PCR. As shown in FIG. 4A CCL22 mRNA levels were lower in the malignant tissues compared with the normal biopsies but this was not significant (P=0.43). A total of 52 samples of paraffin embedded cervical tissues from 50 different patients were assessed for CCL22 protein: non-neoplastic, n=16; CIN, n=17; SCC, n=19. In all cervical biopsies, CCL22 was detected in the epithelial cells ( FIG. 4B-D ). Fourteen of 16 normal samples, 15/17 CIN, 14/19 SCC had CCL22 positive epithelial cells. Infiltrating leucocytes in all biopsies contained CCL22 ( FIG. 4C , D). The epithelial IHC score declined slightly between the CIN lesions and SCCs ( FIG. 4E black bars). However, the stromal score for CCL22 increased from normal to CIN and SCC ( FIG. 4E white bars).
[0000] Experiment 7—CCL17 mRNA and Protein Levels Change with Malignant Expression
[0279] In normal tissues, CCL17 is expressed by vascular and lymphatic endothelial cells but is also produced by macrophages, DC and keratinocytes [16, 17, 55] mRNA was isolated from 14 biopsies of normal cervix, 11 SCC and 4 adenocarcinomas and CCL17 levels assessed by real time RT-PCR. As shown in FIG. 5A levels of CCL17mRNA were higher in SCC compared to normal cervix. A total of 74 samples of paraffin embedded cervical tissues from 70 different patients were assessed for CCL17 protein: non-neoplastic, n=21; CIN, n=33; SCC, n=20. Normal cervical biopsies had low levels of CCL17 in a minority of samples both the epithelium and stroma ( FIG. 5B ). Only 2/19 normal samples had CCL17 positive cells in the epithelium compared with 23/33 CIN samples and 13/20 SCC. The number of stromal cells that were CCL17 positive was increased in CIN ( FIG. 5C ) and SCC ( FIG. 5D ) compared to normal samples. Six of 21 normal biopsies had CCL17 positive stromal cells compared to 25/33 CIN and 15/20 SCC. The epithelial and stromal CCL17 IHC score was increased in CIN and SCC compared to normal biopsies ( FIG. 5E ). When the IHC scores from individual biopsies were analysed, there was a statistically significant difference in CCL17 IHC score in stroma from CIN (P=0.001) and SCC (P=0.002) compared to normal biopsies. There was also a difference in the IHC scores in epithelial areas of CIN (P=0.001) and SCC (P=0.009) compared to normal. These data show that chemokine gradients changed with the transition from intraepithelial neoplasia to invasive disease.
Experiment 8—CCR4 is Functional on Cervical Cancer Cells
[0280] To investigate the biological significance of CCR4 expression on cervical cancer cells a number of cervical cancer cell lines (CaSki, Me180, Hela-Ohio, Hela-S3, Siha, C33A, C41-1) were screened for CCR4 expression. The cell line C-41 expressed cell surface CCR4 in a constitutive manner ( FIG. 6A ). Using FACS analysis it was shown that C-41 cells expressed cell surface CCR4. This cell line also had intracellular CCL22 protein but the other CCR4 ligand CCL17 was not present ( FIG. 6A ). Following stimulation with 100 ng/ml CCL22, cell surface CCR4 protein was internalized on C-41 cells after 2 hours and returned back to the surface after 3 hours ( FIG. 6B ). Following stimulation with 100 ng/ml CCL17, cell surface CCR4 protein was also internalized on C-41 cells after 2 hours and returned back to the surface after 3 hours ( FIG. 6C ). C-41 cells demonstrated a typical bell-shaped chemotactic response towards both CCL17 and CCL22 in trans-well migration assays ( FIG. 6D ). At 10 ng/ml, CCL17 induced significant migration (P=0.036) and also at 100 ng/ml and 1000 ng/ml (P=0.0006 and P=0.0004 respectively). Similar results were seen with CCL22 at 10 ng/ml (P=0.0081), 10 ng/ml (P=0.0009) and at 1000 ng/ml (P=0.0348).
[0281] C-41 cells showed increased proliferation after stimulation with either 10 ng/ml (P=0.017) or 100 ng/ml (P=0.044) of CCL17. 1 ng/ml CCL22; (P=0.026), 100 ng/ml CCL22 (P=0.043), but not 10 ng/ml CCL22 (P=0.195), also simulated C-41 cell growth ( FIGS. 5C and D). CCR4 was therefore functional on this cervical cancer cell line, suggesting that it may also be functional in vivo.
Experiment 9—CCR4 is Expressed on Epithelial and Stromal Cells During Malignant Progression of the Oesophagus
[0282] It was unknown as to whether the expression of CCR4 and changes in chemokine ligand were specific for cervical cancer or whether they were seen in any other epithelial malignancies that have a link with inflammation. Cancer of the oesophagus is an epithelial cancer where examples of all stages of neoplastic progression can be readily obtained, often simultaneously from the same patient. CCR4 expression was examined in 31 specimens from patients with oesophageal cancer. In 27 of the cases, all stages of carcinogenesis of the oesophagus: normal, hyperplasia, dysplasia, in situ carcinoma and invasive cancer, were present in biopsies from the same patient. Four of 31 cases had pre-invasive lesions without invasive cancer areas. As shown in FIG. 7A , there was no detectable CCR4 expression in normal epithelial cells of oesophagus, apart from a few CCR4-positive cells around the basal layer of hyperplastic epithelium ( FIG. 7B ). In 30 of 31 cases CCR4 protein was present on epithelial cells in all stages of pre-invasive lesions (FIG. 7 C,D), that the intensity and percentage of CCR4 expressing cells in dysplastic lesions was much higher than in hyperplastic epithelial cells. Epithelial cells in the invasive cancer were also CCR4-positive ( FIG. 7H ). In some places, there was an abrupt transition between normal and abnormal mucosa FIG. 7C , D). Most interestingly, there were high levels of CCR4 expression in the dysplastic cells, but the cells in the superficial layers, and adjacent normal mucosa were negative. CCR4-positive cells were also present in the stroma, the pattern being the same as in cervical cancer. As shown in FIG. 7E , there were few CCR4-positive cells in the normal submucosa; with malignant progression, there were more CCR4 positive cells infiltrating the stroma ( FIG. 7F-H ).
Experiment 10—CCL17 and CCL22 in Oesophageal Biopsies
[0283] IHC was used to assess CCL17 and CCL22 expression in 23 of the oesophageal samples in which all stages of carcinogenesis were present in each sample. CCL17 was generally absent in both the epithelial and stromal areas of the normal tissues, although there were a few CCL17-positive cells in the stroma and a minority of hyperplastic areas. The number of samples continuing CCL17-positive epithelial or stromal cells increased in dysplasia and was highest in invasive areas with 10/23 of these showing some CCL17 positivity. Of particular note was strong CCL17 immunoreactivity on the endothelial cells or blood/lymphatic vessels in the submucosa of dysplastic but not normal epithelium.
[0284] Similar to the observations in cervical cancer, the levels of stromal positivity for CCL22 also increased with malignant progression. Only 1/23 samples showed CCL22 positive cells in the stroma of the normal areas, but in dysplastic areas and invasive areas 20/23 and 18/23 samples respectively contained CCL22-positive cells in the stroma. The stromal cell CCL22 positivity increased with the degree of dysplasia. Eight of 23 dysplasia I samples had CCL22 positive cells in the stroma; this increased to 19 of 23 samples of dysplasia II and 20/23 samples of dysplasia III. There was one difference between the cervical and oesophageal epithelium in that CCL22 was not detected in normal epithelium although it has been reported to be present in normal intestinal epithelium [15]. Epithelial CCL22 expression increased with malignant progression of the oesophagus; 0/23 samples were positive in the normal areas, 2/23 hyperplasias, 7/23 dysplasias and 14/23 invasive areas had CCL22 positive epithelial cells. Finally, more endothelial cells of blood vessels within the stroma of invasive cancer tissues were positive for CCL22 staining compared with normal and dysplastic epithelium.
[0000] Experiment 11—The results of a Screen for CCR4 Expression in a Wider Range of Tumours
[0285] Using a tumour cDNA library (Cancer Research UK) containing cDNA generated from RNA isolated from 5-10 tumour samples and 2-5 normal samples for 11 different tumour types: lung, colon, bladder, stomach, pancreas, skin, breast, brain, oesophagus, ovary and prostate. The CCR4 mRNA expression levels were measured using quantitative Real Time RT-PCR.
[0286] CCR4 mRNA levels were significantly elevated in cancers of the cervix, oesophagus, kidney, brain, breast and ovary.
Experiment 12—Analysis of Expression of CCR4 in Cervical and Renal Cancer Cell Lines
[0287] FIG. 11 shows the results of Fluorescence Activated Cell Scanning (FACS) analysis on cervical (C41, C33A) and renal cancer cell lines using an anti-CCR4 antibody to detect CCR4 expression. All the cell lines expressed CCR4. The dashed lines in FIG. 11 show the data for an isotype-matched control antibody.
Experiment 13—Effects of Common Cytokines on CCR4 Expression by Tumour Cells
[0288] The most common cytokines present in a tumour are IL-10, TGF-β, FGF, TNF-α. The
[0000] C41 cervical cancer cell line was stimulated in culture with different cytokines (IL-10, TNF-α, TGF-β, FGF; 20 ng/ml) for 24 h. The expression of CCR4 was then determined by FACS analysis. As shown in FIG. 12 , CCR4 was upregulated in terms of percentage of positive cells after IL-10, TGF-β and FGF stimulation (blue line) when compared with the unstimulated cells (black line). The dashed line shows the data for an isotype control. The bold line shows CCR4 expression after stimulation. The results indicate that tumour microenvironment can induce expression of CCR4 on tumour cells.
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Chemokine receptor CCR4 and its ligands CCL1 7 and CCL22 are used as markers for the identification and/or staging of cancer. The level of CCR4, CCL17 and CCL22 are found to increase during malignant tumour progression. CCR4, CCL17 and CCL22 are used as markers for the stratification of cancer patients according to their suitability for treatment with anti-cancer agents. Information of diagnostic character is provided by measuring the level of one or more of CCR4, CCL 17 and CCL22 present in a patient sample. Methods of treatment of cancer patients which agents that modulate the activity of CCR4, CCL17 and CCL22. Methods of screening for agents which modulate the biological activities of CCR4, CCL 17 and CCL22 provide anti-cancer agents.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to tampon pledgets and more particularly to tampon pledgets that provide an indication to a user that a tampon in which the pledget is incorporated, is ready to be changed.
BACKGROUND
[0002] Due to the impracticality associated with removing a tampon to ascertain whether or not it has reached its absorbent limit, it is typically difficult to determine the appropriate time for replacement. Currently there are no indicators that are built into a tampon to signal the consumer that the tampon is close to full capacity. The consumer, therefore, is left with having to rely on instinct when making the determination as to when to change the tampon. This can often result in the tampon being changed prior to reaching full saturation, or subsequent to reaching full saturation when the tampon is changed too late, thereby increasing the potential for leakage past the tampon.
[0003] Based on the foregoing, it is the general object of the present invention to provide a tampon that employs some indication that allows a user to discretely determine when tampon change is necessary.
SUMMARY OF THE INVENTION
[0004] The present invention resides in one aspect in a tampon pledget having at least two layers of absorbent material that are formed into the pledget. A quantity of moisture activated material is positioned in contact with and/or adjacent to one of the layers of absorbent material. Upon contact with menses, the moisture activated material reacts in one of an exothermic and an endothermic manner so that during use, the pledget, when forming part of a tampon, can alert a user when the absorbent capacity of the tampon has been reached.
[0005] Preferably, where the reaction is endothermic, the above-described moisture activated material is made from at least one of salt hydrates, anhydrous salts and organic compounds. Where a salt hydrate is employed, it is preferable that the moisture activated material be at least one of sodium acetate, sodium carbonate, sodium sulfate, sodium thiosulfate, or sodium phosphate. Where anhydrous salts are used, it is preferable that the moisture activated material be at least one of ammonium nitrate, potassium nitrate, ammonium chloride, potassium chloride and sodium nitrate. When the moisture activated material is organic, the preferred materials include one or more of urea and xylitol.
[0006] In an embodiment of the present invention, the moisture activated material is positioned in a packet with the packet being located between layers of material that are ultimately formed into the pledget so that upon formation of the pledget, the packet is located interior of an outer surface defined by the pledget. The packet can be formed from at least two layers of nonwoven material bonded together with the moisture activated material positioned therebetween. The nonwoven material can be bonded together by using one or more of adhesives, heat sealing, stitching, and ultrasonic bonding. The packet can also be formed from a single piece of nonwoven material folded over onto itself with the edges of the folded nonwoven material being bonded together in the above-described manner. Preferably, the moisture activated material is in particulate or powder form; however, the present invention is not limited in this regard as the moisture activated material can also be in sheet form without departing from the broader aspects of the present invention.
[0007] In another embodiment of the present invention, rather than being positioned in the above-described packet, the moisture activated material is dispersed within, and on a surface of a first of the at least two layers of absorbent material. A second of the at least two layers of absorbent material is positioned over the surface of the first layer of absorbent material so that upon formation of the layers of absorbent material into the pledget, the moisture activated material is located interior of an outer surface defined by the pledget. Accordingly, where the pledget forms part of a tampon, once moisture absorbed by the pledget reaches the moisture activated material, an endothermic or exothermic reaction occurs which is discretely detectable by a user and provides an indication regarding the need to change the tampon.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a schematic plan view of a temperature-change packet for use in one embodiment of the present invention;
[0009] FIG. 2 is a cross-sectional view of the temperature-change packet of FIG. 1 ;
[0010] FIG. 3 is a schematic plan view of a continuous length of temperature-change packets;
[0011] FIG. 4 is a schematic plan view of the temperature-change packet of FIG. 1 in place between layers of a tampon pledget; and
[0012] FIG. 5 is a cross-sectional view of a tampon as described herein.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] The tampon pledget of the present invention comprises a moisture activated material that produces either an endothermic or exothermic reaction upon contact with moisture. The moisture activated material reacts to (is “activated by”) contact with menstrual fluid by absorbing heat from, or releasing heat to, the surrounding area. The moisture activated material is located interior of an outer surface of the pledget. Accordingly, once activated, the moisture activated material causes a temperature change within the pledget that is detectable by a wearer of the tampon. A tampon typically includes a removal string at the distal end of the tampon. Preferably, the moisture activated material is disposed at or near the string end of the tampon, so that it will be activated when the tampon is near full saturation due to contact with bodily fluid. Preferably, there is substantially no moisture activated material at the insertion end (i.e., the proximal end) of the tampon.
[0014] In use, the above-described tampon including the pledget having the moisture activated material forming a part thereof is inserted in the body. When the moisture activated material in the tampon comes into contact with menses, the user senses the temperature change and is thereby signaled that the tampon is ready to be replaced.
[0015] The moisture activated material may be a heat-absorbing material that produces an endothermic reaction, such as sodium acetate, sodium carbonate, sulfate, thiosulfate, phosphate or anhydrous salts such as ammonium nitrate, potassium nitrate, ammonium chloride, potassium chloride, and sodium nitrate, or organic compounds such as urea or a sugar such as xylitol.
[0016] Alternatively, the temperature-change material may be a heat-releasing material that produces an exothermic reaction such as aluminum chloride, aluminum sulfate, potassium aluminum sulfate or the like.
[0017] The moisture activated material may be in particulate or powder form and may be packaged in between layers of a permeable, non-woven material to provide a temperature-change packet as shown in FIG. 1 and FIG. 2 . The temperature-change packet 10 includes the moisture activated material 12 that is disposed in between layers 14 and 16 of the permeable, non-woven material. The layers 14 , 16 may be sealed together by an adhesive, heat seal, ultrasonic bond, stitching, or any other suitable means or any combination of the foregoing, to form a perimeter seal 18 around the moisture activated material. The layers 14 and 16 of the permeable, non-woven material may comprise spunbond polypropylene (SBPP), spunbond-meltblown-spunbond (SMS), thermally bonded webs, chemically bonded webs, through-air-bonded carded webs (TABCW), carded-and-needle-punched webs, hydro-entangled webs, cotton/polypropylene webs, PET (polyester) webs, spunlace, airlaids, meltblowns, apertured films, tissues, etc. Preferably, the permeable, non-woven material is suitable for high temperature processing (e.g., handling at temperatures of about 300° F. or higher). In a particular embodiment, the layers 14 and 16 are made from a composite comprising about 30% cotton and about 70% polypropylene fibers, by weight, and has a basis weight of 33 gsm (grams per square meter). A non-woven material found to be useful in making the packets is SH-PPC-33 manufactured by Shalag Nonwoven of Israel. Optionally, the layer 16 may be a folded-over portion of the layer 14 .
[0018] Optionally, the layers 14 and 16 may comprise lengths of material with which a plurality of packets are formed to provide a length 20 of interconnected temperature-change packets 10 as shown in FIG. 3 . The length 20 of temperature-change packets may be wound up in pancake rolls or traverse spools. A length 20 of temperature-change packets 10 may then be installed on a tampon manufacturing machine. The length 20 of temperature-change packets 10 may be unwound and cut into individual temperature-change packets 10 for incorporation into temperature-change pledgets.
[0019] As shown in FIG. 4 , a pledget 22 is formed by placing an individual temperature-change packet 10 on a first layer 24 of pledget material. A second layer 26 of pledget material is then placed on the first layer 24 . The pledget 22 is used to form a tampon with the temperature-change packet 10 therein near the string end of the tampon.
[0020] In another embodiment of the present invention, a moisture activated material is dispensed on top of, and in the central area of, a first layer 24 of pledget material. A second layer 26 of pledget material is placed over the moisture activated material to sandwich the moisture activated material 12 between the layers 24 and 26 of pledget material. The layers 24 , 26 of pledget material are used to form a temperature-change pledget that is used to form the tampon. Preferably, the moisture activated material is disposed near the string end of the tampon.
[0021] In another embodiment, moisture activated material 12 is blended into the binder (polymer) and the absorbent (cellulose, cotton and/or rayon) fibers that form pledget material. For example, particles of moisture activated material 12 are blended into an airlaid web that is used to make layered pledget composites. The moisture activated material-containing airlaid web is incorporated into the pledget material so as to be concentrated near the string end of the tampon.
[0022] A tampon 30 is shown in FIG. 5 . The tampon 30 has a proximal end 32 , a distal end 34 and a removal string 36 attached at the distal end 34 . The tampon 30 comprises a moisture activated material as described herein, principally at the distal end 34 . There is substantially no moisture activated material at or near the proximal end 32 .
[0023] The terms “first,” “second,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. In addition, the terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
[0024] Although the invention has been described with reference to particular embodiments thereof, it will be understood by one of ordinary skill in the art, upon a reading and understanding of the foregoing disclosure, that numerous variations and alterations to the disclosed embodiments will fall within the spirit and scope of this invention and of the appended claims.
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In a tampon pledget, a quantity of moisture activated material is positioned in contact with, or adjacent to a layer of absorbent material used in forming the pledget. Upon contact with menses, the moisture activated material reacts in one of an endothermic and exothermic manner so that in use, the pledget, when forming part of a tampon can thermally alert a wearer when the pledget has reached its absorbent capacity.
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CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. provisional application No. 61/606,096, filed on Mar. 2, 2012, the entirety of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates, in general, to garment storage and, more particularly, to garment wardrobes and closets that are relatively light weight and that may be readily assembled by purchasers.
[0004] 2. General Background of the Invention
[0005] Due to a shortage of built-in closet space in many homes and apartments, freestanding wardrobes have been popular for quite some time. Some freestanding wardrobes are relatively large, bulky, and expensive pieces of fine furniture. However, not all homeowners or renters want to incur the expense of obtaining this type of wardrobe. Other wardrobes are made from relatively inexpensive materials, but are often considered to be unattractive and thus unsuitable for use in the bedroom or other commonly used portions of the home, and are instead relegated to use within a basement or attic of the home.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention is intended to provide a wardrobe that is constructed from relatively inexpensive components and capable of being sold in disassembled form, yet, when readily assembled by the purchaser, is attractive in appearance, and thus suitable for use within bedrooms and other commonly used areas of the home. As such, it is desirable for the present invention to incorporate features not commonly used in wardrobes but rather commonly used in traditional, built-in closets, such as horizontally sliding doors. Traditional sliding closet doors, however, are relatively heavy and cumbersome, particularly for a product intended to be sold in disassembled form and then readily assembled by an unskilled purchaser. The present invention instead employs lightweight fabric doors, yet provides the fabric doors with sufficient rigidity to enable them to be slid back and forth along associated tracks. Moreover, the fabric doors of the present invention releasably attach to the overall wardrobe, enabling them to be removed for repair or replacement, as well as enabling the substitution of differently-colored or differently-patterned doors in accordance with user preference. In addition, the present invention supports the substitution of doors of varying widths, again in accordance with the preference of the user.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0007] FIG. 1 an elevated, exploded perspective view of a first embodiment of the overall present wardrobe invention;
[0008] FIG. 2 is an elevated, exploded perspective view of the wardrobe assembly portion of the first embodiment of the invention;
[0009] FIG. 3A is a top perspective view of the wardrobe rail of the first embodiment of the invention;
[0010] FIG. 3B is a side view of the wardrobe rail of the wardrobe rail of the first embodiment of the invention;
[0011] FIG. 3C is a top plan view of the wardrobe rail of the wardrobe rail of the first embodiment of the invention, partially in section.
[0012] FIG. 4A is a front perspective view of a sliding rail assembly of the first embodiment of the invention; FIG. 4B is a front view of the sliding rail of a sliding rail assembly of the first embodiment of the invention;
[0013] FIG. 4C is a front perspective view of the sliding rail of the first embodiment of the invention;
[0014] FIG. 4D is a side view of two adjacent sliding rails of the first embodiment of the invention and showing, in particular, their relative horizontal spacing upon assembly of the first embodiment of the invention;
[0015] FIG. 4E is a front view of a wheel portion of a sliding rail assembly of the first embodiment of the invention;
[0016] FIG. 4F is a side sectional view of the wheel portion, taken generally along lines 4 F- 4 F of FIG. 4E ;
[0017] FIG. 5 is an elevated, exploded perspective view of the door assembly portion of the first embodiment of the invention;
[0018] FIG. 6A is a side view of a single wardrobe rail of a second embodiment of the invention;
[0019] FIG. 6B is a side view of the single wardrobe rail of FIG. 6A , showing, in particular, the operable positioning of a rolling slider relative to the single wardrobe rail;
[0020] FIG. 6C is a side view of a double wardrobe rail of a third embodiment of the invention;
[0021] FIG. 6D is a side view of the double wardrobe rail of FIG. 6C , showing, in particular, the operable positioning of two rolling sliders relative to the double wardrobe rail;
[0022] FIG. 6E is a combination front view and side view of a wheel of the rolling sliders of FIGS. 6B and 6D ;
[0023] FIG. 6F is a front view of the rolling slider of the second and third embodiments of the invention;
[0024] FIG. 6G is a side view of the rolling slider of the second and third embodiments of the invention and showing, in particular, the use of spacers to provide separation of the wheels and body of the rolling slider;
[0025] FIG. 6H is an exploded perspective view of a rolling slider and associated rail and showing, in particular, the attachment member portion of the rolling slider;
[0026] FIG. 6I is a side perspective view of two rolling sliders within a common wardrobe rail;
[0027] FIG. 6J is a side view of the top portion of a sliding door assembly of the present invention and showing, in particular, the placement of an attachment member and top stiffening member thereof;
[0028] FIG. 6K is a front perspective view of a wardrobe rail of the second embodiment of the present invention and showing, in particular, the releasable attachment of the door assembly to rolling sliders carried by the wardrobe rail
[0029] FIG. 7A is an exploded perspective view of an alternative embodiment of a dual wardrobe rail and sliding rail assembly; and
[0030] FIG. 7B is an enlarged front view of the wardrobe rail of FIG. 7A .
DETAILED DESCRIPTION OF THE INVENTION
[0031] While the present invention is susceptible of embodiment in many different forms, there is shown in the drawings and will herein be described in detail, several specific embodiments, with the understanding that the present disclosure is intended as an exemplification of the principles of the present invention and is not intended to limit the invention to the embodiments illustrated.
[0032] As shown in FIG. 1 , a first embodiment of the present invention is shown as comprising wardrobe assembly 10 , a plurality of vertical tube assemblies 20 , X-frame assembly 30 , a plurality of door assemblies 40 , a plurality of corner bracket caps 60 , garment hang bar 70 , hang bar end caps 80 , a plurality of rail slide assemblies 90 , double hanging bar assembly 100 , and a plurality of fasteners 110 . Fasteners 110 may comprise, for example, M6×35 mm hex head screws, or any other suitable fastener that preferably facilitates assembly of the present invention by the purchaser using only simple hand tools that may be either supplied with the disassembled wardrobe, or that are commonly found in the home. Garment hang bar 70 may constructed from steel tubing having a wall thickness of approximately 0.7 mm. X-frame assembly 30 may be constructed from 6 mm steel rods and attaches to the back of wardrobe assembly 10 across two opposing vertical tube assemblies 20 , thereby providing stiffness and rigidity the frame components of wardrobe assembly 10 .
[0033] As shown in FIG. 2 , wardrobe assembly 10 comprises wardrobe body 11 , wardrobe rail 120 , a plurality of first wardrobe tubes 12 , a plurality of second wardrobe tubes 13 , a plurality of corner brackets 14 , a plurality of grommets 15 , and a plurality of fasteners 110 . The outer side, top, bottom, and back surfaces or wardrobe body 11 are all preferably constructed of a relatively strong fabric material, such as a 600 dernier polyester material. Eight sleeves 16 are formed within wardrobe body 11 proximate the top and bottom surfaces thereof to accommodate the insertion of associated first wardrobe tubes 12 and second wardrobe tubes 13 , which are secured in place by corner brackets 14 and fasteners 110 . Each sleeve is preferably constructed of the same fabric material as the overall wardrobe body. First wardrobe tubes 12 and second wardrobe tubes 13 may be constructed from steel tubing having a wall thickness of approximately 0.7 mm, and corner brackets 14 may likewise be constructed of a steel material.
[0034] As shown in FIG. 1 , corner brackets 14 also receive associated vertical tube assemblies 20 , likewise secured in place by fasteners 110 . A rigid board material 17 is preferably affixed adjacent the inside top and bottom surfaces of wardrobe body 11 to reinforce and provide further rigidity to these surfaces. Grommets 15 are placed through nylon reinforcing webbing disposed on opposing sides of the left and right side surfaces of wardrobe body 11 , proximate the top surface. Double hanging bar assembly 100 includes two opposing hooks cooperating with and grommets 15 which serve as points of hanging attachment, permitting the assembly to be suspended from grommets 15 within the interior of wardrobe body 11 . As described in detail below, each door assembly 40 is releasably attachable to an associated rail slide assembly 90 .
[0035] As shown in FIGS. 3A through 3C , wardrobe rail 120 comprises horizontal portion 121 and two vertical arms 122 . Each vertical arm 122 terminates in a hooked region, formed by horizontal roller support portion 123 and roller retaining portion 124 . Wardrobe rail 120 may be constructed of a rigid polyvinylchloride (“PVC”) material. As shown in FIGS. 4A through 4F , each rail slide assembly 90 comprises door glide rail member 91 , a plurality of wheels 95 and a plurality of tubular rivets 96 . Each rivet 96 , in cooperation with an associated aperture 94 of a tab region 93 of door glide rail member 91 , and an associated aperture 99 of wheel 95 , serves to rotatably affix a wheel 95 adjacent the front surface of glide rail member 91 , with a cylindrical shaft region of each rivet serving as both an axle and a bearing for an associated wheel 95 , about which wheels 95 may freely rotate. As best seen in FIGS. 4D and 4A , each glide rail member 91 includes an elongated raised region 98 , providing a planar, elongated rectangular surface for attachment of releasable fastening member 97 . In a preferred embodiment, releasable fastening member 97 comprises either the male (i.e., hook) or female (i.e., loop) half of a combination hook-and-loop fastener of relatively strong (yet releasable) bonding strength, such as a VELCRO® brand fastener, and is sized to substantially overlie elongated raised region 98 . A suitable adhesive may be employed to securely bond releasable fastening member 97 to elongated raised region 98 .
[0036] Each rail slide assembly 90 is slidably coupled to an associated vertical arm 122 of wardrobe rail 120 by positioning both associated wheel members 95 atop horizontal roller support portion 123 , adjacent roller retaining portion 124 . Horizontal roller support portion 123 accordingly serves as an elongated track, accommodating wheel members 95 to, in turn, permit back-and-forth sliding of door glide rail member 91 relative to wardrobe rail 120 .
[0037] As shown in FIG. 5 , in a first embodiment of the present invention, each door panel assembly includes door panel 41 , having bottom sleeve 42 extending along the entire width of the bottom edge thereof. Bottom weight, which may comprise an elongated rectangular bar of steel or aluminum, may be inserted into bottom sleeve 42 through an aperture disposed at least one end of bottom sleeve 42 . Releasable fastening member 44 extends along substantially the entire top edge of one side of door panel 41 . In a preferred embodiment, releasable fastening member 44 comprises either the male or female half of a combination hook-and-loop fastener of relatively strong bonding strength, such as a VELCRO® brand fastener. A suitable adhesive or stitching may be employed to securely bond releasable fastening member 44 to door panel 41 . Door panel 41 may be constructed of a relatively lightweight fabric material, such as a 300 dernier polyester material.
[0038] Releasable fastening member 44 of door assembly 40 and releasable fastening member 97 of rail slide assembly 90 collectively form the male and female portions of a hook-and-loop fastener, and serve to releasably attach the top edge region of door panel 41 to raised region of 98 of door glide rail member 91 . This, in turn, permits each door panel 41 to slide back and forth proximate the front opening of wardrobe body 11 , as rail slide assembly 90 is slid back and forth by rolling wheel members 95 along the upper surface of horizontal roller support portion 123 of wardrobe rail 120 .
[0039] The releasable attachment of individual door assemblies 40 to associated rail slide assemblies 90 permit door assemblies 40 to be readily removed and replaced to facilitate their cleaning or repair. Moreover, the ease of replacement of door assemblies 40 permits any door panel 41 to be rapidly replaced with one of another color, pattern, and/or size, depending upon the user's preference.
[0040] Second and third embodiments of the present invention are shown in FIGS. 6A through 6K . FIG. 6A shows single wardrobe rail 130 of the second embodiment of the present invention as comprising vertical arms 131 , horizontal legs 132 , and aperture 133 disposed between opposing horizontal legs 132 . FIG. 6C shows double wardrobe rail 140 of the third embodiment of the present invention as comprising three vertical arms 141 , each with associated horizontal legs 142 . As shown in FIG. 6C , the two outer vertical arms 141 each has one associated, inwardly-extending horizontal leg 142 , while a central vertical arm 141 includes two associated horizontal legs 142 , extending in opposing directions. In this manner, two bottom apertures 143 are each disposed between opposing pairs of horizontal legs 142 .
[0041] As shown in FIGS. 6F through 6H , in the second and third embodiments of the present invention, door sliding member 150 comprises slider body 151 , having recessed rectangular region 152 and two pairs of wheels 155 . Each pair of wheels 155 are rotatably attached to opposing sides of slider body 151 , proximate the top edge of slider body 151 . Spacers 154 are employed between each wheel 155 and slider body 151 to facilitate each wheel's rotation. Spacers 154 may comprise separate components, or may be integrally formed, raised portions of slider body 151 . Moreover, an axle extending outwardly from each spacer 154 extends through central aperture 156 of each wheel 155 .
[0042] Releasable fastening member 160 is substantially rectangular in shape and is sized to fit within recessed region 152 of slider body 151 . In a preferred embodiment, releasable fastening member 160 comprises either the male or female half of a combination hook-and-loop fastener of relatively strong bonding strength, such as a VELCRO® brand fastener. A suitable adhesive may be employed to securely bond releasable fastening member 160 to recessed region 152 of slider body 151 .
[0043] As shown in FIGS. 6B , 6 D and 6 G, in the second and third embodiment of the present invention, each door sliding member 150 slidably engages an associated wardrobe rail 130 or 140 , through the engagement of associated wheel members 155 atop horizontal legs 132 or 142 . Crossbar members 153 of slider body 151 serve to further retain each sliding door member 150 in sliding engagement with an associated wardrobe rail 130 or 140 , including inhibiting slider body 151 from rocking back and forth. As shown in FIG. 61 , for each door assembly of the second and third embodiments of the present invention, at least two door sliding members 150 slidably engage a wardrobe rail 130 (or 140 ).
[0044] As shown in FIG. 6J and 6K , door assembly 170 includes door panel 171 having top sleeve 176 extending along the entire width of the top edge thereof. Top sleeve 176 may be formed by folding a top portion 172 of door panel 171 about itself, and then stitching or otherwise attaching the top edge of the door panel 171 at seam 175 , thereby creating an internal channel having end apertures 173 . A stiffening member 174 , which may comprise an elongated rectangular bar or steel or aluminum, and extending along substantially the entire width of door panel 171 , is inserted through aperture 173 and carried within top sleeve 176 .
[0045] As shown in FIGS. 6J and 6K , substantially rectangular releasable fastening members 174 are disposed at opposing top inside corners of door panel 171 . In a preferred embodiment, each releasable fastening member 174 comprises either the male or female half of a combination hook-and-loop fastener of relatively strong bonding strength, such as a VELCRO® brand fastener. A suitable adhesive or stitching may be employed to securely bond releasable fastening member 174 to door panel 171 .
[0046] As shown in FIG. 6K , releasable fastening member 174 of door assembly 170 and releasable fastening member 160 of door sliding member 150 collectively form the male and female portions of a hook-and-loop fastener, and serve to releasably attach the top edge region of door panel 171 to two door sliding members 150 . This, in turn, permits each door panel 171 to slide back and forth proximate the front opening of wardrobe body 11 , as door sliding members 150 are slid back and forth by rolling wheel members 155 along the upper surface of horizontal legs 132 or 142 of wardrobe rail 130 or 140 , respectively.
[0047] The use of a plurality of individual door sliding members 150 , which are individually slidable within an associated rail member, permits door panels 171 of varying widths to be readily accommodated, as the distance between door sliding members 150 can be adjusted to accommodate a particular desired width of door panel 171 . Moreover, as in the first embodiment of the present invention, the releasable attachment of individual door sliding members to door assemblies 170 permits door assemblies 170 to be readily removed and replaced to facilitate their cleaning or repair, or to accommodate the color, pattern, or size preference of the user.
[0048] An alternative embodiment of a dual wardrobe rail and sliding rail assembly is shown in FIGS. 7A and 7B as including rail slide assembly 90 ′, which is somewhat similar in construction to rail slide assembly 90 as described above, but which includes four, rather than two, associated wheels; and double wardrobe rail 140 ′, which is somewhat similar in construction to double wardrobe rail 140 , as described above. In particular, each rail slide assembly 90 ′ comprises door glide rail member 91 ′, four wheels 95 and two tubular rivets 96 . Each rivet 96 , in cooperation with an associated aperture 94 ′ of a tab region 93 ′ of door glide rail member 91 ′, and associated apertures of a pair of wheels 95 , serves to rotatably affix a pair of wheels 95 adjacent opposing sides of the front surface of glide rail member 91 ′, with a cylindrical shaft region of each rivet serving as both an axle and a bearing for two associated wheels 95 , about which wheels 95 may freely rotate.
[0049] With continuing reference to FIGS. 7A and 7B , double wardrobe rail 140 ′ of this embodiment of the present invention is shown as comprising three vertical arms 141 ′, each with associated horizontal legs 142 ′. As best seen in FIG. 7B , the two outer vertical arms 141 ′ each has one associated, inwardly-extending horizontal leg 142 ′, while a central vertical arm 141 ′ includes two associated horizontal legs 142 ′, extending in opposing directions. In this manner, two bottom apertures 143 ′ are each disposed between opposing pairs of horizontal legs 142 ′.
[0050] Many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced other than as specifically described. Various modifications, changes and variations may be made in the arrangement, operation and details of performing the various steps of the invention disclosed herein without departing from the spirit and scope of the invention. The present disclosure is intended to exemplify and not limit the invention.
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A wardrobe that may be sold in disassembled form and be readily assembled by a purchaser includes employs lightweight fabric doors, yet provides the fabric doors with sufficient rigidity to enable them to be slid back and forth along associated tracks. The fabric doors releasably attach to the overall wardrobe, enabling them to be removed for repair or replacement, as well as enabling the substitution of differently-colored or patterned doors in accordance with user preference. Substitution of doors of varying width are supported, again in accordance with the preference of the user.
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This application claims benefit of Provisional Application 60/001,639, filed Jul. 28, 1995.
FIELD OF THE INVENTION
This invention relates to a novel valve apparatus and to a method for reducing water use at manually regulated taps, and more particularly, to an apparatus for reducing water use at taps such as household kitchen and bathroom sinks.
BACKGROUND
As a result of either water costs or shortages, it is often desirable to reduce the amount of water consumed at a manually regulated point of use, particular at devices such as a tap supplying water to a household kitchen sink. Typically, the actual amount of water required to accomplish the task at hand is relatively small compared to the amount of water which is inadvertently wasted while the user's attention is directed elsewhere. For example, it is often inconvenient to shut off the water flow between rinsing separate utensils, or while cutting a freshly rinsed vegetable. While the economic cost of such wasteful practices has only begun to reach the pocketbooks of individual consumers, collectively, society has begun to experience the cost of such practices in many ways. For example, it has become common in certain areas to hear of the denial of water availability certifications which are required before beginning construction of new homes. Also, consumptive water uses have reduced in-stream flows, have contributed to the decline of fish populations, and also have adversely impacted the recreational use of certain lakes and rivers which are used for water supply.
I am aware of various attempts in which an effort has been made to provide an apparatus for reducing water flow at a tap. Such attempts are largely characterized by designs which include some sort of repositionable valve which is controlled by a foot or hand actuated mechanism. For example, one such design is shown in U.S. Pat. No. 5,095,941 issued Mar. 17, 1992 to J. Betz for METHOD AND APPARATUS FOR ACTUATING A FAUCET. In one embodiment, his invention provides a pressure switch which is mounted at or near the floor and is activated by the user's foot, and which allows flow for a predetermined amount of time after the foot valve is actuated. More recently, U.S. Pat. No. 5,386,600 was issued Feb. 7, 1995 to Gilbert, Sr. for LATCHING FOOT PEDAL ACTUATED TAP WATER FLOW CONTROLLER. That patent discloses a latch and release mechanism for regulating water flow through a tap with a foot actuated valve.
For the most part, the documents identified in the preceding paragraph disclose devices which require the supply of an extended mechanical or electrical linkage portion, and in some cases, additional various adjustable parts. Also, in so far as I am aware, the use of a diaphragm valve which utilizes the fluid supply pressure itself for control of the fluid flow has not been exploited heretofore.
Thus, the advantages offered by my simple hydraulically actuated valve design, and its avoidance of electrical or mechanical linkages as a prerequisite to actuate a water flow valve, are important and self-evident.
OBJECTS, ADVANTAGES, AND NOVEL FEATURES
I have now invented, and disclose herein, a novel design for a water flow control valve which does not have the above-discussed drawbacks common to those somewhat similar products heretofore designed or used of which I am aware. Unlike the earlier designs which attempted to provide a mechanical or electrical linkage for use in opening and closing a valve, my design provides a simple means for opening and closing the valve, without resorting to electrical or mechanical components. Further, it is simple to use, easy to install, relatively inexpensive and easy to manufacture, and otherwise superior to those designs heretofore used or proposed. In addition, it provides significant reduction in water consumption in taps which utilize the device.
From the foregoing, it will be apparent to the reader that one important and primary object of the present invention resides in the provision of a novel valve apparatus for reducing the consumption of water in manually regulated water taps, and which improves the reliability, simplicity and safety of such types of devices by reducing or eliminating reliance on electrical wiring or extensive mechanically linked parts.
Other important but more specific objects of the invention reside in the provision of (a) an apparatus for reducing the consumption of water at manually operated taps, and (b) a method for reducing the flow of water at manually operated taps, using the apparatus described herein which:
can be manufactured in a simple, straightforward manner of commonly available materials;
in conjunction with the preceding object, have the advantage that they can be easily and quickly installed by the user in existing, conventional, manually operated household kitchen and bathroom sinks;
which in a relatively inexpensive manner can reduce water consumption at such kitchen and bathroom sinks.
Other important objects, features, and additional advantages of my invention will become apparent to the reader from the foregoing and the appended claims and as the ensuing detailed description and discussion proceeds in conjunction with the accompanying drawing.
SUMMARY OF THE INVENTION
I have now invented and disclose herein a novel valve apparatus for controlling the discharge of fluids, and in particular for controlling the discharge of water from a pressurized water supply system. The valve apparatus is particularly useful for minimizing the amount of water used at household sinks.
My novel valve apparatus is advantageously utilized for control flow of fluid discharge from a pressurized fluid distribution system, such as those systems configured with the valve apparatus being supplied with fluid via an incoming conduit that supplies the fluid under pressure. The valve apparatus includes a primary valve, a pilot valve, and an actuator which is linked to the pilot valve. The primary valve has an inlet adapted to receive fluid under pressure from the incoming conduit, an outlet adapted to discharge the fluid to an outlet conduit, a diaphragm chamber having a pilot portion and a working portion, and a fluid pressure controlled primary diaphragm. The primary diaphragm is located in the primary diaphragm chamber between the pilot portion and the working portion of the primary diaphragm chamber. The primary diaphragm has a pilot side and a working side. The working side of the primary diaphragm is configured to engage at least a portion of the inlet, as well as the outlet. The primary diaphragm is adapted to be responsive to fluid pressure to move between (a) an open position wherein fluid pressure from the inlet disengages the primary diaphragm from the outlet so that fluid is allowed from the inlet to the outlet and thence to the outlet conduit, and (b) a closed position, wherein fluid pressure on the pilot side of the primary diaphragm forces the primary diaphragm to sealingly engage the outlet so that fluid is not allowed from the inlet to the outlet. To release fluid pressure so as to operate the valve, a bleed inlet line from the primary valve is provided operatively connected to a pilot valve. The bleed inlet line has a first end and a second end, with the first end hydraulically connected to the pilot portion of the primary diaphragm chamber. The pilot valve has a bleed inlet which is hydraulically connected to the second end of the bleed inlet line from the pilot portion of the diaphragm chamber. Also, the pilot valve has a bleed outlet for discharge of the bleed fluid, and a pressurizable fluid reservoir located between the bleed inlet and the bleed outlet. The fluid reservoir is adapted to receive pressurized liquid from the bleed inlet line. The pilot valve is operated using a plunger to displace a repositionable pilot diaphragm between (a) a normally closed position wherein the repositionable pilot diaphragm sealingly engages the bleed outlet to block escape of said pressurized fluid through the pilot valve, and (b) an open position, wherein the repositionable pilot pilot diaphragm is displaced from the bleed outlet so as to hydraulically open the bleed outlet for passage of fluid therethrough. In the open position, pressurized fluid from the pilot side of the primary diaphragm chamber is discharged through the pilot valve, relieving pressure on the diaphragm. An actuator, operatively linked to the pilot valve, is provided to enable the pilot valve to be open and closed by manipulation of the actuator. The actuator has an open position and a normally closed position, and is adapted to be moveable to the open position in response to movement of the actuator, so that upon repositioning of the actuator to the open position, the operating link causes the plunger of the pilot valve to reposition the pilot valve diaphragm from a normally closed position to an open position, thereby effecting the release of pressurized fluid out the bleed outlet and releasing fluid pressure on the pilot side of the primary diaphragm, to thereby cause the primary diaphragm to move to the open position, allowing fluid to flow through the primary valve.
My novel valve apparatus provides a simple device for minimizing water use in household sinks. This design provides a significant improvement in the art by reducing complexity and manufacturing costs compared to previous designs known to me for regulating or minimizing flow of liquid at point of use type devices such as kitchen and bathroom sinks.
BRIEF DESCRIPTION OF DRAWING
FIG. 1 is a perspective view of a kitchen sink and the front of a cabinet adjacent thereto, showing the actuator bar utilized in one embodiment of the present invention.
FIG. 2 is a perspective view of the valve apparatus of the present invention, showing use of a primary regulating valve with both hot and cold water lines, and a dual pilot valve which is selectively positioned by use of a front cabinet mounted actuation bar.
FIG. 3 is a cross-sectional view of one embodiment of the present invention, showing a single primary valve and a single pilot valve for regulating the discharge of water from a pressurized conduit, with the pilot valve and the primary valve shown in the closed, no-flow position.
FIG. 4 is a cross-sectional view of the embodiment of the present invention which was just illustrated in FIG. 4 above, showing a single primary valve and a single pilot valve for regulating the discharge of water from a single pressurized inlet conduit, with the pilot valve and the primary valve shown in the open, flow position, so that liquid may flow through the primary valve and be discharged.
FIG. 5 is a cross-sectional view of the pilot valve used in the present invention, shown in the closed, noflow position.
FIG. 6 is a cross-sectional view of the pilot valve used in the present invention, shown in the open, bleed discharge position.
FIG. 7 is an exploded perspective view of a dual pilot valve as used in the present invention, showing the various elements of the pilot valve, including the main body, the diaphragm, the diaphragm seat, plunger, inner housing, and outer housing.
FIG. 8 is a side elevation view, showing the dual pilot valve, and showing in hidden lines, the fluid inlet and outlet conduits from the pilot valve.
FIG. 9 is a cross-section view of a primary fluid valve, shown in the open position.
FIG. 10 is a cross-section view of the primary fluid valve first shown in FIG. 9, now showing the valve in the closed position.
FIG. 11 is a perspective view of a dual pilot valve utilized in the present invention in its operative position interconnected with an actuation bar at the front of a cabinet.
FIG. 12 includes three closely related views, 12A, 12B, and 12C. In FIG. 12A, a partial cut-away view of the internal assembly in an actuation bar, illustrated in the closed, no-flow position, showing pivot pins, pivot bars, and pilot valve interconnection. FIG. 12B is a cross-sectional view of the internals in an actuation bar, showing pivot pins and pivot arms, taken across line 12B--12B of FIG. 12C. FIG. 12C is a partial cut-away view of the internal assembly of an actuation bar, similar to the view of FIG. 12A, but now showing the actuation bar and pivot arms in the engaged (inwardly depressed), liquid flow position.
FIG. 13 is an exploded perspective of another embodiment of my dual pilot valve, similar to that shown in FIG. 7 above, but now showing use of side inlet and exit lines, as well as a modified housing.
FIG. 14 is an exploded perspective of another embodiment of my primary diaphram valve.
FIG. 15 is a perspective view of the embodiment of my primary diaphram valve just set forth in FIG. 15, but now in its fully assembled, operational configuration.
FIG. 16 is a perspective view of a second embodiment of the actuator bar in my invention, which uses a mounting plate in place of a housing for the actuator
FIG. 17 is a partial cut-away view of the internal assembly of the embodiment of my actuator bar first set forth in FIG. 17, showing the spring assembly used to achieve retrograde motion of the pin used to activate the pilot valve.
FIG. 18 is yet another view of the embodiment set forth in FIGS. 17 and 18, now showing the actuator bar in the open, flow position, with the pin allowed to protrude outward when the actuator bar is pressed inward.
In the various figures, similar parts may be indicated by using the same reference numerals with a suffix of one or more prime symbols (', or ", for example), without further mention thereof, and it is to be understood that the latter described embodiments can be referred to with the same name as the initially described part which does not utilize such suffix.
DESCRIPTION
Attention is directed to FIG. 1 of the drawing, where typical kitchen sink 20 with tap 22 having typical hot 24 and cold 26 manual control valves is depicted. At the front 28 of cabinet 30, an actuator 32 with housing 34 is shown. Also, an optional center actuator 32' is shown with center actuator housing 32'. Basically, this FIG. 1 depicts the external appearance of my valve apparatus 36 when installed, the major components of which are as illustrated in FIG. 2.
Turning to FIG. 2, a hot water primary valve 40 is shown installed between hot water inlet conduit 42 and hot water outlet conduit 44. Likewise, cold water primary valve 46 is shown installed between cold water inlet conduit 48 and cold water outlet conduit 50. A dual pilot valve 52 is mounted adjacent linkage 54 with actuator 32. The dual pilot valve 52 is configured to serve both the hot water primary valve 40 and the cold water primary valve 46. The dual pilot valve 52 is connected to a hot water bleed inlet line 56 and a hot water bleed outlet line 58, as well as to similar cold water bleed inlet line 60 and cold water bleed outlet line 62.
If desired, a second, optional actuator 32" with housing 34" can be provided for use with an operator's knee or foot (not shown), for example. In such cases, the configuration is fundamentally the same, although in some case it may be advantageous to use a top and bottom piping arrangement in the pilot valve 52", rather than a bottom piping arrangement as provided in pilot valve 52 above. In such a case, the hot water bleed inlet 48 and bleed outlet line 56 are preferably provided on one end of the pilot valve 52", and the cold water bleed inlet 60' and bleed outlet 62' on the other end of pilot valve 52".
Many important structural and functional details of my novel valve apparatus can be easily seen in FIGS. 3 and 4, where the operation of my valve apparatus is depicted using a single primary valve 70 (similar to either hot 40 or cold 46 primary valves shown in FIG. 2 above) and a single pilot valve 72. As shown, FIG. 3 shows primary valve 70 and pilot valve 72 in the closed position, so that no fluid from inlet conduit 74 is allowed to pass through valve 70 to the outlet conduit 76. FIG. 4 shows the same primary valve 70 and pilot valve 72 in the open position, where fluid from inlet conduit 74 is allowed to pass through valve 70 to the outlet conduit 76.
The method via which the primary valve 70 is maintained in the closed position can be better understood by analysis of the key structural elements of my novel valve apparatus and their interrelationship as seen in FIGS. 3 and 4. The primary valve 70 has an inlet space 78 which is adapted to receive incoming fluid as indicated by reference arrow 80 from the incoming conduit 74. For convenience, a threaded connector 82 may be utilized to join incoming conduit 74 to primary valve 70. An outlet space 84 is provided to discharge the fluid, as indicated by reference arrow 86, to outlet conduit 76. For convenience, a threaded connector 88 may be utilized to join outgoing conduit 76 to primary valve 70. Diaphragm housing 90 and body 92 of primary valve 70 combine to form therebetween a diaphragm chamber 94. The diaphragm chamber 94 houses a fluid pressure controlled primary diaphragm 96. The primary diaphragm 96 has a pilot side 98 and a working side 100, to divide the diaphragm chamber into a pilot portion 102 and a working portion 104 (see FIG. 4 below). The working side 100 of the primary diaphragm 96 is configured to sealingly engage a seat 106 at the upstream end 108 of outlet space 84. Also, the primary diaphragm 96 engages and interacts with fluid (as indicated by reference arrows 110) from at least a portion of inlet 78. The primary diaphragm 96 is made of a long lasting flexible material and is suitable to be responsive to fluid pressure to move between (a) a closed position, wherein fluid pressure on the pilot side 98 of the primary diaphragm 96 forces the primary diaphragm to sealingly engage the seat 106 of outlet 84 so that fluid 80 is not allowed from the inlet space 78 to the outlet 84, and (b) an open position, as shown in FIG. 4, wherein fluid pressure from inlet space 78 disengages the primary diaphragm 96 from seat 106 of the outlet 84 so that fluid 80 is allowed from the inlet space 78 to the outlet 84 and thence to outlet conduit as indicated by reference numeral 86.
To operate the flexible primary diaphragm 96, a bleed inlet line 112 is provided to hydraulically connect a pressurizable fluid reservoir 114 in pilot valve 72 with the diaphragm chamber 94. The bleed inlet line 112 has a first end 114 hydraulically connected via outlet port 116 to the pilot portion 102 of diaphragm chamber 94, and a second end 118 hydraulically connected to bleed inlet 120 of the fluid reservoir 114 in pilot valve 72. The pressurizable fluid reservoir 114 is adapted to receive pressurized liquid, via way of bleed inlet line 112.
A repositionable pilot diaphragm 122 is provided to sealingly engage the seat 124 of bleed outlet 126 from the fluid reservoir 114. The pilot diaphragm 122 is displaceable by a plunger 128 between (a) a normally closed position, as shown in FIG. 3, wherein the repositionable pilot diaphragm 122 sealingly engages the seat 124 of the bleed outlet 126 to block escape of fluid through outlet conduit 130 of pilot valve 72, and (b) an open position, wherein the repositionable pilot pilot diaphragm 122 is displaced from the seat 124 of bleed outlet 126 so as to hydraulically open the bleed outlet 126 for passage of fluid therethrough, so that pressurized fluid from the pilot side 102 of the primary diaphragm chamber 94 is discharged through outlet conduit 130 of pilot valve 72. Preferably, pilot valve 72 is provided with a bleed outlet line 122, connected at a first end with outlet conduit 130 and at a second end to the outlet 84 of primary valve 70, so that fluid is routed to outlet conduit 76 for use, rather than being wasted.
To operate pilot valve 72, an actuator (32 or 32') is provided, preferably at the front 28' of cabinet 30', when the valve apparatus is used in a household kitchen or bathroom sink. The actuator 32' is preferably biased by spring 132 in the normally closed position, as shown in FIG. 3, and is manually depressed in the direction of reference arrow 134, as indicated in FIG. 4, to reach an open position. Actuator 32' includes linkage 136, which has pushblock 137 and pivot arms 138 and 140 (further seen in FIG. 12 below) to react against pivot pin 142 in response to inward movement of actuator 32 (which relieves the tension exerted by spring 132)'. Pivot arms 138 and 140 react against pivot points 143 and 146, respectively (seen in FIG. 12 below) to resultingly manipulate linkage 136 and pin 148 outwardly, so as to move plunger 128 outwardly in the direction of reference arrow 150 in FIG. 4, to open pilot valve 72. The linkage 136 is adapted to be moveable to the open position in response to movement of the actuator 32', so that upon repositioning of the actuator 32' to the open position, the operating linkage 136 causes the plunger 128 of the pilot valve 72 to reposition the pilot valve diaphragm 122 from a normally closed position to an open position. When that happens, pressurized fluid contained in reservoir 114 is released from the pilot side 102 of the primary diaphragm 96, causing the primary diaphragm 96 to move to the open position as shown in FIG. 4.
When the pilot valve 72 is returned to the closed position as set forth in FIG. 3, a small portion of pressurized fluid from supply conduit 80 enters inlet space 78 and then passes through at least one weep passageway 152 in primary diaphragm 96, as indicated by reference arrow 154. The weep passageway 152 is provided with sufficient size so that at least a small volume of pressurized fluid, adequate to exert sufficient pressure on the pilot side 98 of the primary diaphragm 96 to force the diaphragm 96 to sealingly contact seat 106 and thus close valve 70, is able to enter the pilot side 102 of the diaphragm chamber 94.
Structural details of a slightly different pilot valve embodiment, as practiced with a dual pilot valve 72', may be better seen in FIGS. 5, 6, 7, and 8. A main body 160 of dual pilot valve 72' is provided in a generally oval bathtub shape to accommodate two pilot valves 72. At the rear wall (or bottom) 162 of the body 160, a recessed fluid receiving chamber 164 is provided. Protruding from the rear wall 162 is a bleed outlet 126'with a bleed outlet seal face 124'. A raised ledge 166 is provided in rear wall 162 with peripheral groves 168a and 168b around each pilot valve 72 to receive a complementary raised edge seal 170a and 170b of the flexible dual pilot diaphragm 122'. The preferably oval shaped dual pilot diaphragm 122' ideally fits snugly against the raised ledge 166 and extends laterally to the inner oval shaped wall 172 of dual pilot valve 72'. Two recessed, preferably smooth, cymbal shaped recessed concave diaphragm seats 180 are provided in retainer 182 to accommodate individual pilot valve sections 184 and 184 of the dual pilot diaphram 122'. Individual posts 186 and 188 of plunger 128' fit snugly through apertures 190 and 192 of retainer 182 with sufficient length L forward of the inside surface 194 of plunger 128' that posts 186 and 188 may each impinge upon the outside surface 196 of dual pilot diaphram 122' so as to depress the inside surface 198 of pilot diaphram 122' sealingly against the bleed outlet seals 124'. As shown in FIGS. 5 and 6, plunger 128' is moved from its forward, normally closed position to a rearward, open position (as depicted in FIG. 6) via pin 148 which is operably connected to plunger 128 via any convenient means such as threaded connection as illustrated, for example in FIG. 6, via way of threads 200. Pin 148 is located within a threaded tube 202 which is secured at one end at the inner housing 204 of the dual pilot diaphram valve 72', and at the other end at cabinet 30' between knurled knobs 206 and 208. An outer housing 210 or other suitable means can be used to stabilize the pilot valve 72' against movement, as well as to encase the inner housing 204. A locking beveled hook 212 in outer housing 210 and complimentary groove 214 in body 160 of pilot valve 72' may be used to secure outer housing 210.
Turning now to FIGS. 9 and 10, it can be appreciated that the design of primary diaphram 96 can be such that by providing ribs 220, an adequately sized pilot portion 102 of diaphram chamber 94 can be assured so that sufficient fluid can be admitted through weep holes 152 to fully act on the pilot side 98 of the primary diaphram 96 to close the primary valve 70 when desired. Also, by varying the flow through capacity of weep holes 152, the lag time between closing of the pilot valve 72' until closing of the primary valve 70 can be adjusted as desired. For example, with about 0.030 inches diameter for weep holes 152 in a primary valve of about one and one-half inches diameter of primary diaphram 96, only about 0.1 second lag time is experienced after return of actuator 32' to the closed position, before the primary valve 70 closes.
By comparison of FIG. 12 with FIGS. 5 and 6, the movement of actuator 32 or 32' can be appreciated. When actuator (32, or 32') is pushed inward toward cabinet 30, linkage 136 (as described above ) allows pin 148 to move outward, toward actuator 32 or 32'. Via way of pivot arms 138 and 140, acting against pivot pins 143 and 146, respectively, and release of force of spring 132, this retrograde motion configuration is achieved for operation of my novel valve apparatus. As seen in FIG. 12A, when in a no flow configuration, actuator 32 extends outward a distance D N from housing 34. When in a flow configuration, actuator 32 extends outward a distance D F from housing 34. As may be more evident by comparing FIGS. 5 and 6, I prefer a configuration where D F is less than D N . In this fashion, a tap can be left in a normally on configuration with respect manual valves 24 and 26, but neither hot nor cold water will discharge until actuator 32 (or 32') is depressed inward.
Preferably, housing 34 is provided in an elongate hollow open front configuration, in a size adapted to accept an elongated bar type actuator 32 through the hollow open front without appreciable peripheral gap between housing 34 and actuator 32. Preferably, housing 34 is provided in an elongate, open front, hollow, generally trapezoidal shape. However, an alternate configuration is revealed in FIGS. 16, 17, and 18 which may be advantageous in certain situations. In any event, I have found it preferable to provide an actuator bar (32, 32', or 32") which is in elongate, and most preferably, in a hollow arrangement, with partial open interior side 420, but otherwise substantially parallelpiped in configuration.
Specifically, FIGS. 16, 17, and 18 reveal an actuator bar 32" which achieves the retrograde motion with respect to pin 148 as set forth above. This embodiment, however, utilizes a mounting plate 434 instead of housing 34. Mounting plate 434 may be directly mounted to a cabinet 30' (see FIG. 17) via fasteners 436 or other convenient method. In FIG. 17, the partial cut-away view of the internal assembly in actuation bar 32", is illustrated in the closed, no-flow position, showing pivot pins 143' and 146', pivot arms 138' and 140'. The pin 148" with pin housing 54" are shown, in hidden lines, mounted to mounting plate 434; this can be compared to FIG. 16 where pin housing 54" is shown in its operating position. Pin housing 54" preferably includes an elongate, tubular shaft portion 437 for housing a normally solid, cylindrical pin 148". In FIG. 17, the spring 440 is provided to urge pivot block 442, and thus pivot pin 142', inward toward the exterior face 444 of housing 434. Preferably, the interior face 446 of pivot block 442 is biased against the exterior face 444 when actuator 32' is in a "no-flow" or normally closed position. The interior face 446 of pivot block 442 also interfaces with the distal end 448 of actuating pin 148". When the pivot block 442 is urged outward, by outward motion of inboard portions 450 and 452 of pivot arms 138' and 140', respectively, then pin 148" is allowed to move to its outward and open position, as seen in FIG. 18. This is achieved because stationary pivot block 454 acts against pivot pin 143', and stationary pivot block 456 acts against pivot pin 146', at the same time that actuator pivot block 460 acts against outboard pivot pin P 1 , and a second actuator pivot block 462 acts against outboard pivot pin in P 2 Pivot blocks 460 and 462 may be retained within actuator 32' by any convenient affixment device, such as fasteners 464 and 466, respectively. Actuator 32' is held in place, with respect to mounting plate 434, by any convenient affixment device, such as fasteners 470 and 472, which are attached to stationary pivot blocks 454 and 456, respectively. Also, for temporarily holding the actuator 32" in an open position (to allow fluid flow), an outward biased pin 467 in housing 468 may be temporarily locked in detent 469 in block 454.
As can readily be appreciated by reference to FIG. 13, the use of a H-shaped notch 480 in distal end 358 of pin housing 54" allows the pilot valve 52" to be quickly and easily mounted into an operating position. This is particularly true where external threads 482 are provided on the proximal end of the pin housing 54", so that the threads 482 can be interfitted in firm meshing engagement with internal threads 484 which define a through passageway aperture in mounting plate 434. In this fashion, pin housing 54" allows caged, sliding, reversible passage of pin 148" therethough, and between the interior side 446 of pivot block 442 and the exterior side 448 of plunger 334. Ideally, as in the embodiment just illustrated, the effective length of actuating pin 148" is carefully sized so that it provides a firm, repositionable, reliable device to operatively connect the actuator 32" with the plunger 334 of the pilot valve. However, other linking devices may be used to accomplish the same function and to achieve the same result, and so long as the linkage between manipulating an actuator is coupled with repositioning a pilot valve.
Turning now to FIG. 13, yet another embodiment of a dual pilot valve 52" is depicted. A main body 300 of dual pilot valve 52" is provided in a generally oval bathtub shape to accommodate two pilot valves 72 (not visible, but similar to FIG. 7 above). Protruding from a first end 302 of rear wall 304 is a bleed inlet connection line 306 and a bleed outlet connection line 308. Protruding from a second end 310 of rear wall 304 is a second bleed inlet connection line 312 and a second bleed outlet connection line 314. A raised ledge 316 is provided in rear wall 318 with peripheral groves 320 around each pilot valve 72 to receive a complementary raised edge seal 322 similar to that more fully depicted in FIG. 7 above. Individual posts 330 and 332 (in hidden lines) of plunger 334 fit snugly through apertures 334 and 336 of retainer 340 with sufficient length L forward of the inside surface 342 of plunger 334 that posts 330 and 332 may each impinge upon the outside surface 342 of dual pilot diaphram 322 so as to depress the inside surface 344 of pilot diaphram 322 sealingly against the bleed outlet seals (not shown, but similar to FIG. 7 above). As shown in FIG. 13, plunger 334 is moved from its forward, normally closed position to a rearward, open position (as depicted in FIG. 6) via pin 148" in pin housing 54". Pin housing 54" is operably connected to plunger 334 via any convenient means such as snap fitting 350 connection as illustrated, where there is an insertion aperture 352 and a catchment aperture 354 in housing 356 for a notched generally H-shaped distal pin end 358.
A further embodiment of my primary diaphram valve is also illustrated in FIGS. 14 and 15. Valve 70' has leading thereto a fluid supply line 74'. A threaded connector 88' interfittingly cooperates with threads 400 on valve 70' to provide a pressurized fluid supply line. A monolithic block main body 402 is provided for valve 70'. Diaphram seat 106' is provided, against which primary diaphram 96' sealingly engages. Diaphragm housing 90' and monolithic block main body 402 of primary valve 70' combine to form therebetween a diaphragm chamber 94', as described herein above with regard to valve 70. Preferably, diaphram housing 90'uses threads 404 for threaded engagement with interior threads 406 provided in valve body 402. A bleed nipple 408 is provided in diaphram housing 90'. A bleed discharge nipple 410 is provided on the outlet line 412 of valve, so that bleed fluid can be discharged into outlet line 412. Threaded coupling 82' is provided and is sealingly attached to body 402 via outlet nipple 416, which has outer threads 418 to interfittingly engage interior threads (not shown, but similar to FIG. 9 above) in outlet line 412. The fully assembled valve 70' is thus shown in FIG. 15.
It is to be appreciated that the novel valve apparatus and method for regulating the flow of water from a tap which is provided by the present invention is a significant improvement in the state of the art of water saving devices for use in pressurized water supply systems such as household kitchen and bathroom sinks. My novel valve apparatus is relatively simple, and it substantially decreases the cost and complexity involved in installing water saving valves in existing home sink applications.
It is thus clear from the heretofore provided description that my novel valve apparatus, as mounted on a household sink, is an appreciable improvement in the state of the art of devices for reducing water use in homes. Although only a few exemplary embodiments of this invention have been described in detail, it will be readily apparent to those skilled in the art that my novel valve apparatus and method of employing the same may be modified from those embodiments provided herein without materially departing from the novel teachings and advantages provided by this invention, and may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Therefore, the embodiments presented herein are to be considered in all respects as illustrative and not restrictive. As such, the claims are intended to cover the structures described herein, and not only structural equivalents thereof, but also equivalent structures. Thus, the scope of the invention, as indicated by the appended claims rather than by the foregoing description, is intended to include variations from the embodiments provided which are nevertheless described by the broad meaning and range properly afforded to the language of the claims, or to the equivalents thereof.
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A fluid diaphram valve and interconnected pilot valve apparatus for control flow of fluid discharge from a pressurized fluid distribution system. The apparatus has a primary valve with an inlet adapted to receive fluid under pressure, and an outlet adapted to discharge fluid to an outlet conduit. A diaphram chamber is provided in the primary valve which is responsive to fluid pressure controlled by a pilot diaphram valve. Upon release of fluid pressure in the pilot diaphram valve, the primary valve allows passage of fluid to the outlet conduit. Bleed fluid from the pilot valve is also discharged into the outlet conduit and is thus saved for use. Upon closure of the pilot valve, a bleed port in the primary diaphram in the primary valve allows repressurization and seating of the primary diaphram, thus terminating fluid flow through the primary valve. A novel, retrograde motion actuator is also described for use in manual operation of the pilot valve from a fixed location such as cabinets below kitchen sinks.
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TECHNICAL FIELD
[0001] This invention relates in general to the field of filters, and more specifically to a PLL loop filter that can be integrated. The loop filter can be used in a fully integrated PLL design such as a PLL synthesizer, etc.
BACKGROUND
[0002] The biggest component in a type 2 PLL (using a three-state charge-pump) is the capacitor that provides the zero in the PLL transfer function. Given this capacitor's typical large capacitance value, it is not possible to integrate it, which in turn adds extra cost in manufacturing the PLL circuit. A need thus exist in the art for a filter architecture that allows for the integration of this capacitor and therefore provides for improved and manufacturability of the PLL.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] The features of the present invention, which are believed to be novel, are set forth with particularity in the appended claims. The invention, may best be understood by reference to the following description, taken in conjunction with the accompanying drawings, in the several figures of which like reference numerals identify like elements, and in which:
[0004] [0004]FIG. 1 shows a block diagram of a prior art radio frequency synthesizer.
[0005] [0005]FIG. 2A shows an electrical model of a prior art loop filter.
[0006] [0006]FIG. 2B shows an electrical model of a loop filter in accordance with the invention.
[0007] [0007]FIG. 3 shows an AC simulation model used in simulating the present invention.
[0008] [0008]FIGS. 4A and 4B show the AC response of the simulation model of FIG. 3.
[0009] [0009]FIG. 5 shows a transient simulation model that uses the same PLL parameters as those used in the AC simulation model of FIG. 3 in accordance with the invention.
[0010] [0010]FIGS. 6A shows a transient response simulation data at node CPout of FIG. 5.
[0011] [0011]FIGS. 6B and 6C show transient response simulation data at node “cntr” of FIG. 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0012] The present invention provides a way of reducing the value of the passive components used in a filter such as a type two, third order PLL loop filter. This in turn allows in many cases the complete integration of the loop filter. The architecture proposed in the preferred embodiment uses two charge-pumps that work with opposite phase and different values. Generally, in the invention an on-chip current source (e.g., charge pump) provides the functionality of a large value (non-integratable) capacitor in a filter.
[0013] While the specification concludes with claims defining the features of the invention that are regarded as novel, it is believed that the invention will be better understood from a consideration of the following description in conjunction with the drawing figures, in which like reference numerals are carried forward.
[0014] Referring now to FIG. 1, there is shown a schematic of a prior art radio frequency (RF) synthesizer architecture 100 . The series resistor R 2 and capacitor C 2 provides a zero in the loop filter during the transient. The large value capacitor, C 2 works like a big accumulator that receives any excess charge given from the charge pump to the capacitor C 1 . Capacitor C 1 is generally an order of magnitude smaller than capacitor C 2 . Since capacitor C 2 is located in parallel to the charge pump, it receives almost all the charge given by the charge pump. When the charge pump is in its third state, any excess charge is shared among all the capacitors (C 1 and C 2 ), with the time constant defined by the values of the capacitors and resistors.
[0015] In accordance with the present invention, capacitor C 2 in FIG. 1 is eliminated or at least its value reduced enough so that it can be integrated into an integrated circuit. This is accomplished by using an additional current source such as a charge pump that works in the opposite phase as the charge pump in FIG. 1. It is worth noting that the complete elimination of capacitor C 2 is not necessary, what is required is the reduction of its capacitance value enough so that it can be integrated. To show how this is accomplished, two loop filters are reviewed. The first loop filter is the one used in FIG. 1 and is highlighted in FIG. 2A, and the new loop filter in accordance with the invention is shown in FIG. 2B.
[0016] If the same current pulse is applied to the circuits in FIG. 2A and 2B we will need to calculate the pulse of current of the same length but opposite phase to be given to the circuit in FIG. 2B, shown by current 16 , in order to get the same output voltage variation for the two circuits in the steady state condition of the capacitor, where C=C 2 /K. Given this, we set i 0 =I 2 , C 3 =C 1 and C 2 =K*C 0 . This gives the result of:
I 6 I 0 = K - 1 k .
[0017] If for example, we want to reduce the capacitance value of capacitor C 2 by a factor of 10 , we have to use a current I 6 =0.9I 0 .
[0018] The above result is proved using two simulation models of a PLL loop used in an synthesizer, one model is for the open loop AC simulation used to test the loop stability which is shown in FIG. 3. A second model is used for a transient simulation which is shown in FIG. 5. In the AC model shown in FIG. 3, the main charge pump providing current Ip works in opposite phase compared with an auxiliary charge pump providing current Ir and exchanges charge with the loop filter though the node labeled “PIPPO.” The parameters used with the AC model of FIG. 3 include, Icp=400 micro-ampere (uA), Kv=60 MHz/V, a=0.75 and N=2000. The values of all the capacitors used in the loop filter are small enough to be capable of being integrated.
[0019] Results for the AC model shown in FIG. 3 are shown in FIG. 4A and 4B. In FIG. 4A the AC response in dB (decibels) versus frequency (Hertz) is shown, while in FIG. 4B the relationship of phase (degrees) versus frequency (Hertz) is shown. The simulation results show that the PLL is stable with 50 degrees of phase margin and 15 kHz of bandwidth.
[0020] In FIG. 5 there is shown a RF synthesizer used for transient simulation model. The PLL parameters used for this model are the same used in the AC simulation in FIG. 3. The radio frequency synthesizer model 500 shown in FIG. 5 includes an oscillator 502 . The output of the oscillator is then coupled to a divider 504 for reducing the frequency of the signal. A phase/frequency detector (PFD) 506 has an input port for receiving the output signal from divider 504 . A main charge pump (CP) 508 is then coupled to the outputs of PFD 506 , while a current source in the form of a second auxiliary charge pump 510 is coupled at its inputs in opposite fashion to CP 508 so that it can operate in opposite phase to CP 508 .
[0021] Synthesizer 500 includes a loop filter section 520 in accordance with the invention section that uses a second charge pump 510 in order to reduce the value of one of the capacitors of the loop filter so that it may be integrated. A conventional VCO 516 is then coupled to the output of the loop filter and a second divider 518 is coupled between the VCO output and the return loop input to the PFD 506 .
[0022] The results of the transient simulation model of FIG. 5 are shown in FIGS. 6 A- 6 C.
[0023] [0023]FIG. 6A shows the transient response at node CPout while FIGS. 6B and 6C show the transient response at node “cntr” 514 . Although looking at the transient simulation data of FIG. 6C 300 it is is not enough to lock the PLL in-phase, the control voltage at that point is very close to the final steady state voltage at the PLL locked condition.
[0024] The present invention provides a solution to the problem of how to integrate the large capacitor found in a filter such as some types of PLL loop filters. The invention allows for the reduction of at least a factor of 10 the size of the capacitor used, by using an a current source such as an auxiliary charge pump matched with the main one, but operating with opposite phase. Allowing for the integration of the loop filter's large capacitor, in turn allows for the design of a fully integrated PLL or RF synthesizer that are typically less expensive to manufacture than those using a prior art design requiring an off-chip capacitor. By using a second charge pump and no other active components, means less noise sources and hence better phase noise performance.
[0025] While the preferred embodiments of the invention have been illustrated and described, it will be clear that the invention is not so limited. Numerous modifications, changes, variations, substitutions and equivalents will occur to those skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
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A phase-lock loop (PLL) filter architecture includes a first charge pump ( 508 ) and a second change pump ( 510 ). The second charge pump ( 510 ) operates in opposite phase of the first charge pump ( 508 ) in order to take away excess charge from the loop filter capacitor(s) . By using a second charge pump as described, the PLL filter does not require the use of a large capacitor and can therefore be integrated.
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FIELD OF THE INVENTION
[0001] This invention relates to method of lamination and an apparatus comprising first and second laminating rollers defining a laminating gap therebetween and at least one gapping block positioned between the first and second rollers such that the gapping block determines and maintains a minimum gap width. The gapping block comprises a rigid gapping block body, which may be adjustable in width, and four or more load wheels rotatably attached to the gapping block body which ride on a portion of the first and second rollers.
BACKGROUND OF THE INVENTION
[0002] U.S. Pat. No. 6,347,585 discloses a gap adjusting device for a rotary press comprising two rollers separated by an adjustable eccentric member.
[0003] U.S. Pat. No. 5,456,871 discloses a system for adjusting a calendaring gap which employs load measuring units and active feedback, typically mediated by a microprocessor.
[0004] U.S. Pat. App. Pub. No. US2002/0014509 A 1 discloses a nipping roller gap adjusting device having a minimum gap setting means which includes an opposing pair of stops, one attached to a moving assembly that bears a roller and the other attached to the apparatus frame.
SUMMARY OF THE INVENTION
[0005] Briefly, the present invention provides an apparatus comprising first and second rollers defining a gap therebetween and at least one gapping block positioned between the first and second rollers such that the gapping block determines and maintains a minimum gap width. The gapping block comprises a rigid gapping block body and four or more load wheels rotatably attached to the gapping block body and is positioned between the first and second rollers such that at least two load wheels contact each roller. In a further embodiment, the width of the gapping block may be adjustable.
[0006] In another aspect, the present invention provides a method of laminating two or more sheet materials together by passing the sheets concurrently into a gap between a first roller and a second roller of a laminating apparatus, which apparatus additionally comprises at least one gapping block positioned between the first and second rollers such that the gapping block determines and maintains a minimum gap width.
[0007] In another aspect, the present invention provides a method of laminating two or more sheet materials together by passing the sheets concurrently into a gap between a first roller and a second roller of a laminating apparatus, which apparatus additionally comprises at least one gapping block positioned between the first and second rollers such that the gapping block determines and maintains a constant gap width which remains constant throughout the lamination.
[0008] In another aspect, the present invention provides an adjustable gapping block comprising: a first gapping block body element having two or more load wheels rotatably attached; a second gapping block body element having two or more load wheels rotatably attached, where the second gapping block body element is assembled with said first gapping block body element so as to allow linear motion of the two elements relative to each other in the direction of gapping block body width, and where at least one surface of either gapping block body element is canted with respect to a facing surface of the other gapping block body element when so assembled; a wedge disposed between the facing surfaces; and an adjusting screw to determine the position of the wedge between the facing surfaces, thereby determining the gapping block body width.
[0009] In this application, “to laminate” means to bond together two or more sheet materials.
[0010] It is an advantage of the present invention to provide a method of lamination which prevents damage to the continuous web during intermittent lamination of noncontinuous sheets to a continuous web.
BRIEF DESCRIPTION OF THE DRAWING
[0011] [0011]FIGS. 1 and 2 illustrate a gapping block according to the present invention.
[0012] [0012]FIGS. 3 and 4 are cross-sections of the gapping block depicted in FIGS. 1 and 2.
[0013] [0013]FIG. 5 is a cross-section of an apparatus according to the present invention taken through the axes of the two rollers of the apparatus.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0014] With reference to FIGS. 1 - 4 , a gapping block according to the present invention comprises a gapping block body which comprises a first gapping block body element 10 and a second gapping block body element 20 . Two load wheels 31 , 32 are rotatably attached to the first gapping block body element 10 . Two load wheels 33 , 34 are rotatably attached to the second gapping block body element 20 . Additional load wheels may be mounted to either gapping block body element. Alternately, where no adjustment to gapping block body width will be needed, the gapping block body can be a single body element to which four or more load wheels are mounted. Arrow A indicates the dimension which represents body width of the gapping block. In use with a pair of rollers, the gapping block body width is the linear dimension of the gapping block body measured in the direction parallel to the measurement of the gap width between the first and second rollers. In use, motion of the gapping block body elements in a direction perpendicular to the gapping block body width must be prevented. First gapping block body element 10 may comprise arms 15 which prevent motion of second gapping block body element 20 in one or more direction perpendicular to the gapping block body width. In addition, one or more lateral constraints attached to or forming a part of the apparatus frame (shown in FIG. 5, discussed below) may prevent motion of second gapping block body element 20 relative to first gapping block body element 10 in one or more directions perpendicular to the gapping block body width. First and second gapping block body elements 10 , 20 may be bolted to one or more lateral constraints after adjustment of the gapping block body width through tapped holes 12 , 22 .
[0015] First gapping block body element 10 and second gapping block body element 20 comprise facing surfaces 11 and 21 , respectively. One or both of facing surfaces 11 and 21 is canted. By interaction with surfaces 11 and 21 , wedge 40 may be used to adjust gapping block body width. Adjusting screw 41 may be used to alter the position of wedge 40 and thereby the gapping block body width. In one embodiment, adjusting screw 41 has threaded shaft which engages a tapped hole in a lateral constraints attached to or forming a part of the apparatus frame (shown in FIG. 5, discussed below). Typically, first gapping block body element 10 is bolted to one or more lateral constraints through tapped holes 12 , gapping block body width is adjusted by means of adjusting screw 41 , and then second gapping block body element 20 is bolted to one or more lateral constraints through tapped holes 22 .
[0016] With reference to FIG. 5, an apparatus according to the present invention comprises gapping blocks as described above comprising first gapping block body element 10 , second gapping block body element 20 , load wheels 32 , 34 , wedge 40 , and adjusting screw 41 . Lateral constraints 50 prevent motion of second gapping block body element 20 relative to first gapping block body element 10 in a direction perpendicular to the gapping block body width. Lateral constraints 50 are attached to the apparatus frame by connections not shown. First gapping block body elements 10 may be bolted to lateral constraints 50 by through holes 51 and tapped holes 12 . Adjusting screws 41 have threaded shafts which engages tapped holes 53 in lateral constraints 50 . Gapping block body width is adjusted by means of the action of adjusting screws 41 on wedges 40 . Second gapping block body elements 20 may then be bolted to lateral constraints 50 by through holes 52 and tapped holes 22 .
[0017] The apparatus additionally comprises a first roller 60 comprising a pressing zone 61 having a radius r p1 and two gapping block zones 62 , 63 having a radius r g1 . As shown, the first roller additionally comprises axle portions 64 , 65 which interact with bearing surface mechanisms 72 . Second roller 80 comprising a pressing zone 81 having a radius r p2 and two gapping block zones 82 , 83 having a radius r g2 . Typically, r p1 equals r p2 and r g1 equals r g2 . As shown, the first roller additionally comprises axle portions 84 , 85 which interact with bearing surface mechanisms 92 . A narrow laminating gap is formed between first roller 60 and second roller 80 , which are not in contact. The laminating gap of the embodiment shown in FIG. 5 is too narrow to be clearly depicted. Either or both of first roller 60 and second roller 80 may be driven by known means such as motors and the like. Typically both are driven. Typically first roller 60 and second roller 80 are geared together so that they have the same speed at the gap. In one embodiment, first roller 60 and second roller 80 are driven by a belt drive mechanism interacting with pulleys 68 and 88 .
[0018] Bearings comprise bearing housings 71 , 91 and bearing surface mechanisms 72 , 92 which are of known types such as ball bearings, roller bearings, needle bearings, and the like. Bearing housings 71 , 91 are attached to the apparatus frame 100 such that pressure can be brought or maintained on bearing housings 71 , 91 which tends to bring together first and second rollers 60 , 80 . The bearing housings may be fixedly attached to frame 100 or attached by means of pneumatic or hydraulic pistons 101 and cylinders 102 , as shown. Bearing mechanisms may form a part of drive mechanisms for either or both rollers.
[0019] In the laminating method according to the present invention, two or more sheet materials are pressed together by passing them concurrently into a narrow gap between first roller 60 and second roller 80 . Typically one or both of first roller 60 and second roller 80 are driven; more typically both. Heat, solvents or adhesives may be applied to one or more layers to aid in bonding. First roller 60 and second roller 80 may be heated by any suitable method but are typically internally heated by a method such as electrical heating or circulation of hot air, water or oil.
[0020] The apparatus and method according to the present invention are used to advantage where intermittent lamination is desired, i.e., where one or more of the layers to be laminated is not continuously present in the laminating gap during lamination. In this case, the product may be a continuous web with non-continuous patches of additional sheet materials laminated thereto. In the case of intermittent lamination, the continuous web could be crushed or damaged if the full laminating pressure were applied when the non-continuous sheet material was not present in the gap. This damage to the continuous web may be prevented by use of the method and apparatus according to the present invention, which maintains a minimum gap width. In addition, if the full laminating pressure were applied when the non-continuous sheet material was not present in the gap, the leading edges of the intermittent laminate may be rounded during the laminating process, which may be avoided by use of the method and apparatus according to the present invention.
[0021] The apparatus according to the present invention has the additional advantage that bearing clearance in the roller bearings is removed from consideration in determining gap width, and therefore variation in bearing clearance is also removed from consideration. Variation in bearing clearance may be especially problematic where laminating rolls are heated. More accurate and consistent gap width may be set using the apparatus according to the present invention. In addition, the apparatus according to the present invention can be used for fixed-gap lamination, where the gap width is essentially constant throughout lamination. To achieve fixed-gap lamination, sufficient force must be applied to the rollers to overcome any resisting force generated by the materials to be laminated.
[0022] The apparatus and method according to the present invention are used to advantage in the lamination of catalyst decals to polymer electrolyte membranes, in particular membranes of sulfonated fluoropolymer membranes such as Nafion™ or Flemion™. Catalyst decals typically comprises a thin layer of a catalyst dispersion on a backing layer. After lamination of the catalyst dispersion to the polymer electrolyte membrane, the decal backing layer is removed. The apparatus and method according to the present invention are used to advantage with cast membranes of delicate or thin films, typically 100 micrometers in thickness or less, more typically 50 micrometers in thickness or less, and more typically 30 micrometers in thickness or less.
[0023] Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and principles of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth hereinabove. All publications and patents are herein incorporated by reference to the same extent as if each individual publication or patent was specifically and individually indicated to be incorporated by reference.
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An apparatus and method for lamination are provided, which are advantageously used in intermittent lamination and fixed-gap lamination, the apparatus comprising first and second laminating rollers defining a laminating gap therebetween and at least one gapping block positioned between the first and second rollers such that the gapping block determines and maintains a minimum gap width. The gapping block comprises a rigid gapping block body, which may be adjustable in width, and four or more load wheels rotatably attached to the gapping block body which ride on a portion of the first and second rollers.
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BACKGROUND OF THE INVENTION
The invention relates to a circuit arrangement for a position-sensitive radiation detector, which, when electromagnetic radiation is received, supplies two output currents I 1 , I 2 , the amplitude of which depends upon the coordinates of the point of incidence of the electromagnetic radiation. The circuit arrangement, to which the output currents I 1 , I 2 are supplied, generates a signal that depends only on the particular coordinate and not on the intensity of the incident radiation. The circuit arrangement includes (1) a first device, to which an output current can be supplied and which generates a signal that is proportional to the product of the output current and time, and (2) a second device, to which an output current is supplied and which generates a signal that is proportional to the product of the output current and time.
In numerous fields of technology, it is necessary to know exactly the point of incidence of electromagnetic radiation (hereinafter "EMR"). For example, the point of incidence of an electron beam on the target of an electronic beam vaporizer source must be determined accurately, in order to be able to control it so that as uniform a surface temperature as possible is achieved over a particular area and, with that, a constant evaporation rate over this area. A strictly visual control is unsuitable for a fully automatic control system. Components are therefore used which respond to a particular radiation. These components react, for example, to the UV light or to the X-rays, which are formed when an electron beam strikes a target. In contrast to conventional photocells, light-dependent resistances or the like, which change their electric state as a function of the total amount of the incident radiation, and which are therefore not in a position to indicate space coordinates, the aforementioned components must have properties which make it possible to allocate space coordinates.
So-called lateral diodes, for example, are such components. These are position-sensitive semiconductor photodiodes of large surface, which utilize the lateral photoeffect. These photodiodes are also referred to as "PSD's" (position sensitive detectors). Provided that a suitable bias has been selected, unidirectional lateral diodes, a portion of the sensitive surface of which is struck by electromagnetic radiation, supply two output currents, the sum of which is proportional to the incident radiation and the difference between which is proportional to the intensity and proportional to the positional coordinates of the center of gravity of the incident radiation. The difference between the currents or a voltage proportional to this difference is referred to as a positional signal that has not been normalized. For many applications, however, the normalization of this signal, that is, the formation of a signal that is exclusively proportional to position, is required.
Various circuit arrangements have already been proposed to achieve such a normalization (see FIGS. 45 and 6 of the European Patent No. 85114404.8--Publication No. 0 184 680). These circuit arrangements are based on the fundamental concept that, by dividing the sum of the currents by the difference between the currents or the reverse, the influence of the intensity of the irradiation is eliminated and only the influence of the space coordinates is left in the current difference. This division is carried out by means of an analog divider, which divides a voltage that is proportional to the difference between the currents by a voltage that is proportional to the sum of the currents.
With such an arrangement, it is a disadvantage that the maximum permissible fluctuation range of the sum of the currents or of the intensity of the radiation striking the lateral diode is limited by the dynamics of the analog divider. Systems with high dynamics and operating according to the principle described above can be realized only by using expensive, precision components; otherwise, it is necessary to switch over the amplification factor of the preselectors. It is a further disadvantage of the known circuit arrangement that the achievable position resolution falls as the sum of the currents or the radiation intensity decreases.
Moreover, evaluation electronics for a differential photodiode sensor with the reciprocal transfer process of a capacitor and a pulse-width modulated output voltage are known, for which only one capacitor is used for two photodetectors for the reciprocal transfer process by a luminosity-proportional charging current of the photodiodes (German Patent Publication No. 3,531,378). For this system of evaluation electronics, the positional signal is obtained from the variable pulse-width repetition ratio of a pulse-width modulated square-wave voltage; that is, the positional signal is represented by the d.c. voltage fraction of this square-wave voltage, obtained by deep-pass filtration.
It is a disadvantage of this known system of evaluation electronics that the threshold frequency of the evaluation electronics is reduced by the low-pass filtration. Moreover, the total duration of an integration cycle depends upon the magnitude of the two charging currents. Therefore, when one of the input currents becomes very small, the total time for obtaining the data points is very long. The long integration cycle, as well as the reduction in the threshold frequency, make it apparent that the known system of evaluation electronics is not particularly suitable for recognizing points of incidence of EMR in rapid motion.
SUMMARY OF THE INVENTION
It is an objective of the present invention to provide a circuit arrangement which indicates the exact position of an EMR beam incident on a radiation-sensitive element even when the intensity of this beam fluctuates and when this beam is moving rapidly.
This objective as well as other objectives which will become apparent from the discussion that follows, are achieved, according to the present invention, in a circuit arrangement of the type described at the beginning of this specification, wherein:
(a) only the one output current is supplied to the first device and only the other output current is supplied to the second device;
(b) a third device is provided for the comparison of two signals, this device having a first input, to which a signal with specified value is applied, and a second input, to which a signal is applied that is composed of the signals, or parts thereof, coming from the first and second devices;
(c) a fourth device is provided, which has a first input, to which the output signal of the first device is supplied, and a second input, to which the output signal of the second device is supplied, and which forms the difference between the two output signals; and
(d) a fifth device is provided, which stores the output signal of the fourth device at the time at which the two input signals of the third device are of equal magnitude.
The principal advantages achieved with the invention are that an analog divider may be omitted and that the position resolution is largely independent of the radiation intensity, since the measurement-relevant voltage difference of the output voltages at the outputs of the devices, to which the output signals of the radiation-sensitive elements are supplied, is independent of the radiation intensity. Moreover, the circuit arrangement of the invention has a high sensitivity or a low response threshold. Since the integration time is determined only by the sum of the two currents and is completely independent of their magnitude, this time is very short. As a result, the speed is increased. Furthermore, the inventive circuit arrangement does not require a switch for changing over from one integrating device to the other.
Preferred embodiments of the invention are shown in the drawing and described in greater detail in the following specification.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a circuit arrangement for the display of a y coordinate, which can also be used for the display of an x coordinate; and,
FIG. 2 shows a circuit arrangement with preamplifier for the display of a y coordinate, which can also be used for the display of the x coordinate.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, a unidirectional lateral diode 1 is shown, which is provided with a bias voltage U v and has two terminals 2, 3. From these terminals 2, 3, conductors lead to the negative input of an operational amplifier 4, 5, the positive inputs 6, 7 of which are grounded. The current which flows from terminal 2 of the lateral diode 1 to the negative input of the operational amplifier 4 is labelled I 1 , while the current which flows from terminal 3 of the lateral diode 1 to the negative input of the operational amplifier 5, is labelled I 2 . The negative input of each of the two operational amplifiers 4, 5 is connected over a capacitor 8, 9 with the respective output 10, 11 of the corresponding operational amplifier 4 or 5, respectively. Parallel to the capacitor 8, 9, a controllable switch 12, 13 is provided, which can be triggered over a conductor 14. The outputs 10, 11 of the operational amplifiers 4, 5 are connected to one another over two resistors 15, 16 connected in series. From the connecting conductor 17 between the two resistors 15, 16, a further conductor leads to a first input of an operational amplifier 18. A reference voltage U REF is applied to a second input of this amplifier 18.
The output of the operational amplifier 4 is connected over a resistor 19 with the negative input of a further operational amplifier 20, while the output of the operational amplifier 5 is connected over a resistor 21 to the positive input of this amplifier 20. The output of the operational amplifier 20 is connected over a resistor 22 with the negative input of this amplifier 20, while the positive input of this amplifier 20 is grounded over a resistor 23. From the output of the operational amplifier 20, an additional conductor leads to the sample-and-hold circuit 24, that presents a voltage U y at the output. This sample-and-hold circuit 24 is triggered by a control device 25 which, in addition, receives signals from the operational amplifier 18 and delivers signals to the switch 12, 13. The operational amplifiers 4, 5 together with the capacitors 8, 9, form integrator stages, in which the currents I 1 and I 1 , which are supplied by the unidirectional lateral diode 1, are integrated. Such integrator stages may be formed, for example, by operational amplifiers which are sold by Burr Brown under the designation OPA 356. The following equations are valid for the output voltages U 1 and U 2 , respectively of the integrators:
U.sub.1 =kI.sub.1 t (1)
U.sub.2 =kI.sub.2 t (2)
In these equations, t is the integration time, while k is a proportionality factor. It follows from Equations (1) and (2) that
U.sub.1 -U.sub.2 =kI.sub.1 t-kI.sub.2 t=kt(I.sub.1 -I.sub.2) (3)
U.sub.1 +U.sub.2 =kI.sub.1 t+kI.sub.2 t=kt(I.sub.1 +I.sub.2) (4)
The proportionality factor is assumed to be the same for the two integrators.
The operational amplifier 18 represents a comparator, which can be realized, for example, with an operational amplifier sold by Burr Brown under the designation OPA 37.
This comparator compares the reference voltage U REF , which is applied at its one input, with the voltage U M at its other input. This last-mentioned voltage U M is the arithmetic mean of the output voltages U 1 and U 2 of the integrators 4, 8 and 5, 9 respectively. The following equation applies:
U.sub.M =(U.sub.1 +U.sub.2)/2 (5)
If the voltage U M reaches the value U REF , the comparator 18 initiates the following cycle of operations:
The comparator 18 triggers the control unit 25, which in turn activates the sample-and-hold circuit 24, which takes over the value of the voltage U D at the output of the operational amplifier 20. This voltage U D is the difference between U 1 and U 2 , because the operational amplifier 20 serves as a subtracting amplifier. A sample-and-hold circuit of the type described is sold, for example, by Burr Brown under the designation SHC 298. The integration capacitors 8 and 9 are then discharged by closing switches 12 and 13 respectively, as a result of which the output voltages U 1 and U 2 each assume the value of 0 volts. The switches 12 and 13 are sold, for example, as electronic switches by National Semiconductor Corp. under the designation CD 4066. By subsequently opening switches 12, 13, a new integration cycle is initiated.
In this connection, it is important that the measurement or storage of the instantaneous voltage difference U D is always carried out at that particular time at which the following equation applies for the sum of the voltages U 1 and U 2 :
U.sub.1 +U.sub.2 =k'U.sub.REF =constant (6)
U REF denotes a constant, suitably selected voltage, while k' represents a proportionality factor. In the present example, it follows from Equations (5) and (6) that k' is 2 because
(U.sub.1 +U.sub.2)/2=U.sub.M
U.sub.1 +U.sub.2 =k'U.sub.REF
with
U.sub.M =U.sub.REF
It follows from Equations (3), (4), (5) and (6) that, for the voltage U y applied at the output of the sample-and-hold circuit 24,
U.sub.y =k'U.sub.REF (I.sub.1 -I.sub.2)(I.sub.1 +I.sub.2) (8)
This follows from U y =U 1 -U 2 =(I 1 -I 2 )kt. From Equation (4)
k×t=(U.sub.1 +U.sub.2)(I.sub.1 +I.sub.2)
Inserting this value for kt into the equation for U y
U.sub.y =(I.sub.1 -I.sub.2)(U.sub.1 +U.sub.2)(I.sub.1 +I.sub.2)
However, since U 1 +U 2 =k'U REF , then
U.sub.y =k'U.sub.REF (I.sub.1 -I.sub.2)/(I.sub.1 +I.sub.2)
It can be seen from Equation (8) that the voltage U y represents a quantity which depends only on the coordinates and no longer on the magnitude of the sum of the currents I 1 and I 2 . In the present example, it is assigned to the y coordinate.
The selection of U REF depends on the magnitude of the capacitors 8 and 9. The following relationship applies:
t=k'C.sub.8,9 U.sub.REF /(I.sub.1 +I.sub.2)
in which C 8 ,9 refers to the capacitance of the capacitors 8, 9. Within technical limits, the magnitude of U REF does not affect the normalization of the position signal by the circuit arrangement.
In FIG. 2, a circuit arrangement is shown, which largely corresponds to that of FIG. 1. In contrast to the latter, it has preamplifiers, comprising operational amplifiers 30, 31, ahead of the integrators 4, 8 or 5, 9. The feedback branch of the operational amplifiers 30, 31, is formed by a parallel circuit of a capacitor 32, 33 and a resistor 34, 35. These preamplifiers amplify the currents I 1 , I 2 , which come from the lateral diode 1. The conductor 36, to which the bias voltage U v , is applied, is connected through a capacitor 37 to ground. Restistors 38 and 39 are provided between the inputs of the operational amplifiers 4 and 5 and the outputs of the amplifiers 30 and 31, respectively.
It goes without saying that the circuit arrangements of FIGS. 1 and 2, although they are shown only for displaying the y coordinate, can also be provided in a corresponding manner for displaying the x coordinate.
With two circuit arrangements like those of FIG. 1 and FIG. 2, the x, y positions of a beam within an x, y field can be determined if, for example, a arrangement such as that shown in FIG. 2 of the aforementioned European Patent Application No. 01 84 680 is selected.
There has thus been shown and described a novel circuit arrangement for a position-sensitive radiation detector which fulfills all the objects and advantages sought therefor. Many changes, modifications, variations and other uses and applications of the subject invention will, however, become apparent to those skilled in the art after considering this specification and the accompanying drawing which disclose the preferred embodiment thereof. All such changes, modifications, variations and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention which is limited only by the claims which follow.
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The invention relates to a circuit arrangement for a position sensitive radiation detector which produces a current or voltage signal (U Y ) that depends exclusively on the coordinates x and y of the point of incidence of electromagnetic radiation on the EMR sensitive surface of a lateral diode (1). For this purpose, the circuit arrangement has integrators (4, 5), in which the voltages (U 1 , U 2 ) are formed, which are proportional to the integral over time of the output currents (I 1 , I 2 ) of the lateral diode (1). The difference between the voltages (U 1 , U 2 ) is used as a signal, which depends exclusively on the coordinates at that particular time, at which the arithmetic mean of these voltages (U 1 , U 2 ) has reached a preselected, constant value.
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RELATED APPLICATION DATA
[0001] The present application is a non-provisional application based on, and claiming the priority benefit of, co-pending U.S. provisional application Serial No. 60/410,090, which was filed on Sep. 12, 2002, and is expressly incorporated herein by reference.
FIELD OF THE DISCLOSURE
[0002] The present invention generally relates to a method of accessorizing body parts, hair, etc. and, more particularly, to a method of accessorizing body parts, hair, etc. with self-adhesive styling tape.
BACKGROUND OF THE DISCLOSURE
[0003] The idea of decorating portions of the body and hair is known in the prior art, and is especially popular with children for both dress-up and amusement purposes. For example, use of necklaces, earrings, bracelets, anklets, and chokers have long been used to decorate the body. Similarly, many devices are known in the prior art that enable one to style or manage hair that also include an aesthetic benefit to the user. For example, items such as pony tail holders, pins, bungees, scrunchies, rubber bands, and barrettes have all been used to hold, manage, or otherwise decorate the hair.
[0004] Each of the above mentioned items, whether used to decorate the body, or whether used to manage the hair have, however, one or more undesirable qualities. For example, none of the above mentioned items are easily adapted to be used as both decoration for the body and for management of the hair.
[0005] Similarly, items used for decorating the body, such as the necklaces, earrings, and bracelets, may have additional undesirable qualities such as cost and safety concern. The cost of jewelry, for example, whether real, fake, or costume, may be very expensive when purchased for a child to use or play with. The jewelry may also create a safety concern, especially when used by a young child. A child may, for example, swallow an earring and/or get choked by a necklace or the like. The jewelry may also be difficult for a child to use, considering the complexity and diminutive size of some of the clasps or locking mechanisms.
[0006] The devices used to manage hair may have additional undesirable qualities, such as being uncomfortable and/or difficult to use. A device, such as a pony tail holder and a barrette may be hard and rigid in construction, which can cause discomfort for the wearer, especially while sleeping or during activities. The devices, such as the scrunchie, may also be difficult to use in that it may require know-how and or dexterity, or the assistance of another individual to correctly manipulate the hair into the device or vice versa.
SUMMARY OF THE INVENTION
[0007] In accordance with one aspect of the disclosure, a method of using styling tape for body part and hair accessorizing is disclosed. The method may include cutting a self-adhesive tape into a strip and stretching it to obtain at least some tension. The user may wrap the self-adhesive strip around a bundle of hair or a body part, and may press the self-adhesive strip onto itself to retain the strip on the bundle of hair or body part.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] [0008]FIG. 1 is a perspective view of two strips of styling tape, wherein one of the strips includes cut-out portions;
[0009] [0009]FIG. 2 is a perspective view of the styling tape of FIG. 1 on a wrist;
[0010] [0010]FIG. 3 is a perspective view of the styling tape FIG. 1 around a bundle of hair; and
[0011] [0011]FIG. 4 is a perspective view of a roll of styling tape.
[0012] While the method and device described herein are susceptible to various modifications and alternative constructions, certain illustrative embodiments thereof are shown in the drawings and will be described below in detail. However, there is no intention to limit the invention to the specific forms disclosed, but on the contrary, the intention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the invention and the appended claims.
DETAILED DESCRIPTION
[0013] Referring to the drawings, and with specific reference to FIG. 1, a styling tape strip is generally depicted by reference numeral 22 . As shown therein, the styling tape strip 22 includes a first surface 23 , a second surface 25 , a first end 30 , and a second end 32 .
[0014] In one exemplary embodiment, the styling tape strip 22 may be constructed with latex, and more specifically with natural rubber latex. The styling tape strip 22 may have many desired qualities including, but not limited to, being self-adhesive, being perforated, colorfiil, and cutable with scissors, as well as allowing the skin to breathe and/or absorb virtually no moisture. The styling tape strip 22 may have enough inherent adhesiveness to adhere two styling tape strips 22 and/or two portions of the same styling tape strip 22 securely together, but may lack the adhesiveness to securely stick to objects, such as hair and skin by itself. As such, the styling tape strip 22 may be used to securely adhere to itself, while not securely adhering to skin. The styling tape strip 22 may, however, be constructed of any other material that is able to accomplish the intended purpose.
[0015] The styling tape strip 22 may be cut with ordinary scissors into a great variety of shapes, such as swirls, hearts, stars, waves, flowers, letters, numbers, and other various indicia, and the resulting cut-out shapes 24 may be adapted to stick to a separate, additional styling tape strip 22 . Similarly, the styling tape strip 22 itself may be cut with ordinary scissors into a great variety of elongate shapes. In use, the strip 22 may be wrapped around any number of objects, including but not limited to, bundles of hair, clothing, a neck, a wrist, fingers, etc.
[0016] In one exemplary embodiment, as shown in FIG. 4, the user may unroll a portion of tape from a roll of self-adhesive styling tape 20 , and cut the strip 22 from the unrolled portion. The strip 22 may be of a variety of widths and lengths, as desired by the user. The strip 22 , for example, may be the full width of the tape as unrolled from the roll of self-adhesive tape, or may be cut into any smaller width desired. Similarly, the strip 22 may be cut into any length as needed for the intended accessorizing purpose. For example, the user may desire to use the strip 22 to fit around a bundle of hair, for which a short strip 22 may be used, or the user may desire to make a choker necklace from the strip 22 , for which a longer strip 22 would be needed.
[0017] The user may desire to use one or more cut-outs 24 with the strip 22 , as seen in FIGS. 1 and 2, by creating the cut-outs 24 and attaching them to the strip 22 . The cut-outs 24 may be attached to the strip 22 in several ways, including, but not limited to, using the self-adhesive properties of the tape, glue, pins, fasteners etc. If using the self-adhesive properties of the cut-outs 24 and/or the strip 22 , the user may press the second surface 25 of the cut-outs 24 and the first surface 23 of the strip 22 firmly together, thereby attaching the cut-outs 24 to the strip 22 . The cut-outs may be of a different color than the strip 22 , and like the strip 22 , may have a plurality of colors.
[0018] In one exemplary embodiment, the user may stretch or elongate the strip 22 prior to or during placement of the strip 22 around the body part or bundle of hair. For example, either as or before the user places the strip 22 around an object, the user may stretch the strip 22 or otherwise place the strip 22 into tension. The user may stretch the strip 22 as little or as much as desired, depending on the intended use of the strip 22 . If the strip 22 , for instance, is used to create a chocker necklace around the neck of a child, the strip 22 may be stretched only enough to prevent sagging of the strip 22 , whereas if the strip 22 is used to hold the bundle of hair together, the strip 22 may be stretched enough to ensure that the strip 22 properly secures the bundle of hair.
[0019] In one exemplary embodiment, to wrap the strip 22 around the object (FIGS. 2 and 3), such as the body part or the bundle of hair, the user may hold the first end of the strip 30 against or near the object and proceed to bring the second end 32 of the strip 22 around the object, toward the first end 30 , such that the second surface 25 of the strip 22 abuts the object. To secure the ends 30 , 32 to each other, the user may press the second surface 25 of the second end 32 , and the first surface 23 of the first end 30 together, thereby securing the ends 30 , 32 to each other. Additionally and/or alternatively the strip 22 may be secured to the strands of hair and/o to itself using tape, glue, pins, other various types of fasteners, including but not limited to, hook and loop, snaps, VELCRO®, etc.
[0020] While the foregoing detailed description has been described with reference to specific examples, which are intended to be illustrative only and not to be limiting of the disclosure, it will be apparent to those of ordinary skill in the art that changes, additions or deletions may be made to the disclosed embodiments without departing from the spirit and scope of the invention.
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A method of using styling tape for body part and hair accessorizing is disclosed. The method may include cutting a self-adhesive tape into a strip or other elongate shape and stretching it to obtain at least some tension. The user may wrap the self-adhesive strip around a bundle of hair or a body part, and may press the self-adhesive strip onto itself to secure the strip or other elongate shape.
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FIELD OF THE INVENTION
This invention relates to blood collectors and more particularly relates to a new and improved blood collector.
BACKGROUND OF THE INVENTION
The collection of blood samples from a patient are integral in the diagnosis of disease, and the monitoring of therapy. One method of collecting blood is commonly referred to as the "fingerstick". This method involves cutting the skin with a lancing device and collecting the blood from the resulting wound.
The earliest collecting devices were glass tubes, sometimes manufactured with special shapes such as tapered ends. About 10 years ago, manufacturers began introducing specially designed plastic collectors in which the collected blood sample could be directly centrifuged to yield serum or plasma. However, these devices have a number of deficiencies.
One problem associated with these prior blood collectors is that most of them rely on gravity which requires that the drop of blood accumulating at the wound must become large enough to flow down a spout or a funnel which is plastic. Plastic is hydrophobic and therefore, non-wetable, which makes the flow of blood down a plastic spout or funnel very difficult. Furthermore, due to the difficult passage of the blood over a plastic surface, the blood may have time to clot before reaching the anticoagulant usually located in or near the bottom of the blood collector. The clotting may be serious enough to block the flow of blood, or micro-clots may form which interfere with the subsequent analysis of the blood especially the counting of cells in a blood cell counter. Therefore, the prior blood collectors are very technique dependent to prevent the clotting of blood during the blood collection process.
Another problem associated with prior blood collecting devices is that they are generally unsuitable for use with new, smaller, automated blood analyzers developed in recent years. For example, the pipettor associated with one of these newer instruments cannot reach the prepared plasma or serum in most of the prior art collectors because the blood collector is too long and/or too narrow.
Another type called the KABE Collector has several deficiencies which are identified in the detailed description relating to prior art, infra.
SUMMARY OF THE INVENTION
Apparatus for transferring a blood specimen from a droplet source to a collection tube via a capillary tube has a glass anticoagulant-coated capillary tube or a plain untreated tube and a collection tube with a stopper having an X-slit membrane for admission of the capillary tube into the collection tube with the stopper on. A separating gel may be located in the collection tube to provide plasma or serum separation when the collection tube is centrifuged.
The capillary and collection tubes are preferably sold together but separated from each other. This packaging method is more efficient in the use of space. They are assembled by pushing the capillary tube through the slit membrane of the stopper when in place on the collection tube. A colored band preferably identifies the depth of insertion for proper collection without touching any gel that is provided. As is well known in the art the same colored band can also serve to identify the type of anticoagulant contained therein. The blood is allowed to fill the capillary tube by capillary action and to then flow out of the other end of the capillary tube into the collection tube. The capillary tube is then withdrawn and the slit membrane closes, sealing the contents of the collection tube for later centrifuging, if required.
DESCRIPTION OF THE DRAWINGS
Other features and benefits of the invention can be more clearly understood with reference to the specification and the accompanying drawings in which:
FIG. 1 is a side plan view of a blood collector representatively configured and operable in accordance with the principles of the prior art.
FIG. 2 is a perspective view of a new and improved blood collector.
FIG. 3 is a cross-sectional view of the blood collector of FIG. 2.
FIG. 4 is a top plan view of the blood collector of FIG. 3.
FIG. 5 is a cross-sectional view of the blood collector of FIG. 2 with the capillary tube in position.
FIG. 6 shows the blood collector being used to obtain a specimen.
FIG. 7 shows the specimen being drained into the collection device.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring initially to FIG. 1 of the drawing, a blood collection device representatively configured and operable in accordance with the principles of the prior art is indicated generally at 10, and comprises a cylindrical tube 12, into which a pierced stopper 14 rigidly holding a plastic capillary tube 16 is inserted with or without an anticoagulant inner coating. The volume of the tube 12 is large compared to the volume of the plastic capillary tube 16 with the result that the blood sample or the resulting plasma or serum is located near the bottom of the tube making it less accessible to pipetting or pipettors. The unit is sold in this configuration necessitating a plastic capillary to avoid breakage and presenting the risk of the tube being pushed into the gel in transit and/or prior to use and ruining it. The tube 12 having a rounded bottom 13 is unable to stand alone, and requires a support stand or tube rack.
Following specimen collection, the stopper 14 and capillary tube 16 are removed as a unit from the tube 12. The tube 12 is then sealed by inserting an attached plug top 18 into the tube. The plug top 18 is attached to the tube 12 with a tether 20.
Referring now to FIG. 2, the new and improved blood collection device is shown generally at 22, and comprises a short cylindrical tube 24 whose volume more closely approximates that of the capillary tube 36, into which a predetermined amount of separation gel 26 has (optionally) been deposited. The tube has a flat or support bottom 28 enabling it to stand unsupported on a flat surface. The tube 24 is sold packaged with a stopper 30 inserted into the mouth 32 of the tube 24.
A glass capillary tube 36 having an insertion alignment ring 38 is also packaged with the unit for sale but provided separately and apart from the stopper 30 allowing a more effective (e.g. hydrophyllic) glass capillary tube to be used. The capillary tube 36 typically has an anti-coagulant coating on its inner surface using the known heparin or EDTA anti-coagulants as examples. The body of the collection tube 24 is typically formed of a plastic or other material suitable for use in and dimensioned for mounting to conventional centrifuging equipment.
In use, and as illustrated in FIGS. 3, 4 and 5, the tube 24 I has the stopper 30 fitted in it at the point of sale providing a closure formed by an X shaped slit 34 in a membrane 35 closing the mouth of the tube. The operator inserts the capillary 36 to the point where the mark 38 is aligned with the top of the stopper 30. This insures proper positioning of the capillary tube 36 and avoids the danger of the capillary tube 36 being pushed into a gel 26 which is typically provided at the bottom of the tube 24 for plasma and serum separation.
The operator then pierces an appropriate skin region as illustrated in FIG. 6 to allow a first droplet 40 of a blood to accumulate. With the capillary tube 36, still inserted in the collection tube 24, in a roughly horizontal or slightly inclined position the mouth of the tube 36 is touched to the droplet 40 causing, by capillary action, the tube 36 to fill with the blood from the droplet 40. At this point the capillary tube 36 and collection tube 24 are turned vertical allowing the blood to flow into the bottom of the collection tube 24. Any remaining portion of blood in the tube 36 may typically be wicked off by touching the inner end of the capillary tube 36 to the inner wall of the collection tube 24. Additional emptying of the capillary tube 36 may be accomplished by use of a small pipette bulb, as is known in the art, applied to the outer end of the capillary tube 36.
If the capillary tube 36 of the apparatus 22 contains an anticoagulant, the collecting tube 24 can be centrifuged immediately to yield plasma. In addition, the blood in the collecting tube 24 is immediately available for analyses on whole blood such as the counting of the blood cells.
If the capillary tube contains no anticoagulant, the thus filled collection tube 24 is then typically allowed to stand for half an hour and allowed to clot before centrifuging to yield serum.
Where it is desired to collect more anticoagulated blood than can be delivered by a single capillary tube 36 it is preferable to use separate tubes because the dosage of anti-coagulant applied to each capillary tube 36 is usually only sufficient to provide anti-coagulant protection to that amount of blood. Typically after the droplets 40 have been transferred to the bottom of the collection tube 24 it will be briefly shaken in order to insure complete mixing of blood and anti-coagulant.
If the capillary tube 36 contains n anticoagulant then the inner end of the capillary tube can be put in contact with the inner wall of the collection tube 24 and a continuous flow of blood established filling the collection tube to its capacity.
The above described embodiments of the present invention are presented by way of example only. The scope of the invention being limited solely as indicated in the following claims.
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Apparatus for transferring a blood specimen from a droplet source to a collection tube via a capillary tube. A glass anticoagulant-coated or an untreated capillary tube and a collection tube with a stopper having an X-slit membrane for admission of the capillary tube into the collection tube with the stopper on. A separating gel may be located in the collection tube to provide plasma and serum separation when the collection tube is centrifuged.
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BACKGROUND OF THE INVENTION
This invention relates to fluid pumps and more particularly to a centrifugal type of fluid pump. The invention also relates to fuel controls for gas turbine engines.
A problem with centrifugal impeller pumps, which operate during low flows, is the recirculation of flow from the collector thereof back into the impeller section. This flow recirculation contributes significantly to a reduction in pump efficiency and increases undesirable heating of the fluid being pumped.
Prior art devices which restrict the impeller discharge area or collector inlet area have demonstrated that a reduction in recirculating flow engenders a noticeable improvement in pump efficiency. However, the available mechanical systems in the prior art for controlling the inlet area on the collector do not allow for precise positioning of the valve which dictates the inlet area. Hence, the mechanical systems of the prior art which are employed to regulate the collector inlet area have not been adapted for the precise control to render them suitable for certain applications, such as aircraft applications.
SUMMARY OF THE INVENTION
The invention is directed to a restricting valve for the inlet of the collector of a centrifugal type pump. A restricting valve of the invention is adapted to be precisely positioned so that a pump incorporating the restricting valve may be suitably employed in applications having the aforementioned requirements.
A pump of the invention comprises a restricting valve in the form of a ring mounted on the pump housing such that rotation of the ring controls the inlet area of the collector. Rotary motion of the ring is produced by a suitable actuator (such as an electric or fluid motor); and axial motion of the ring, which affects either a reduction or an enlargement of the inlet area of the collector, is beget by a cam means which imparts a small axial motion to the ring for a larger rotary motion in thereof. In a preferred embodiment of the invention slots in the ring receive pins which are fixedly secured to the housing such that rotary motion of the ring produces a corresponding axial movement of the ring. In yet another preferred embodiment to the invention, the ring may serve not only to restrict the collector inlet area but also to reduce the volume of the collector itself.
Accordingly, it is a primary object of the invention to provide a centrifugal type impeller pump with a restricting valve for the inlet area of the collector wherein the valve is capable of being precisely positioned.
This and other objects and advantages of the invention will become more readily apparent from the following detailed description, when taken in conjunction with the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view, in cross section, of a centrifugal type impeller pump of the invention.
FIG. 2 is a sectional view of the pump of FIG. 1 taken along the line 2--2 of FIG. 1.
FIG. 3 is a view taken along the line 3--3 of FIG. 1 showing the engagement between the ring and a pin.
FIG. 4 depicts an alternative form of ring which restricts not only the collector inlet area but also the collector volume.
FIG. 5 is a block diagram depicting a pump of the invention incorporated in a fuel control system for a gas turbine engine.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to FIG. 1, there is shown a centrifugal type impeller pump 8 of the invention having an impeller housing 10, an actuator housing 12 and a bearing housing 14, the latter being depicted in phantom. The various housings are complimentary sections which together form the pump body. A plurality of bolts 16 extend through passages in their respective housings to engage nuts 18 for maintaining the assembled relationship. The impeller housing 10 is constituted by an inlet section 10a, a main section 10b having an impeller chamber 20 formed therein, and a peripheral section 10c in which is defined a peripheral manifold or collector 22 which receives the impeller fluid.
A rotatable shaft 24 is mounted in concentric relationship to the impeller chamber 20 and carries upon its end an impeller 26 securely mounted thereupon in the conventional manner by an impeller nut 28. The impeller 26, which is of a well known type, comprises a web section 29 with radially extending vanes 30 fashioned thereupon. The impeller 26 also includes the usual suction eye 32 which lies radially inwardly of the vanes. In addition, the impeller 26 carries labyrinth seals to furnish a pressure breakdown means to minimize leakage through the running clearance which must necessarily be provided between the impeller and the impeller housing, the labyrinth seals being designated 34 and 36. A sealing element 38 comprises threads 40 on the rear portion thereof so that it may be secured in threaded engagement to the bearing housing 14 with its interior periphery engaging the labyrinth seal 36. A flange 38a on the sealing element 38, together with an intermediate cylindrical surface of the sealing element 38, functions to position a cylindrical valve seat 42 adjacent the inlet of the collector 22.
As best shown in FIGS. 1 through 3, the restricting valve of the invention is constituted by a cylindrical sleeve or ring 44 mounted upon a portion 46 of the outside surface of the section 10b of the impeller housing 10 in coaxial relationship with the impeller housing and the impeller 26. The portion 46 of the outside surface of the impeller housing 10 serves as a bearing and a guide for the rotational and axial movement of the ring 44. As is shown in FIG. 3, the ring 44 comprises three helical slots 44a which are spaced in an equidistant manner around the ring 44. Three pins 48 are fixedly connected to the main section 10b of the impeller housing 10 and are spaced in an equidistant manner around the impeller housing so as to define angles of 120 degrees therebetween. A bearing 50 surrounds each pin 48 beneath an upper flange 22 (FIG. 1) integral with the pin to thereby define a roller which is received in the slot 44a. The rear face 44b of the ring 44 is in confronting relationship to the valve seat 42 such that the spacing therebetween is determinative of the inlet area of the collector 22.
Rotation of the ring 44 relative to the impeller housing 10 in a clockwise direction as viewed from the inlet results in a progressive reduction in the inlet area of the collector 22 and conversely a rotation of the ring 44 in a counterclockwise direction affects a progressive increase in the inlet area of the collector 22. It will be noted that the portion 46 of the outer surface of the impeller housing performs the combined functions of acting as a cylindrical guide member for axial movement of the ring 44 as well as serving as a bearing for supporting the ring 44 during rotation thereof.
A preferred actuator for rotating the ring 44 is illustrated in FIG. 2 under the general designation 54. The actuator 54 comprises a piston 56 mounted for axial sliding movement within a bore 58 in the actuator housing 12. The mouth of the bore 58 is covered by a plug 60 having a conduit 62 for the admittance of a control pressure generated by an appropriate control device. A spring 64 functions to bias the piston 56 to the left wherein the inlet area of the collector 22 is at a maximum value. Attached to the right side of the piston 56 in concentric relationship thereto is a shaft 66 which is slideably mounted within a smaller bore 68 in the actuator housing 12. A link 70, having universal couplings 72 and 74 at its ends, interconnects the end of the shaft 66 with the ring 44 such that axial movement of the piston 56 and the shaft 66 imparts rotary motion to the ring 44. An adjustable stop abuttment 76 is arranged within the actuator housing 12 to contact a radial projection 78 integral with the ring 44 to limit the minimum size of the inlet area when a control pressure is applied to the underside of the piston 56, which is not balanced by the opposite force exerted by the spring 64.
FIG. 4 shows an alternative version of the ring which controls the inlet area of the collector. In this modification the ring includes a flange 80 having a sliding seal on its upper edge whereby the ring may not only control the inlet area to the collector but also the collector volume itself. This is advantageous because the recirculation of flow within the collector is reduced, and thereby the frictional loss in the fluid is also reduced, and the efficiency of the pump is increased.
A fuel control application, for which the pump of the invention is particularly well suited, is outlined in FIG. 5. For the purposes of describing the operation of the illustrated pump, assume that the pump is adapted to supply fuel to a gas turbine engine of an aircraft and hence constitutes a part of a fuel control therefor. A gas turbine engine, which is operated at a high altitude, has far lower fuel flow requirements than at sea level. When the fuel flow rate falls below a predetermined level at which recirculation problems are encountered in the pump, a pressure generating device, which may assume many forms, increases the pressure applied to the lower face of the piston 56. Assuming that the engine has a fuel control in which a constant head is always maintained across a metering valve 84 (which is in series flow relationship with the impeller pump 8) by a pressure regulator 86, the position of the metering valve 84 may be utilized to control the pressure generating device 82 since valve position is an indication of the flow to the engine and hence the flow through the pump. Typical metering valves and pressure regulators are shown in FIG. 1B of U.S. Pat. No. 3614269. The increase in pressure in the lower face of the piston 56 is sufficient to cause the piston to be driven against the bias of the spring 64 until the projection 78 contacts the abuttment 76. During the stroke of the piston 56 the ring 44 rotates and simultaneously moves in an axial direction towards the seat 42. When the projection 78 establishes contact with the abuttment 76, the inlet area of the collector 22 will have been reduced to a predetermined extent whereby recirculation in the impeller cavity is ameliorated. As long as flow through the pump remains below the predetermined level, pressure is continuously applied to the lower face of piston 56, thereby to maintain the projection 78 in contact with the abuttment 76. However, when the flow to the pump exceeds the predetermined level, the pressure generating device 82 relieves the pressure on the lower face of piston 56, thereby permitting the spring 64 to force the piston back to its original position wherein the inlet area of the collector is at its maximum value. During the return stroke of piston 56, the ring 44, of course, rotates in the opposite direction and the face 44a withdraws from the valve seat 42.
It should be noted that certain applications may make it necessary for the ring 44 to be capable of assuming a plurality of intermediate positions in which the inlet area of the collector (or collector volume) is somewhere between its maximum and minimum values. In such a situation, a proportional position control system may be utilized in such a manner that the ring position is a linear (or non-linear) function of the flow rate whereby the ring may be continuously positioned as the sensed flow rate varies. Moreover, other ring positioning schemes are also within the ambit of the invention.
Obviously, many variations and modifications are possible in light of the above teachings without departing from the invention as defined in the claims.
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A centrifugal type impeller pump has a restricting valve to control the inlet area of the collector for reducing recirculating flow from the collector to the impeller. The restricting valve includes a ring mounted upon the pump housing for rotary and axial motion. Rotary motion is imparted to the ring by an actuator. Cam slots in the ring and pins secured to the housing produce axial motion of the ring as the ring rotates. Precise positioning of the ring is possible because large motions of the actuator can be utilized to provide small changes in ring position. The axial position of the ring is determinative of the inlet area of the collector.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Divisional Application of U.S. application Ser. No. 09/711,600 filed Nov. 13, 2000 now U.S. Pat. No. 6,457,921, issued Oct. 1, 2003, that claims benefit of U.S. Provisional Patent Application Serial No. 60/165,402 filed Nov. 13, 1999.
BACKGROUND
1. Field of Invention
This invention relates to a pneumatic inflation system for use with a freight carrier, such as a tractor-trailer, along with reusable air bags inflatable with the inflation system for bracing freight and cargo during transit, thereby preventing damage to the freight.
2. Description of Prior Art
Transporting large freight over long distances is an integral part of virtually every industry. Trucks, railroad cars, airplanes, ships, etc., are all commonly used to transport goods. In general terms, however, a freight carrier, such as a tractor-trailer, temporarily stores the freight during transport. To this end, freight protection within the carrier has remained unchanged for many years. Damaged freight is considered a part of doing business. With specific reference to tractor-trailers, there are currently three methods used for protection of freight during transit.
One method used is load locks. Load locks protect the load from leaning or falling out of the end of the trailer. Load locks do not protect the entire load from damage. Load locks are cumbersome, difficult to maneuver, heavy and often fail during transit. Another method is the use of low grade, unreliable, one-time use, paper dunnage bags. These bags are used once and then cut up by the user at the destination, generating significant waste. Third, vinyl or plastic inflatable dunnage bags are also used in freight carriers where it is customary to fill the spaces between the cargo, or between the cargo and the walls of the freight carrier, to prevent the cargo from shifting and damaging either the cargo itself, and/or the walls of the freight carrier. These bags are inflated at the shipping dock. Typically, the freight protection is installed/provided when the freight is initially placed into the trailer. Trailer door is shut and the freight protection devices that were installed are expected to withstand the hazards of travel to the destination. Air bags often deflate during transit due to changes in pressure in and outside the trailer as the driver ascends and descends in the mountains. Air bags and other freight protection devices also fail and fall to the floor of the trailer over the rough roads and driver maneuvers. Unfortunately, once the tractor-trailer has left the dock, it is impossible to re-inflate the air bags, as a pressurized air source is no longer available.
SUMMARY
In accordance with one aspect of the present invention, a trailer pneumatic inflation system for use with a freight carrier, such as a tractor-trailer, is provided. The inflation system is available to inflate reusable air bags to cushion freight during shipment from one location to another. In one preferred embodiment, the inflation system includes an air control unit and an air coupler device. The air control unit is fluidly connectable to a compressed air storage reservoir of a tractor-trailer and supplies air to the air coupler device. In one preferred embodiment, the air control unit includes a brake protection valve and a control valve. The brake protection valve substantially disconnects the inflation system from the air storage reservoir in the event that the air pressure of the reservoir drops below a predetermined value, thereby preventing possible failure of the trailer's braking system. The control valve is available for a user to conveniently shut the inflation system off. In another preferred embodiment, the air control unit and the air coupler device are both mounted to the underside of a freight carrier defined by a front, a back, and opposing sides. The air control unit is positioned in close proximity to the carrier's air storage reservoir, whereas the air coupler device is positioned adjacent one of the sides.
In another preferred embodiment, the inflation system is available to inflate a plurality of inflatable bags useful for protecting freight stored within the freight carrier. The inflatable bags are preferably configured to be re-useable and each includes upper and lower latching tabs. These latching tabs are configured to receive a coupling device that secures the respective inflatable bag to the freight. With this configuration, the inflatable bag will not undesirably slide downwardly relative to the freight during transit.
Accordingly, several objects and advantages of the preferred embodiments of the present invention are:
(a) to provide ability for the driver to make adjustments in freight protection during transit from origin to destination;
(b) to provide a trailer pneumatic inflation system in combination with inflatable air bags that can stabilize any type of cargo;
(c) to provide a trailer pneumatic inflation system in combination with inflatable air bags that will reduce driver tension, minimizing concern about shifting of the cargo in any direction;
(d) to provide a trailer pneumatic inflation system in combination with inflatable air bags that is easy and quick to install to stabilize cargo;
(e) to provide a trailer pneumatic inflation system that works secondary to the air braking system;
(f) to provide ability to inflate the air bags from the tractor-trailer;
(g) to provide a fail safe inflation device that ensures protection of the tractor-trailer;
(h) to provide on-board inflatability of air bags;
(i) to provide use of the truck trailers compressed air source (air tank);
(j) to provide continuous freight protection regardless of pressure and temperature changes within and outside the trailer, rough roads and hazardous travel using aligning and safety flaps on the air bags;
(k) to provide freight protection to the entire load;
(l) to provide an appropriate type of air bag suitable to protect the size of freight being hauled;
(m) to provide for a reduction of waste in the transportation industry, providing a reusable inflatable air bag over the one-time use paper air bag; and
(n) to provide for reliable freight protection device.
Further advantages are to provide inflatable air bags that can be made from any suitable material of engineering choice, such as plastic, vinyl, paper or the like. Further advantages are' to provide lateral restraint and proper distribution of air bags using aligning flaps that can be fastened to each other using any suitable material of engineering choice such as a bungee cord, rubber band, rope, elastic material or the like. Further advantages are to provide vertical restraint and proper distribution of air bags using safety flaps that can be fastened to freight using any suitable material of engineering choice such as a bungee cord, rubber band, rope, elastic material or the like.
Still further objects and advantages will become apparent from a consideration of the ensuing description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of a truck in combination with a semi-trailer and incorporating a trailer pneumatic inflation system in accordance with the present invention;
FIG. 2 is a schematic view of the trailer of FIG. 1;
FIG. 3 a bottom view of the trailer of FIG. 1, including the inflation system in accordance with the present invention;
FIG. 4 an enlarged, cross-sectional view of an air control unit and air coupler device of the inflation system of FIG. 3;
FIG. 5 is an enlarged, cross-sectional view of the air control unit of FIG. 4;
FIG. 6 is a side view of the air coupler device of FIG. 3;
FIG. 6A is a perspective view of the air coupler device of FIG. 6;
FIG. 7 is a top, schematic view of freight secured within a trailer by inflatable bags in accordance with the present invention;
FIG. 8 is a side view of an air bag in accordance with the present invention;
FIG. 9 is a rear view of the tractor-trailer of FIG. 7;
FIG. 10 is a top, schematic view of freight stagger loaded and secured within a trailer.
FIG. 11 is a rear view of a tractor-trailer with short cargo secured by inflatable bags in accordance with the present invention;
FIG. 12 is a rear view of the tractor-trailer with tall cargo secured by inflatable bags in accordance with the present invention;
FIG. 13 is a side, perspective view of an alternative air coupled, including a glad hand;
FIG. 13A is a perspective view of the air coupler device of FIG. 13;
FIG. 13B is a side view of an alternative inflation system in accordance with the present invention, including the air coupler device of FIG. 13;
FIG. 14 is a side, perspective view of an alternative air coupler device, including a glad hand;
FIG. 14A is a perspective view of the air coupler device of FIG. 14;
FIG. 14B is a side view of an alternative inflation system in accordance with the present invention, including the air coupler device of FIG. 14 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein like reference numerals designate corresponding structure throughout the views, and referring in particular to FIGS. 1 through 6A a pneumatic inflation system 49 for use with a freight carrier pursuant to a preferred embodiment of the present inventions and FIGS. 13 through 14B pursuant to an alternative embodiment of the present inventions.
As a point of reference, the inflation system 49 is highly useful with the trucking industry. To this end, FIG. 1 shows a truck 16 in association with a freight carrier or trailer 15 . Notably, the inflation system 49 can also be used with other types of freight carriers, such as any other container, cargo space, railroad car, or any other suitable transport container which may also be inside an aircraft or on a ship. By way of example, the instant transport container is intended to be part of a road vehicle. A tractor compressor (not shown) is driven by the truck's 15 engine (not shown) and supplies air to a pressurized air storage reservoir 17 (FIG. 3 ). Although not shown in the drawings for ease of illustration, air lines pass rearwardly from the tractor compressor too the air storage reservoir 17 through a tractor protection valve to a glad hand between the tractor 16 and trailer 15 . As is known in the art, the air storage reservoir 17 is mounted to an underside of the trailer 15 , and is normally used to control the trailer's 15 air brake and/or air suspension systems.
With reference to FIGS. 2 and 3, the inflation system 49 of the present invention preferably includes an air control unit 31 , an air coupling device 29 and an air hose 53 . The air control unit 31 and the air coupling device 29 are mounted to an underside of the trailer 15 (shown best in FIG. 3 ), with the air control unit 31 preferably in close proximity to the air storage reservoir 17 and the air coupling device 29 adjacent one of the opposing sides of the trailer 15 . The air control unit 31 is fluidly connected to the air storage reservoir 17 by tubing 32 B, and supplies pressurized air to the air coupling device 29 . The air hose 53 , in turn, in fluidly connectable to the air coupling device 29 , and is available for inflating or otherwise providing pressurized air to a wide variety of auxiliary components associated with the trailer 15 , such as inflatable dunnage bags, pneumatic tools, tires, etc.
The air coupling housing 29 has an air hose adapter to receive the air hose 53 having an externally threaded fitting adapted to be connected to the main passage at the tapped portion of air coupler hosing 29 . In a preferred embodiment, the hose 53 terminates at a nozzle apparatus 54 which is preferably in the form of a pistol-shaped nozzle, having a hand grip. Alternatively, the hose 53 can be connected to a wide variety of other devices.
FIG. 3 is an under side view of the trailer 15 incorporating the trailer pneumatic inflation system 49 . As previously described, the trailer 15 has the air storage reservoir 17 that, for example, is coupled to an appropriate compressor on the truck 16 (FIG. 1 ), so that air pressure within the reservoir 17 may be maintained at a particular pressure, for example 120 psi. FIG. 3 shows a position of the air control unit 31 mounted within close proximity to the air storage reservoir 17 . As is known in the art, the air storage reservoir 17 has one or more exit ports. An air line or tubing 32 B fluidly connects one of these ports, and thus the air storage reservoir 17 , to the air control unit 31 . So as to minimize the opportunity for damage to the tube 32 B, the air control unit 31 is mounted to the trailer 15 as close as possible to the air storage reservoir 17 . In a preferred embodiment, then, the tubing 32 B has a length less than approximately 12 inches.
The air coupler device 29 is located in the front of a trailer tandem coupled to a floor or slider box of a trailer 15 so that a dockworker in charge of loading a trailer, for example at a loading dock, has control in tapping an air source. To this end, the air coupler device 29 is preferably mounted to the trailer 15 adjacent one of the sides thereof. With this preferred location, the air coupler device is readily accessible by a user for connecting the hose 53 (FIG. 2) thereto. The air control unit 31 is fluidly connected to the air coupler device 29 by an air line or tubing 32 .
FIG. 4 is a longitudinal cross-sectional view depicting one preferred embodiment of the pneumatic inflation system 49 in an open position. The air line 32 B fluidly connects the air storage reservoir 17 (FIG. 3) to the air control unit 31 (an additional air line 32 C may further be provided to complete this fluid connection). The second the air line 32 from the air control unit 31 provides controlled air flow to the air coupler device 29 . Finally, the air hose 53 connects to the air coupler device 29 using a compressed air coupling. The air hose 53 is connected to the inflation nozzle apparatus 54 , which is preferably in the form of a pistol-shaped nozzle, having a handgrip, supplied with compressed air from the hose 53 .
FIG. 5 is an enlarged, sectional view of one preferred embodiment of the air control unit 31 . The air control unit 31 preferably includes an enclosure 27 , a brake protection valve 47 and a control valve 48 . The enclosure 27 of the air control unit 31 is constructed of corrosive resistant and temperature resilient material, such as stainless steel, aluminum, plastic, etc., with a door 27 A having a latching mechanism (not shown) that provide a tight seal to keep the weather, road dust, corrosion, salt, debris and other foreign material from entering the enclosure 27 . As previously described, the enclosure 27 is configured for mounting in close proximity to the air storage reservoir 17 (FIG. 3) of the trailer 15 (FIG. 3 ). The enclosure 27 forms openings 18 on each respective end. An externally and internally threaded, tubular shaft 42 is inserted through one (or top, relative to the orientation of FIG. 5) opening 18 . On the outside of the enclosure 27 , a sealing ring 45 , a metal spacer 44 , and a nut 43 having a threaded hole, encircle the threaded shaft 42 . On the inside of the enclosure 27 , a metal spacer 44 and a nut 43 having a threaded hole, encircle the threaded shaft 42 . This allows the nuts 43 to be screwed tightly onto the enclosure 27 to provide an airtight seal. One end of a threaded nipple 46 is threaded into shaft 42 within enclosure 27 with another end threaded into the brake protection valve 47 .
The brake protection valve 47 controls the flow of air into the pneumatic inflation system 49 and out of an air storage reservoir 17 (FIG. 3 ). Should the air pressure in the air storage reservoir 17 fall below 60 psi, the brake protection valve 47 will close, ceasing to allow air to pass from the air storage reservoir 17 into the inflation system 49 . This will maintain enough air pressure in air storage reservoir for effective braking of the truck 16 and the trailer 15 , shown in FIG. 1 . Other system shut off pressure values, such as 50 psi or 40 psi, are equally acceptable. A threaded hex nipple 46 A is threaded into another (preferably downstream) end of the brake protection valve 47 and one end of the control valve 48 . The control valve 48 has an interior opening there through so that when it is aligned with an airline, the control valve 48 is open as shown in FIGS. 4 and 5. When a knob 48 A is rotated a quarter turn, the control valve 48 is turned off. Thus, if the second air line 32 shown in FIG. 3 is damaged at any time, an operator of the equipment, dockperson, or other personnel could rotate the knob 48 A on the control valve 48 to shut off air completely within the air control unit 31 , allowing the air storage reservoir 17 to return and maintain full psi. One end of threaded nipple 46 is threaded into the other side (preferably downstream) of the control valve 48 and into another externally and internally threaded, tubular shaft 42 (lower shaft 42 in FIG. 5 ). The threaded shaft 42 is inserted through the lower opening 18 in the enclosure 27 . On the inside of enclosure 27 , a nut 43 having threaded hole and a metal spacer 44 encircle threaded shaft 42 . On the outside of the enclosure 27 , a sealing ring 45 , metal spacer 44 , and nut 43 having threaded hole, encircle the lower threaded shaft 42 . This allows nuts 43 to be screwed tightly onto enclosure 27 to provide an airtight seal.
During use and in accordance with one preferred embodiment, pressurized air is delivered from the air storage reservoir 17 (FIG. 3) to the air control unit 31 . The air control unit 31 effectively defines an inlet (for example, the shaft 42 otherwise connected to the brake protection valve 47 ). Air flows from the inlet to the brake protection valve 47 . Assuming sufficient pressure is present, the brake protection valve 47 allows the air to flow (downstream) to the control valve 48 . If the control valve is “open,” air flow continues downstream to an outlet defined by the air control unit 31 (for example, the shaft 42 fluidly connected downstream of the control valve 48 ). Thus, the air control unit 31 is configured to receive pressurized air from the air supply reservoir 17 , and selectively allows the air to flow to the air coupler device (FIG. 4 ), depending upon operational parameters of the air storage reservoir 17 (via, for example, the brake protection valve 47 ) and manual or operator settings (via, for example, the control valve 48 ). Alternatively, a number of other designs for the air control unit 31 can be employed to achieve these objectives. For example, the brake protection valve 47 and the control valve 48 can be reversed and/or replaced with other component(s).
FIGS. 6 and 6A are side and perspective views, respectively, of one preferred embodiment of the air coupler device 29 . In general terms, the air coupler device 29 includes tubing for receiving air from the air control unit 31 (FIG. 5) and for selective fluid connection to the hose 53 (FIG. 2 ), along with an enclosure 28 . The enclosure 28 is preferably constructed of corrosive resistant and temperature resilient material, such as stainless steel, aluminum, plastic, etc., and includes a door 28 A having a latching mechanism (not shown) that provide a tight seal to keep weather, road dust, corrosion, salt, debris and other foreign material from entering the enclosure 28 . The enclosure 28 is configured for mounting to the front of a trailer tandems coupled to a floor or slider box of a trailer 15 so that a person in charge of loading the trailer 15 has easy access to the air coupler device 29 . The enclosure 28 preferably has one opening 18 . An externally and internally threaded tubular shaft 42 is inserted through the opening 18 , shown in FIG. 6, and defines an intake port. On the outside of the enclosure 28 , a sealing ring 45 , a metal spacer 44 , and a nut 43 having a threaded hole, encircle the threaded shaft 42 . On the inside of the enclosure 28 , a metal spacer 44 and nut 43 having threaded hole, encircle threaded shaft 42 . This allows nuts 43 to be screwed tightly onto enclosure 28 to provide an air tight seal. One end of a threaded hex nipple 46 A is threaded into a downstream end of the shaft 42 within enclosure 28 . Another end of the threaded hex nipple 46 A is threaded into a female body section 30 A of a valve quick disconnect coupling. A stem end (or exit port) of a male half 41 of a valve quick disconnect coupling connects to an air hose 53 , shown in FIG. 2 .
During use, the air coupler device 29 receives air, at the intake port, from the air control unit 31 when the air control unit 31 is “open”. A user then selectively couples the hose 53 (FIG. 2) to the exit port of the air coupler device 29 , such that when connected, the air coupler device 29 provides a conveniently accessible source of pressurized air. Thus, a user is not required to crawl under the trailer 15 (FIG. 2) to access the air coupler device 29 . Further, by forming the air coupler device 29 to be separately positionable relative to the air control unit 31 , the air control unit 31 can be positioned as close as possible to the air storage reservoir 17 (FIG. 3) without impeding the desired convenient access to a source of pressurized air. Notably, were the line 32 between the air control unit 31 and the air coupler device 29 severed or otherwise damage, the brake protection valve 47 (FIG. 5) would automatically shut the inflation system 49 off, so that the air supply reservoir would not drop below a minimum pressure level.
As described in greater detail below, the air coupler device 29 can assume a wide variety of forms other than the one preferred embodiment illustrated in FIGS. 6 and 6A. Regardless, the air coupler device 29 provides a conveniently accessible, pressurized air source for connection to the hose 53 (FIG. 3 ). The hose 53 can be used for a number of applications, including pneumatic tools, cleaning purposes, etc. In one preferred embodiment, the inflation system 49 is employed to inflate inflatable dunnage bags as described below.
FIG. 7 is a top view of freight, such as pallets, 25 (twenty four are shown) arranged in a centerline configuration between trailer walls of cargo space and secured by a plurality of centerlining air bags 19 in accordance with the present invention. Arrows indicate a flow pattern of refrigerated air passing within the trailer 15 to cool the freight 25 . Narrow voids between walls of the trailer 15 and cartons on pallets 25 arranged two abreast are occupied by the centerlining air bags 19 . Bungee cords, rubber bands, ropes or other suitable elastic material 26 are attached to each of the air bags 19 and can be used as guides to ensure proper distribution of the bags 19 within the trailer 15 and provide lateral restraint evenly throughout the trailer 15 .
FIG. 8 shows one preferred embodiment of the air bag 19 as being an elongated inflatable reusable sleeve made of durable flexible plastic, rubber elastomeric material (which returns to its original shape) or from inflatable cloth-like material. The air bag 19 preferably includes an inflation valve 22 , a deflation or exhaust valve 21 , aligning tabs 20 and safety or latching tabs 20 A. The aligning tabs 20 are affixed to opposite sides of the air bag 19 and form an opening therein. The safety or latching tabs 20 A are affixed to a top and bottom, respectfully, of the bag 19 . Bungee cords, rubber bands, ropes or other suitable elastic material 26 (FIG. 7) may be utilized to fasten the bags 19 to each other via the aligning tabs 20 within a cargo trailer 15 , where desired, to provide lateral restraint and proper distribution of the bags 19 . Further, bungee cords, rubber bands, ropes or other suitable elastic material may be utilized to fasten the bag 19 to the freight 25 within the trailer 15 , where desired, to provide vertical restraint and proper distribution the bag 19 between the freight 25 and the trailer 15 , as described below.
FIG. 9 is a rear view of the trailer 15 with the freight 25 centerlined and secured by the invention. Arrows indicate a flow pattern of refrigerated air. Narrow voids between walls of a truck trailer and cartons on the freight 25 arranged two abreast are occupied by one of the inflatable centerlining air bags 19 .
FIG. 10 is a top view of freight, such as pallets, 25 (twenty four are shown) arranged in a staggered configuration between walls of the trailer 15 of a cargo space and secured by air bags 23 . The air bags 23 are highly similar to that previously described, but are under 6 feet in height. Narrow voids between walls of a transport container and cartons on pallets arranged two abreast are occupied by the air bags 23 . In accordance with the present invention, lateral shifting of cargo is avoided or reduced by providing a plurality of inflatable air bags 23 or 24 depending upon the height of the cargo.
FIG. 11 and FIG. 12 show a rear view of the trailer 15 with short palletize cargo 25 and tall palletized cargo 25 , respectively, and secured by air bags 23 , 24 , respectively. Narrow voids between walls of the trailer 15 and the freight 25 arranged two abreast are occupied by inflatable, under six feet tall, air bags 23 (FIG. 11) or over six feet tall air bags 24 (FIG. 12 ). Selection of the appropriate air bag will depend upon height of the freight 25 . In either case, the safety latching tabs 20 A are available for securing the bags 23 or 24 to the freight 25 , such as with a rope, bungee cord, etc. (not shown). Unlike other available dunnage bags, the safety latching tabs 20 A, in conjunction with the coupling device (e.g., rope, bungee cord, etc.), prevents the bag 23 , 24 from sliding downwardly during transit.
Returning to FIGS. 1-3, as previously described, the inflation system 49 can assume a wide variety of forms. With specific reference to the air coupler device 29 , existing components of the trailer 15 , such as a glad hand, can be utilized by, an incorporated into, the present invention. In this regard, FIG. 13 and FIG. 13A are side and perspective views, respectively, of an alternative embodiment air coupler device 29 A. The air coupler device 29 A includes the enclosure 28 as previously described, tubing, and a glad hand 50 . The enclosure 28 preferably has three openings 18 . Externally and internally threaded, tubular shafts 42 are inserted through each of the openings 18 , as shown in FIG. 13 . On the outside of the enclosure 28 , a sealing ring 45 , a metal spacer 44 , and nut 43 having a threaded hole, encircle each of the threaded shafts 42 . On the inside of the enclosure 28 , a metal spacer 44 and a nut 43 having threaded hole, encircle each of the threaded shafts 42 . This allows nuts 43 to be screwed tightly onto the enclosure 28 to provide an air tight seal. One of the shafts 42 is connected to the glad hand 50 , while the other two shafts are fluidly connected by a valve plug 48 , including elbow nipples 59 . The valve plug 48 includes a control 48 A for manually opening and closing the valve plug 48 .
As shown in FIG. 13B, the air coupler device 29 A is fluidly connected to the air control unit 31 at an intake port (defined by one of the tubular shafts 42 as illustrated in FIG. 13 B). Air flows from the intake port through the valve plug 48 (which an operator can manually turn on or off). Assuming the valve plug 48 is open, air flows to the glad hand 50 , such as by tubing 32 . Finally, the glad hand 50 is selectively connectable to the hose 53 (for example, via line 32 A) for supplying pressurized air to the hose 53 . Glad hands, such as the glad hand 50 , are well known in the art. The glad hand 50 serves as the exit port for the air coupler device 29 A.
FIGS. 14 and 14A are side and perspective views, respectively, of another alternative embodiment air coupler device 29 B. The air coupler device 29 B includes an enclosure 28 and a glad hand 51 . The enclosure 28 preferably has one opening 18 . An externally and internally threaded, tubular shaft 42 is inserted through the opening 18 , as shown in FIG. 14 A. On the outside of the enclosure 28 , a sealing ring 45 , a metal spacer 44 , and nut 43 having a threaded hole, encircle the threaded shaft 42 . On the inside of the enclosure 28 , metal spacer 44 and nut 43 having threaded hole, encircle the threaded shaft 42 . This allows nuts 43 to be screwed tightly onto the enclosure 28 to provide and air tight seal. Another end of threaded hex nipple 46 A is threaded into the glad hand 51 . In the embodiment of FIGS. 14 and 14A, the glad hand 51 is of a type known in the art and includes a shut off valve 51 A. As is known in the art, the valve 51 A can be manually operated to control air flow through the glad hand 51 .
As shown in FIG. 14B, the air coupler device 29 B is fluidly connected to the air control device 31 for receiving pressurized air therefrom. In this regard, the glad hand 51 provides the intake port, via the tubular shaft 42 , for the air coupler device 29 B. Further, the glad hand 51 provides the exit port, via the line 32 A, for selectively delivering pressurized air to the hose 53 upon connection of the hose 53 to the glad hand 51 and activation of the shut off valve 51 A.
While the present invention has been described with reference to the above preferred embodiments and alternative embodiments, it will be understood by those skilled in the art, that various changes may be made and equivalence may be substituted for elements thereof without departing from the scope of the present invention. In addition, modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is intended that the invention carrying out this invention, but that the present invention includes all embodiments falling within the scope of the appended claims and their legal equivalents.
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A pneumatic inflation system for use with a freight carrier, such as a tractor-trailer, is provided. The inflation system is available to inflate reusable air bags to cushion freight during shipment from one location to another. In one preferred embodiment, the inflation system includes an air control unit and an air coupler device. The air control unit is fluidly connectable to a compressed air storage reservoir of a tractor-trailer and supplies air to the air coupler device. In one preferred embodiment, the air control unit includes a brake protection valve and a control valve. The brake protection valve substantially disconnects the inflation system from the air storage reservoir in the event that the air pressure of the reservoir drops below a predetermined value, thereby preventing possible failure of the trailer's braking system. The control valve is available for a user to conveniently shut the inflation system off. In another preferred embodiment, the air control unit and the air coupler device are both mounted to the underside of a trailer defined by a front, a back, and opposing sides. The air control unit is positioned in close proximity to the trailer's air storage reservoir, whereas the air coupler device is positioned adjacent one of the sides.
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FIELD OF INVENTION
[0001] The present invention is directed to an LED, and arrays of same. In particular, the LED emits energy in the ultra-violet (optical wavelength greater than or equal to 150 nm and less than or equal to 410 nm) portion of the electromagnetic spectrum.
BACKGROUND OF THE INVENTION
[0002] Consideration has been given to using single color LED's, such as red, blue or green LED's, in combination with fluorescent and phosphorescent materials to produce another desired color. While certain materials respond fluorescently or phosphorescently to light from the visible portion of the spectrum, and thus would respond to visible LED's, there are a number of materials which respond to the relatively higher-energy photons emitted in the ultraviolet portion of the spectrum. Furthermore, UV-emitting LED's may, in combination with the appropriate phosphor, prove to be a source of white light providing a high level of satisfaction. That is, white light generated from a UV LED and accompanying phosphor may lack the artifacts of a colored light source employed to produce light from an LED emitting in the colored portion of the visible spectrum. For example, this phenomenon is believed to affect blue LED's when used to excite a phosphor during production of white light, where the generated white light is believed to exhibit a blue component. Accordingly, recent interest has focused upon the use of a UV-emitting LED.
[0003] At least certain prior art LED devices emit light in directions that may be undesirable, such as through the sides of the diode, as opposed to only substantially through the preferred side for the emission of energy. Depending upon the end use for which the LED is employed, this may not be a problem. However, as indicated, there may be instances where emissions in undesired directions have substantial unwanted consequence. For example, in UV-induced fluorescence detection applications, stray UV light can dramatically increase the background noise in the photodetection of fluorescent light. Further, in such application, it is preferred that a focused beam of UV light is provided to generate sufficient fluorescence for localized photodetection. At the very least, emissions in undesired directions may be indicative of an inefficient device.
SUMMARY OF THE INVENTION
[0004] The present invention is directed towards a source of ultraviolet energy, wherein the source is a UV-emitting LED's. In an embodiment of the invention, the UV-LED's are characterized by a base layer material including a substrate, a n-doped semiconductor material, a multiple quantum well, a p-doped semiconductor material, and corresponding n- and p-metallization in contact with the n- and p-layers respectively. The base layer material has a mesa configuration that may be rounded on a boundary surface, or which may be non-rounded, such as a mesa having an upper boundary surface that is flat. In other words, the p-type metal resides upon a mesa formed out of the base structure materials. In a more specific embodiment, the UV-LED structure includes passivation layers and bond pads positioned at appropriate locations of the device. In a more specific embodiment, the p-type metal layer is encapsulated in the encapsulating layer.
[0005] In yet another embodiment, LED's substantially as described above, are arranged spatially and/or arrayed in particular arrangements that vary, for example, the number of rows of diodes, the number of diodes per row, diode spacing, the amount of n-metal present between each mesa, and diode offsets—that is, the offset between diodes of a given row and the diodes of an adjacent row, as indicated later in this paper. In yet another embodiment, circular diodes of specified diameters are employed. In one specific embodiment, the diode diameters are about 100 μm or even less. Such arrangements and combinations thereof, have been found to improve the output of UV energy, for example, by improving current spreading through the LED's. Furthermore, the arrangement and combinations provide the artisan with the ability to adjust the output from the device and/or minimize, if not eliminate, undesired effects that result where unwanted material defects enter the field of emission, which would otherwise interfere with the emission of light.
[0006] It is believed that the structures described herein are capable of transmitting a collimated band of energy, which is desirable for devices in which narrow transmission bands are desired. For example, a device of the present invention, emitting collimated energy, may be employed in a device detecting the presence or absence of a given thing, and/or for the measurement of same, where for instance, the presence, absence, or measurement of that phenomena is in some way related to the measurement of the emission after it encounters (or does not encounter) the thing to be detected or measured. In these instances, generalized emissions (such as through the side of the device), could render the measurement less accurate or reliable.
[0007] Also, it is believed that output from the diodes of the present invention are substantially limited to the UV-portion of the electromagnetic spectrum. In other words, the output is substantially devoid of emissions in the visible portion of the spectrum, such as visible light in the yellow portion of the spectrum. This may be due to improved current spreading which allows higher current densities and “swamping out” of defect emission by near-band-edge emission. However, having smaller mesas, less than 100 um in diameter, also reduces the optical volume of n- and p-cladding layers, which may be plagued with sub-band-edge luminescent structural and point defects, allowing light to escape the mesa in a shorter optical path length.
[0008] In another aspect of the present invention, LEDs of the present invention are arrayed in linear, triple, and compact arrays, as described herein. In a more specific embodiment of the invention, the LEDs are circular in shape, having diameters not exceeding 100 μm, and are spaced by a predetermined amount of n-metallization layer, as measured linearly, between adjacent diodes.
[0009] In another aspect of the invention, the LED's of the present invention have mesas that are provided with a rounded boundary surface contour resembling, for example, a hemisphere or parabola, an ellipse, or combinations thereof.
[0010] In one aspect, the term “collimated” light or energy refers to a parallel or substantially parallel band of energy emitted from its diode source, with lateral energy spreading, away from the cross-sectional area of the diode, limited to approximately +/−15° as measured radially from a line extending from the edge of the emission source, in the direction of the emitted energy.
BRIEF DESCRIPTION OF THE FIGURES
[0011] FIG. 1 is a LED of the present invention, depicted in cross-section;
[0012] FIG. 1 a is a top plan view of the LED of the present invention;
[0013] FIG. 2 depicts the formation of a LED of the present invention, in cross-section, at a relatively early stage of production;
[0014] FIG. 2 a is atop plan view of the LED depicted in FIG. 2 ;
[0015] FIG. 3 depicts the formation of a LED of the present invention, in cross-section, subsequent to the FIG. 2 depiction;
[0016] FIG. 3 a is a top plan view of the LED depicted in FIG. 3 ;
[0017] FIG. 4 depicts the formation of a LED of the present invention, in cross-section, subsequent to the FIG. 3 depiction;
[0018] FIG. 4 a is a top plan view of the LED depicted in FIG. 4 ;
[0019] FIG. 5 depicts the formation of a LED of the present invention, in cross-section, subsequent to the FIG. 4 depiction;
[0020] FIG. 5 a is a top plan view of the LED shown in FIG. 5 depiction;
[0021] FIG. 6 depicts the formation of a LED of the present invention, in cross-section, subsequent to the FIG. 5 depiction;
[0022] FIG. 6 a is a top plan view of the LED shown in FIG. 6 ;
[0023] FIG. 7 depicts the formation of a LED of the present invention in cross-section, subsequent to the FIG. 6 depiction;
[0024] FIG. 7 a is a top plan view of the LED shown in FIG. 7 ;
[0025] FIG. 8 is a cross-sectional view of a substrate employed in the LED of the present invention;
[0026] FIG. 9 is a cross sectional view of a circular LED of the present invention;
[0027] FIG. 10 is a cross sectional view of adjacent LED's (and the region between them);
[0028] FIG. 11 is a top plan view of 25 μm circular diodes;
[0029] FIG. 12 is a top plan view of 50 μm circular diodes;
[0030] FIG. 13 is a top plan view of 100 μm circular diodes;
[0031] FIG. 14 is a top plan view of 25 μm circular diodes in an offset linear array;
[0032] FIG. 15 is a top plan view of a compact array;
[0033] FIG. 16 is a top plan view of a triple array;
[0034] FIG. 17 is a top plan view of a single linear array;
[0035] FIG. 18 is a top plan view depicting a particular arrangement;
[0036] FIG. 19 is a cross sectioned view of an embodiment of the present invention;
[0037] FIG. 20 is a cross sectional view of an embodiment of the present invention;
[0038] FIG. 21 is a cross sectional view depicting collimation in the LED's shown in FIG. 20 .
[0039] FIG. 22 is a cross sectional view of an embodiment of the present invention.
[0040] FIG. 22 a is a cross sectional view of the embodiment shown in FIG. 22 .
[0041] FIG. 23 is a cross sectional view showing the parabolic mirror effect of light leaving the mesa of the structure shown in FIG. 24 .
[0042] FIG. 24 is a cross sectional view of a particular arrangement of LEDs of the type shown in FIG. 22 .
DETAILED DESCRIPTION OF THE INVENTION
[0043] An LED 10 of the present invention is depicted in FIG. 1 . It should be understood that the LED will be incorporated into arrays including a plurality of LED's, which is discussed and shown later in this disclosure.
[0044] LED 10 includes the following components: base layer 12 , p-metal layer 14 , encapsulant 16 , mesa 18 , n-metallization layer 20 , passivation layer 22 , p-bond pad 24 and n-bond pad 26 (not shown in FIG. 1 ). The bond pads are used to connect the device to a suitable package.
[0045] Base layer 12 is a multiple component element. As depicted in FIG. 8 , base layer 12 includes a substrate 30 , such as a substrate of sapphire, silicon carbide, zinc oxide, gallium nitride, and any combination of a gallium nitride-aluminum-indium alloy of the formula Al x In y Ga l-x-y N, wherein x+y<1, and GaAF. An epitaxial layer of an n-doped containing material 32 is deposited upon the substrate 30 . Here the n-doped material may be any conventional material, such as GaN doped with silicon. As shown in FIG. 8 , a silicon dopant is present in one or more delta doped layers, that is, one or more discreet layers 34 of dopant. A delta-doped arrangement may be advantageous in terms of promoting structural integrity of the device and/or facilitating spreading of current through the base structure. However, other doping schemes may be employed instead of delta doping. An active region of multiple quantum wells (MQW's) 36 is positioned upon the n-cladding layer. MQW's may be constructed of material known to be suited for this purpose, such as alternating layers of undoped aluminum indium gallium nitride alloys, doped or undoped, of any stoichiometry, having different ratios of aluminum, indium, and gallium for quantum confinement. A layer of p-doped material 38 , such as GaN, AlGaN, or AlInGaN (any stoichiometry) doped with Mg, is deposited upon the MQW layer.
[0046] Group III-nitride epitaxial films are typically deposited using MOCVD (metal organic chemical vapor deposition), MBE (molecular beam epitaxy), HVPE (hydride vapor phase epitaxy) or other epitaxial deposition technique. The substrate can be any variety of materials: sapphire, silicon, SiC, GaN, AlN, InN, AlIn, AlInGaN with any alloy combination, lithium gallate, etc.
[0047] Before epitaxy, the precleaned wafers are annealed at high temperature in hydrogen and subsequently in ammonia. An optional template layer for nucleation, followed by a III-nitride template layer, are then deposited. A cladding layer is then deposited (typically n-cladding) followed by an active region (typically a multiple quantum well) a blocking layer (typically undoped) and another cladding layer (typically p-doped). The cladding layers are either uniformly doped, delta-doped, or grown as doped superlattices. N-type doping usually involves Si incorporation whereas p-type doping usually involves Mg incorporation.
[0048] Fabrication usually begins with a surface cleaning using solvents (for degreasing) and acids (for metal and oxide removal). Patterning of all mask levels is readily done with standard photoresist-based microfabrication techniques. The p-contact metallization (typically Ni, Pt, Ag, or Ni/Au) is typically defined first using e-beam evaporation or sputtering. P-contact encapsulation (via selective sputtering of TiW, for example) is preferred to prevent p-contact segregation at high temperature anneals and at high forward bias over time. Placing TiW between the n-contact metallization and n-bond metallization has also been found to help encapsulate the n-contact and prevent alloying between contact and bond metallization. If a rounded (i.e., parabolic, elliptical, spherical) mesa is fabricated, then it may be so done using reactive ion etching (RIE) and inductively coupled plasma (ICP) etching or etching with a chlorine-based chemistry by reflowing resist via elevated heating over time, by grading the photomask in absence of reflow, or by combining both. It should be kept in mind that the chemistry of the resist is quite important for controlling the mesa sidewall geometry. For example, AZ1512 positive resist for sidewall formation has been used successfully. N-contact metallization (typically Ti/Al) is then deposited using e-beam evaporation or sputtering, followed by passivation (typically sputtered SiO 2 ) and bond metal deposition (typically Ni/Au).
[0049] Devices may be packaged using GE COB (Chip On Board) flip-chip technology to avoid a silicon submount. In this case, the chip is mounted directly to a PCB board with solder bumps.
[0050] Turning now to FIGS. 2-7 , and then back to FIG. 1 , a process for fabricating LED's of the present invention and arrays of same, shall be described. FIG. 2 depicts a p-metal layer 14 deposited over the base layer 12 . P-metal layer may be selected from nickel, rhodium, silver, aluminum, palladium or alloys of same, alloys of Ni—Au, NiO—Au, NiO—Ag, indium-tin-oxide alloys and silver oxide, to enumerate just a few suitable materials. The p-metal can be a non-transparent, reflective or semi-reflective material, such as NiAu, in which case the light generated by the diodes is reflected by the p-pad metal and exits the back of the device. However, arrangements wherein the p-metal metallization is transparent, allowing light to exit the top of the device, are acceptable. A transparent p-metallization can be constructed of thin layers of nickel, platinum, silver, alloys of NiO—Au, NiO—Ag, alloys of In—Sn—O, AgO, rhodium, palladium or platinum.
[0051] FIG. 3 depicts the device after the p-metal 14 layer has been formed into circular diodes. It should be noted that other diode shapes might be employed, depending upon the intended usage of the completed structure; however, a circular geometry is desired for maximal current spreading. The p-metal may be formed by applying a photoresist layer (either positive or negative photoresist) that has been patterned upon the p-metal layer, with openings provided in the photoresist to correspond to locations where p-metal is to be removed. After developing the resist, the device is subjected to a wet etch in order to remove the p-metal at derived locations. Subsequent to etching, the photoresist is removed from the device. While one diode is shown in FIG. 3 , it will be appreciated that in many instances a plurality of diodes will be formed the base layer 12 , in accordance with the desired diode diameter, pattern, and spacing of same as described later in this disclosure.
[0052] The p-metal can be patterned by dry etching techniques, such as RIE and ICP etching. As shown in FIG. 3 a , the p-metal has been patterned into a circular shape, while other shapes can be employed, circular diodes are well suited to the production of a source of collimated light.
[0053] FIG. 4 depicts the device after an encapsulant 16 has been applied over and encapsulates the p-metal layer. The encapsulating layer may be applied by standard photolithographic techniques employing a positive or negative photoresist patterned into a mask, development of the mask, application of the encapsulating material, and removal of the mask. A Ti—W alloy may be employed as the material for the encapsulating layer. Because TiW cannot be easily selectively wet-etched, reactive-ion-etching and/or resist liftoff are preferred for selectively patterning TiW encapsulation over the p-contact metallization.
[0054] FIG. 5 shows device 10 after formation of the mesa 18 . As shown, mesa 18 is formed where a preselected portion of base layer 12 is removed from around the p-metal layer 14 . Mesas can be formed by patterning a resist (either positive or negative) upon the device, developing the resist in pre-selected areas, selective removal of undeveloped or developed resist and subsequently etching (via wet or dry techniques), portions of substrate selected for removal. ICP etching or RIE etching have been found to be well suited for this process step. Though the dry etch process also removes layers of the resist mask as well as the GaN alloy, the thickness of the resist mask prevents complete removal during dry etching, which usually consists of a chlorine-based chemistry. The remaining resist mask is subsequently chemically stripped from the surface.
[0055] As shown in FIG. 8 , when forming the mesa in the substrate 30 , a portion of the n-doped containing material, active region 36 , and p-doped containing material 38 have been removed. However, other arrangements are possible, where only a portion of p-doped material 38 and/or active region 36 are removed during mesa formation. Also, it should be noted that the arrangements other than shown in FIG. 8 are possible, wherein for example, the location of the n-doped layer and p-doped layer are reversed, and/or additional doped or undoped layers are present.
[0056] FIG. 6 depicts the device after n-metal layer 20 , such as titanium, aluminum, titanium-aluminum alloy, titanium tungsten aluminum alloy, TiW, tantalum alloy, or tantalum has been deposited upon the device. A resist is applied to the device, developed at selected locations, removed at undeveloped or developed locations (depending on the use of negative or positive resist), and the n-metal is deposited in the desired areas. The resist is then removed from the device.
[0057] The n-metal layer is deposited so as to enclose the p-metal layer and mesa within a boundary of n-metal layer, as depicted in FIG. 6 a . Sizing of the p-metal layer, and spacing from the p-metal layer and mesa edge, will be discussed later in this disclosure.
[0058] As shown in FIG. 6 , the n-metal layer has been deposited on the same side of the base layer on which the p-metal has been deposited. This arrangement is employed where a non-conductive material, such as sapphire, is employed as substrate 30 . Where the base layer is an electrically conductive material, such as the silicon carbide, or Al x In y G a1-x-y N alloys discussed previously, the n-contact layers may be formed on the side of the substrate opposite the side on which the p-metal layer is positioned.
[0059] FIG. 7 depicts the device after formation of a passivation layer 22 , which may be a layer of SiO 2 , SiN, or any suitable oxide or nitride. Passivation layer 20 is positioned over the n-metal contact and extends over the mesa edge to partially encapsulate the p-metal layer 14 , with an opening in the passivation layer provided in the top in order to provide electrical contact between p-bond pad and the p-metal layer. The passivation layer may be deposited in accordance with photolithographic techniques previously disclosed, with subsequent removal of the mask.
[0060] FIG. 1 shows the LED after the p-bond pad 24 has been formed to contact the p-metal layer 14 . If the p-metallization is chosen to be reflective, it is preferred that the p-bond metal not cover the entire p-metallization, so that area is open for light extraction from the top of the device. For example, the p-bond pad and or the p-metallization may be deposited in a grid type pattern to facilitate the transmission of light through the bond pad. The p-bond pad may be applied in accordance with conventional photolithographic techniques as described herein, including wet etching or dry etching after application and development of a mask patterned from a photoresist. The p-bond pad electrically connects the diode to a package or to an electric source. The p-bond metal may consist of Ni & Au, with interlayers of TiW to prevent alloying and metal absorption during high temperature soldering.
[0061] As shown in FIG. 9 , the applicants have learned that, where the diode is circular and has a diameter of 25 μm, the passivation layer 22 should overlap with the p-metal layer 14 for about 2 μm on the upper side of the p-metal layer. For diodes of larger diameters (e.g. 50 μm and 100 μm), the passivation layer/p-metal layer overlap should be about 5 μm.
[0062] The applicants have further found that the linear distance occupied by the n-metal layer, as measured laterally, between adjacent diodes (See FIG. 10 ), is dependent upon on diode diameter. For example, where an array of about 25 μm diameter diodes are arranged in a linear array, about 10 μm of n-metal should be present (a linear array is what its name implies, a number of diodes arranged in a single line). About 20 μm of n-doped metal should be present between arrays of about 25 μm circular diodes in a triple, compact, or an offset linear array. See FIGS. 11 and 14 . (A triple array is arrangement of three lines of diodes. The diodes of one line may be may be offset from the diodes of the other line. A compact array is an arrangement of four or more lines of diodes. The diodes of a given line may be offset from the diodes of adjacent line or adjacent lines. An offset linear array is an arrangement of two lines of diodes. The diodes of a given line may be offset from the diodes of adjacent line or adjacent lines.) For 50 μl diameter diodes in a linear array, about 10 μm of n-metal layer should be present between adjacent diodes. See FIG. 12 . 20 μm should be present between 50 μm diodes arranged in a triple array or an offset linear array, and about 25 μm of n-metal should be present between adjacent 50 μm diodes arranged in a compact array. See FIG. 12 . For 100 μm circular diodes, about 20 μm of n-metal layer should be present between adjacent diodes arrayed in a linear array, about 30 μm of n-metal should be present between adjacent diodes arranged in a triple array or an offset linear array, and about 35 μm of n-metal should be present between adjacent diodes arranged in a compact array (see FIG. 13 ). The guidelines set forth above are summarized in Table 1 below.
TABLE 1 Array Type Linear Triple Compact 25 μm 10 20 20 50 μm 10 20 25 100 μm 20 30 35
[0063] The applicants have found that, for compact arrays, a 10×10 arrangement is well suited for 25 μm diodes. For 50 μm and 100 μm diodes, the arrangements may be, respectively, 7×7 and 4×4.
[0064] The applicants have further found that the distance between the p-metal layer 14 and edge of the mesa 18 should be about 6 μm (see, e.g. FIGS. 9 and 11 ), and that the distance between the n-metal layer 20 to the mesa 18 should be about 6 μm. See, e.g. FIG. 10 . Thus, about 12 μm should be present between the p-metal and the n-metal layer. This arrangement is well suited for linear arrays, compact arrays, and triple arrays.
[0065] FIGS. 11 through 14 illustrate circular diodes arranged in linear arrays and in offset arrays. Linear arrays are effective at emitting energy over a concentrated area however, such area is relatively narrow. Arrangements such as compact arrays or offset arrays broaden the area over which energy is emitted, however the emissions tend to be more efficient (as a function of current applied to the diodes) where diodes are smaller and the number of rows of diodes are relatively few. Thus, it may be appreciated that the offset and/or triple array arrangement provides a relatively fair balancing of two desirable attributes: providing a fairly broad area of coverage and a fair degree of efficiency of energy output based on applied current. Further, as the desired UV focal feature for particle detection is a narrow line width greater than or equal to a single particle diameter and smaller than twice the diameter of a single particle, linear arrays allow for a dense focal line beam to be imaged with simple optics.
[0066] FIG. 15 demonstrates a compact array format arrayed upon a substrate having approximate dimensions of about 1000 μm×600 μm. Suitable array formats are for 25 μm diodes, 10×10, for 50 μm diodes, 7×7, and 100 μm diodes, 4×4. Approximate spacing between the positive bond pad 24 and negative bond pad 26 in approximately 250 μm, as shown in FIG. 16 . The negative bond pad is positioned on or within the substrate, and makes electrical contact with the n-metal, which is formed upon the substrate in a manner that permits it to contact the n-pad and complete the circuit.
[0067] FIG. 16 shows an triple array arranged upon a substrate having approximate dimensions of about 600 μm×600 μm. Suitable array formats are, for 25 μm diodes, 3×10, for 50 μm diodes, 3×7, and for 100 μm diodes, 3×4. Spacing between the diodes is as indicated previously. Approximate spacing between the positive bond pad 24 and the negative bond pad is approximately 250 μm. Triple arrays, where the lines of diodes are offset, provide a firewall effect to decrease, if not eliminate, the possibility that a particle traveling through the field of emission will not encounter emitted UV-energy. Such an arrangement is well suited to a detection system where the encounter between a particle and emitted energy will result in a measurable effect.
[0068] As shown in the figures, the diodes of adjacent rows are offset by the length of one-half mesa. However, the diodes may be offset in other arrangements, such as one-third to one-half mesa in length.
[0069] FIG. 17 shows a single linear array shown in a substrate having approximate dimensions of 600 μm×600 μm. Suitable arrangements are, for 25 μm diameter diodes, 10 diodes, for 50 μm diodes, 7 diodes and for 100 μm diodes: 4 diodes.
[0070] The applicants have learned that the p-bond pad metal 24 should be distanced about 20 μm from the n-metallization metal. Also, the pad metal should cover the p-metal by about 20 μm from the edge of the p-metal. See FIG. 18 .
[0071] FIG. 19 depicts a side view of a plurality of diodes, with the passivation layer not shown. Here, the mesas resemble trapezoids with the p-metal layer 14 situated at the peak and the n-metal situated in the valleys. P- and n-bond metal may be on top of the p- and n-metallization.
[0072] FIG. 20 depicts a plurality of diodes wherein the sidewalls of the mesas are rounded. A rounded arrangement may be advantageous in terms of collimating the transmission of light, as shown in FIG. 21 . That is, where the sidewalls of the mesas are rounded, substantially all light is emitted from the center of the diode. Rounded mesa sidewalls can be produced by engaging in a reflo process prior to etching.
[0073] Mesa height should be approximately 500 Å to 20 μm, with about 7000 Å being well suited for producing collimated light.
[0074] As further shown in FIG. 22 , for parabolic mesas, it has been found that a specific arrangement in which the distance between the edges of the p-contact and n-contact is greater than or equal to the edge-to-edge distance (x), but preferably 2x, of the p-contact, yields collimated light.
[0075] Due to the high resistivity of the p-cladding layers, i.e.—sheet resistance typically greater than 10,000 ohms per square, the active region is defined largely by the size of the p-contact metallization.
[0076] As shown in FIG. 23 , good results are obtained when the height of the rounded region of the mesa is 0.5 to 5 μm. Also the edge-to-edge distance of the mesa should be about 5 to 5000 μm.
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The present invention is directed towards a source of ultraviolet energy, wherein the source is a UV-emitting LED's. In an embodiment of the invention, the UV-LED's are characterized by a base layer material including a substrate, a p-doped semiconductor material, a multiple quantum well, a n-doped semiconductor material, upon which base material a p-type metal resides and wherein the base structure has a mesa configuration, which mesa configuration may be rounded on a boundary surface, or which may be non-rounded, such as a mesa having an upper boundary surface that is flat. In other words, the p-type metal resides upon a mesa formed out of the base structure materials. In a more specific embodiment, the UV-LED structure includes n-type metallization layer, passivation layers, and bond pads positioned at appropriate locations of the device. In a more specific embodiment, the p-type metal layer is encapsulated in the encapsulating layer.
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BACKGROUND OF THE INVENTION
This is a division of application Ser. No. 558,109, filed December 5, 1983, abandoned.
The invention relates to antigens, means and methods for the diagnosis of lymphadenopathy and acquired immune deficiency syndrome.
The acquired immune deficiency syndrome (AIDS) has recently been recognized in several countries. The disease has been reported mainly in homosexual males with multiple partners, and epidemiological studies suggest horizontal transmission by sexual routes as well as by intravenous drug administration, and blood transfusion. The pronounced depression of cellular immunity that occurs in patients with AIDS and the quantitative modifications of subpopulations of their T lymphocytes suggest that T cells or a subset of T cells might be a preferential target for the putative infectious agent. Alternatively, these modifications may result from subsequent infections. The depressed cellular immunity may result in serious opportunistic infections in AIDS patients, many of whom develop Kaposi's sarcoma. However, a picture of persistent multiple lymphadenopathies has also been described in homosexual males and infants who may or may not develop AIDS. The histological aspect of such lymph nodes is that of reactive hyperplasia. Such cases may correspond to an early or a milder form of the disease.
SUMMARY OF THE INVENTION
It has been found that one of the major etiological agents of AIDS and of lymphadenopathy syndrome (LAS), which is often considered as a prodromic sign of AIDS, should consist of a T-lymphotropic retrovirus which has been isolated from a lymph node of a homosexual patient with multiple lymphadenopathies. The virus appears to be distinct from the human T-cell leukemia virus (HTLV) family (R. C. Gallo and M. S. Reitz, "J. Natl. Cancer Inst.", 69 (No. 6), 1209 (1982)). The last mentioned virus has been known as belonging to the so-called HTLV-1 subgroup.
The patient was a 33-year-old homosexual male who sought medical consultation in December 1982 for cervical lymphadenopathy and asthenia (patient 1). Examination showed axillary and inguinal lymphadenopathies. Neither fever nor recent loss of weight were noted. The patient had a history of several episodes of gonorrhea and had been treated for syphilis in September 1982. During interviews he indicated that he had had more than 50 sexual partners per year and had travelled to many countries, including North Africa, Greece, and India. His last trip to New York was in 1979.
Laboratory tests indicated positive serology (immunoglobulin G) for cytomegalovirus (CMV) and Epstein-Barr virus. Herpes simplex virus was detected in cells from his throat that were cultured on human and monkey cells. A biopsy of a cervical lymph node was performed. One sample served for histological examination, which revealed follicular hyperplasia without change of the general structure of the lymph node. Immunohistological studies revealed, in paracortical areas, numerous T lymphocytes (OKT3 + ). Typing of the whole cellular suspension indicated that 62 percent of the cells were T lymphocytes (OKT3 + ), 44 percent were T-helper cells (OKT4 + ), and 16 percent were suppressor cells (OKT8 + ).
Cells of the same biopsied lymph node were put in culture medium with phytohemagglutinin (PHA), T-cell growth factor (TCGF), and antiserum to human α interferon ("The cells were grown in RPMI-1640 medium supplemented with antibiotics, 10 -5 M β-mercaptoethanol, 10 percent fetal calf serum, 0.1 percent sheep antibody to human α interferon, neutralizing titer, 7 IU at 10 -5 dilution and 10 percent TCGF, free of PHA"). The reason for using the antiserum to α-interferon was to neutralize endogenous interferon which is secreted by cells chronically infected by viruses, including retroviruses. In the mouse system, it had previously been shown that anti-serum to interferon could increase retrovirus production by a factor of 10 to 50 (F. Barre-Sinoussi et al., "Ann. Microbiol. (Institut Pasteur)" 130B, 349 (1979). After 3 days, the culture was continued in the same medium without PHA. Samples were regularly taken for reverse transcriptase assay and for examination in the electron microscrope.
After 15 days of culture, a reverse transcriptase activity was detected in the culture supernatant by using the ionic conditions described for HTLV-I (B. J. Poiesz et al. "Proc. Natl. Acad. Sci. U.S.A." 77, 7415 (1980)). Virus production continued for 15 days and decreased thereafter, in parallel with the decline of lymphocyte proliferation. Peripheral blood lymphocytes cultured on the same way were consistently negative for reverse transcriptase activity, even after 6 weeks. Cytomegalovirus could be detected, upon prolonged co-cultivation with MRC5 cells, in the original biopsy tissue, but not in the cultured T lymphocytes at any time of the culture.
BRIEF DESCRIPTION OF THE DRAWING
This invention will be more fully described with reference to the FIGURE, which shows curves representative of variation of reverse transcriptase activity and [ 3 H] uridine activity as a function of successive fractions of LAV virus in a sucrose gradient.
DETAILED DESCRIPTION
The invention relates to the newly isolated virus as a source of the above-said antigen which will be defined later.
The newly isolated virus, which will hereafter be termed as LAV1, will however be described first.
The virus is transmissible to cultures of T lymphocytes obtained from healthy donors. Particularly virus transmission was attempted with the use of a culture of T lymphocytes established from an adult healthy donor of the Blood Transfusion Center at the Pasteur Institute. On day 3, half of the culture was cocultivated with lymphocytes from the biopsy after centrifugation of the mixed cell suspensions. Reverse transcriptase activity could be detected in the supernatant on day 15 of the coculture but was not detectable on days 5 and 10. The reverse transcriptase had the same characteristics as that released by the patient's cells and the amount released remained stable for 15 to 20 days. Cells of the uninfected culture of the donor lymphocytes did not release reverse transcriptase activity during this period of up to 6 weeks when the culture was discontinued.
The cell-free supernatant of the infected co-culture was used to infect 3-day-old cultures of T lymphocytes from two umbilical cords, LC1 and LC5, in the presence of Polybrene (2 μg/ml). After a lag period of 7 days, a relatively high titer of reverse transcriptase activity was detected in the supernatant of both cord lymphocyte cultures. Identical cultures, which had not been infected, remained negative. These two successive infections clearly show that the virus could be propagated on normal lymphocytes from either new-borns or adults.
In the above co-cultures one used either the cells of patient 1 as such (they declined and no longer grew) or cells which had been pre-X-rayed or mitomycin C-treated.
The LAV1 virus, or LAV1 virus suspensions, which can be obtained from infected cultures of lymphocytes have characteristics which distinguish them completely from other HTLV. These characteristics will be referred to hereafter and, when appropriate, in relation to the FIGURE. It shows curves representative of variation of reverse transcriptase activity and [ 3 H] uridine activity respectively versus successive fractions of the LAV1 virus in the sucrose gradient, after ultracentrifugation therein of the virus contents of a cell-free supernatant obtained from a culture of infected lymphocytes.
The analysis of LAV1 virus by resorting to reverse transcriptase activity can be carried out according to the procedure which was used in relation to virus from patient 1. The results of the analysis are illustrated in the FIGURE. Cord blood T lymphocytes infected with virus from patient 1 were labelled for 18 hours with [ 3 H]uridine (28 Ci/mmole, Amersham; 20 μCi/ml). Cell-free supernatant was ultracentrifuged for 1 hour at 50,000 rev/min. The pellet was resuspended in 200 μl of NTE buffer (10 mM tris, pH 7.4, 100 mM NaCl, and 1 mM EDTA) and was centrifuged over a 3-ml linear sucrose gradient (10 to 60 percent) at 55,000 rev/min for 90 minutes in an IEC type SB 498 rotor. Fractions (200 μl) were collected, and 30 μl samples of each fraction were assayed for DNA RNA dependent polymerase activity with 5 mM Mg 2+ and poly(A)-oligo-(dT) 12-18 as template primer; a 20-μl portion of each fraction was precipitated with 10 percent trichloroacetic acid and then filtered on a 0.45-μm Millipore filter. The 3 H-labelled acid precipitable material was measured in a Packard β counter.
That the new virus isolate was a retrovirus was further indicated by its density in the above sucrose gradient, which was 1.16, and by its labelling with [ 3 H]uridine (see FIGURE). A fast sedimenting RNA appears to be associated with the LAV1 virus.
Virus-infected cells from the original biopsy as well as infected lymphocytes from the first and second viral passages were used to determine the optimal requirements for reverse transcriptase activity and the template specificity of the enzyme. The results were the same in all instances. The reverse transcriptase activity displayed a strong affinity for poly(adenylate-oligodeoxy-thymidylate)[poly(A)-oligo(dT) 12-18 ], and required Mg 2+ with an optimal concentration (5 mM) and an optimal pH of 7.8. The reaction was not inhibited by actinomycin D. This character, as well as the preferential specificity for riboseadenylate-deoxythymidylate over deoxyadenylate-deoxythymidylate, distinguish the viral enzyme from DNA-dependent polymerases.
Electron microscopy of ultrathin sections of virus-producing cells shows two types of particles, presumably corresponding to the immature and mature forms of the virus: immature particles are budding at the cell surface, with a dense crescent in close contact with the plasma membrane. Occasionally, some particles remain in this state, while being freed from the cell surface.
Mature particles have a quite different morphology with a small, dense, eccentric core (mean diameter: 41 nM). Most of virions are round (mean diameter: 139 nM) or ovoid, but in some pictures, especially in the particles seen in the original culture from which the virus was isolated, a tailed morphology can also be observed. The latter form can also be observed in cytoplasmic vesicles which were released in the medium. Such particles are also formed by budding from vesicle membranes.
Morphology of mature particles is clearly distinct from HTLV, whose large core has a mean diameter of 92 nM.
Helper T-lymphocytes (Leu 3 cells) form the main target of the virus. In other words the LAV1 virus has particular tropism for these cells. Leu 3 cells are recognizable by the monoclonal antibodies commercialized by ORTHO under the trademark OKT4. In contrast enriched cultures of Leu 2 cells, which are mainly suppressor or cytotoxic cells and which are recognized by the monoclonal antibodies commercialized by ORTHO under the trademark OKT8 did not produce, when infected under the same conditions, any detectable RT activity even 6 weeks after virus infection.
In most cases of AIDS, the ratio of OKT4 + over OKT8 + cells which is normally over 1, is depressed to values as low of 0.1 or less.
The LAV1 virus is also immunologically distinct from previously known HTLV-1 isolates from cultured T lymphocytes of patients with T lymphomas and T leukemias. The antibodies used were specific for the p19 and p24 core proteins of HTLV-1. A monoclonal antibody to p19 (M. Robert-Guroff et al. "J. Exp. Med." 154, 1957 (1981)) and a polyclonal goat antibody to p24 (V. S. Kalyanaraman et al. "J. Virol.", 38, 906 (1981)) were used in an indirect fluorescence assay against infected cells from the biopsy of patient 1 and lymphocytes obtained from a healthy donor and infected with the same virus. The LAV1 virus-producing cells did not react with either type of antibody, whereas two lines of cord lymphocytes chronically infected with HTLV- 1 (M. Popovic, P. S. Sarin, M. Robert-Guroff, V. S. Kalyanaraman, D. Mann, J. Minowada, R. C. Gallo, "Science" 219, 856 (1983)) and used as controls showed strong surface fluorescence.
In order to determine which viral antigen was recognized by antibodies present in the patient's sera, several immunoprecipitation experiments were carried out. Cord lymphocytes infected with virus from patient 1 and uninfected controls were labelled with [ 35 S]-methionine for 20 hours. Cells were lysed with detergents, and a cytoplasmic S10 extract was made. Labelled virus released in the supernatant was banded in a sucrose gradient. Both materials were immunoprecipitated by antiserum to HTVL-1 p24, by serum from patient 1, and by serum samples from healthy donors. Immunocomplexes were analyzed by polyacrylamide gel electrophoresis under denaturing conditions. A p25 protein present in the virus-infected cells from patient 1 and in LC1 cells infected with this virus was specifically recognized by serum from patient 1 but not by antiserum to HTLV-1 p24 obtained under similar conditions or serum of normal donors. Conversely, the p24 present in control HTLV-infected cell extracts was recognized by antibodies to HTLV but not by serum from patient 1.
The main protein (p25) detected after purification of 35 S-methionine-labelled virus has a molecular weight of about 25,000 (or 25K). This is the only protein recognized by the serum of patient 1. By analogy with other retroviruses, this major protein was considered to be located in the viral core.
This can be confirmed in immuno-electron microscopy experiments, which show that the patient's serum can agglutinate the viral cores. Conversely, an antiserum raised in rabbit against an ether treated virus did not precipitate the p25 protein.
The viral origin of other proteins seen in polyacrylamide gel electrophoresis of purified virus is more difficult to assess. A p15 protein could be seen after silver staining, but was much weaker after 35 S-methionine perhaps due to the paucity of this amino-acid in the protein. In the higher MW range, a contamination of the virus by cellular proteins, either inside or outside the viral envelope, is likely. A 36K and a 42K protein and a 80K protein were constantly found to be associated with the purified virus and may represent the major envelope proteins.
No p19 (or having a molecular weight of about 19,000) was isolated from LAV1 extracts.
The invention concerns more particularly the extracts of said virus as soon as they can be recognized immunologically by sera of patients afflicted with LAS or AIDS. Needless to say any type of immunological assay may be brought into play. By way of example immunofluorescence or immunoenzymatic assays or radio-immunoprecipitation tests are particularly suitable.
As a matter of fact and except under exceptional circumstances sera of diseased patients do not recognize the intact LAV1 virus, or viruses having similar phenotypical or immunological properties. The envelope proteins of the virus appeared as not detectable immunologically by the patients' sera. However, as soon as the core proteins become exposed to said sera, the immunological detection becomes possible. Therefore, the invention concerns all extracts of the virus, whether it be the crudest ones--particularly mere virus lyzates--or the more purified ones, particularly extracts enriched in the p25 protein or even the purified p25 protein or in protein immunologically related therewith. Any purification procedure may be resorted to. By way of example only, one may use purification procedures such as disclosed by R. C. Montelaro et al, J. of Virology, June 1982, pp. 1029-1038.
The invention concerns more generally extracts of any virus having similar phenotype and immunologically related to that obtained from LAV1. Sources of viruses of the LAV type consist of T-lymphocytes cultures isolatable from LAS-- and AIDS--patients or from hemophiliacs.
In that respect other preferred extracts are those obtained from two retroviruses obtained by propagation on normal lymphocytes of the retroviruses isolated from:
(1) lymph node lymphocytes of a caucasian homosexual with multiple partners, having extensive Kaposi sarcoma lesions and severe lymphopenia with practically no OKT4 + lymphocytes in his blood;
(2) blood lymphocytes of a young B hemophiliac presenting neurotoxoplasmosis and OKT4 + /OKT8 + ratio of 0.1.
These two retroviruses have been named IDAV1 and IDAV2, respectively, (for Immune Deficiency Associated Virus). Results of partial characterization obtained so far indicate similarity--if not identity--of IDAV1 and IDAV2 to LAV1:
same ionic requirements and template specificities of reverse transcriptase,
same morphology in ultrathin sections,
antigenically related p25 proteins: serum of LAV1 patient immunoprecipitates p25 from IDAV1 and IDAV2; conversely, serum from IDAV2 patient immunoprecipitates LAV1 p25.
IDAV1 patient serum seemed to have a lower antibodies titer and gave a weak precipitation band for LAV1 and IDAV1 p25 proteins. The p25 protein of IDAV1 and IDAV2 was not recognized by HTLV p24 antiserum.
These similarities suggest that all these three isolates belong to the same group of viruses.
The invention further relates to a method of in vitro diagnosis of LAS or AIDS, which comprises contacting a serum or other biological medium from a patient to be diagnosed with a virus extract as above defined and detecting the immunological reaction.
Preferred methods bring into play immunoenzymatic or immunofluorescent assays, particularly according to the ELISA technique. Assays may be either direct or indirect immunoenzymatic or immunofluorescent assays.
Thus the invention also relates to labelled virus extracts whatever the type of labelling: enzymatic, fluorescent, radioactive, etc.
Such assays include for instance:
depositing determined amounts of the extract according to the invention in the wells of titration microplate;
introducing in said wells increasing dilutions of the serum to be diagnosed;
incubating the microplate;
washing the microplate extensively;
introducing in the wells of the microplate labelled antibodies directed against blood immunoglobulins, the labelling being by an enzyme selected among those which are capable of hydrolysing a substrate, whereby the latter then undergoes a modification of its absorption of radiations, at least in a determined wavelength band; and
detecting, preferably in a comparative manner with respect to a control, the amount of substrate hydrolysis as a measure of the potential risk or effective presence of the disease.
The invention also relates to kits for the above-said diagnosis which comprise:
an extract or more purified fraction of the above-said types of viruses, said extract or fraction being labelled, such as by a radioactive enzymatic or immunofluorescent label;
human anti-immunoglobulins or protein A (advantageously fixed on a water-insoluble support such as agarose beads);
a lymphocyte extract obtained from a healthy person;
buffers and, if appropriate, substrates for the visualization of the label.
Other features of the invention will further appear as the description proceeds of preferred isolation and culturing procedures of the relevant virus, of preferred extraction methods of an extract suitable as diagnostic means, of a preferred diagnosis technique and of the results that can be achieved.
1. VIRUS PROPAGATION
Cultured T-lymphocytes from either umbilical cord or blood, or also bone marrow cells from healthy, virus negative, adult donors are suitable for virus propagation.
There is however some variation from individual to individual in the capacity of lymphocytes to grow the virus. Therefore, it is preferable to select an adult healthy donor, which had no antibodies against the virus and whose lymphocytes repeatly did not release spontaneously virus, as detected by reverse transcriptase activity (RT) nor expressed viral proteins.
Lymphocytes of the donor were obtained and separated by cytophoresis and stored frozen at -180° C. in liquid nitrogen, in RPMI 1640 medium, supplemented with 50% decomplemented human serum and 10% DMSO until used.
For viral infection, lymphocytes were put in culture (RPMI 1640 medium) with phytohemagglutinin (PHA) at the concentration of 5×10 6 cells/ml for 3 days.
Then, the medium was removed and cells resuspended in viral suspension (crude supernatant of virus-producing lymphocytes, stored at -80° C.). Optimal conditions of cell/virus concentrations were 2×10 6 cells for 5 to 10,000 cpm of RT activity, the latter determined as previously described. After 24 hours, cells were centrifuged to remove the unadsorbed virus and resuspended in culture PHA-free medium and supplemented with PHA-free TCGF (interleukin 2): (0.5-1 U/ml, final concentration), POLYBREN (Sigma) 2 μg/ml and anti-interferon α sheep serum, inactivated at 56° C. for 30 minutes (0.1% of a serum which is able to neutralize 7 U of α leucocyte interferon at a 1/100,000 dilution).
Virus production was tested every 3 days by RT activity, determination on 1 ml samples.
The presence of anti-interferon serum is important in virus production; when lymphocytes were infected in the absence of anti-human-α-interferon serum, virus production, as assayed by RT activity, was very low or delayed. Since the sheep antiserum used was raised against partly purified α leukocyte interferon, made according to the Cantell technique, the role of components other than interferon cannot be excluded.
Virus production starts usually from day 9 to 15 after infection, and lasts for 10-15 days. In no cases, the emergence of a continuous permanent line was observed.
2. VIRUS PURIFICATION
For its use in ELISA, the virus was concentrated by 10% polyethyleneglycol (PEG 6000) precipitation and banded twice to equilibrium in a 20-60% sucrose gradient. The viral band at density 1.16 is then recovered and usable as such for ELISA assays.
For use in RIPA radio-immune precipitation assay, purification in isotonic gradients of Metrizamide (sold under the trademark NYCODENZ by Neygaard, Oslo) were found to be preferable. Viral density in such gradients was very low (1.10-1.11).
Metabolic labelling with 35 S-methionine of cells and virus (RIPA) followed by polyacrylamide gel electrophoresis were performed as above described, except the following modifications for RIPA. The virus purified in NYCODENZ was lysed in 4 volumes of RIPA containing 500 U/ml of aprotinin. Incubation with 5 μl of serum to be tested was made for 1 hour at 37° C. and then 18 hours at +4° C. Further incubation of the immunocomplexes with protein A SEPHAROSE beads was for 3 hours at +4° C.
3. PREPARATION OF THE VIRUS EXTRACT FOR ELISA ASSAYS
Virus purified in sucrose gradient as above described is lysed in RIPA buffer (0.5% SDS) and coated on wells of microtest plates (Nunc).
Preferred conditions for the ELISA assay are summed up hereafter.
After addition to duplicate wells of serial dilutions of each serum to be tested, the specifically fixed IgGs are revealed by goat anti-human IgG coupled with peroxidase. The enzymatic reaction is carried out on ortho-phenylene-diamine as substrate and read with an automatic spectrophotometer at 492 nM.
On the same plate each serum is tested on a control antigen (a crude cytoplasmic lysate of uninfected T-lymphocytes from the same donor) is used in order to eliminate unspecific binding, which can be high with some sera.
Sera are considered as positive (antibodies against the virus) when the difference between O.D. against the viral antigen and O.D. against control cellular antigen was at least 0.30.
Hereafter there is disclosed a specific test for assaying the above-mentioned disease or exposure to disease risks.
Method
This ELISA test is for detecting and titration of seric anti-retrovirus type LAV antibodies.
It comprises carrying out a competition test between a viral antigen (cultivated on T lymphocytes) and a control antigen constituted by a lysate of the same though non-infected lymphocytes.
The binding of the antibodies on the two antigens is revealed by the use of a human antiglobulin labelled with an enzyme which itself is revealed by the addition of a corresponding substrate.
Preparation of the Viral Antigen
The cellular cultures which are used are T lymphocytes of human origin which come from:
• umbilical cord blood,
• bone marrow,
• blood of a healthy donor.
After infection of the cells by the virus, the supernatant of the infected cell culture is used. It is concentrated by precipitating with 10% PEG, then purified (two or three times) on a (20-60%) sucrose gradient by ultracentrifugation to equilibrium.
The viral fractions are gathered and concentrated by centrifugation at 50,000 rotations per minute for 60 minutes.
The sedimented virus is taken in a minimum volume of buffer NTE at pH 7.4 (Tris 0.01M, NaCl 0.1M, EDTA 0.001M).
The proteic concentration is determined by the Lowry method.
The virus is then lysed by a (RIPA+SDS) buffer (0.5% final) for 15 minutes at 37° C.
Preparation of the Control Antigen
The non-infected lymphocytes are cultured according to the preceeding conditions for from 5 to 15 days. They are centrifuged at low speed and lysed in the RIPA buffer in the presence of 5% of the product commercialized under the name of ZYMOFREN (Specia) (500 μ/ml). After a stay of 15 minutes at 4° C. with frequent stirrings with vortex, the lysate is centrifuged at 10,000 rotations per minute. The supernatant constitutes the control antigen. Its concentration in protein is measured by the Lowry method.
Reagents
1--Plates=NUNC--special controlled ELISA
2--Buffer PBS: pH 7.5
3--TWEEN 20
4--Carbonate buffer: pH=9.6 (CO 3 Na 2 =0.2M; CO 3 HNa =0.2M)
5--Non fetal calf serum: which is stored in frozen state (BIOPRO),
6--Bovine serum albumin (BSA) SIGMA (fraction V)
7--Human anti IgG (H+L) labelled with peroxidase PASTEUR, in tubes of 1 ml preserved at 4° C.
8--Washing buffer=PBS buffer, pH 7.5+0.05% TWEEN 20
Dilution of the conjugate is carried out at the dilution indicated in PBS buffer+TWEEN 20 (0.05%)+bovine albumin 0.5 g per 100 ml.
9--Dilution buffer of sera=PBS buffer+0.05% TWEEN 20+0.5 g BSA bovine serum albumin per 100 ml
10--Substrate=OPD
• Citrate buffer pH=5.6 trisodic citrate (C 6 H 5 Na 4 O 3 , 2H 2 O), 0.05M; citric acid (C 6 H 8 O 7 , 1H 2 O), 0.05M.
• Hydrogen peroxide=at 30% (110 volumes)--used at 0.03% when using citrate buffer.
• Orthophenylene diamine=SIGMA 74 mg per 25 ml of buffer--which is diluted in buffer extemporaneously.
Preparation of the Plates
The plates which are used have 96 U-shaped wells (NUNC=ELISA). They include 12 rows of 8 wells each, numbered from 1 to 12.
The distribution of antigens is as follows:
100 μl of the viral antigen, diluted in carbonate buffer at pH 9.6, are deposited in each of the wells of rows (marked ⊕)
1--2--5--6--9--10
100 μl of the control antigen, diluted in carbonate buffer at pH 9.6, are deposited in each of the wells of rows (marked ⊖)
3--4--7--8--11--12.
The dilution of the viral antigen is titrated at each viral production. Several dilutions of viral antigen are tested and compared to positive and negative known controls (at several dilutions) and to human anti-IgG labelled with peroxidase, the latter being also tested at several dilutions.
As a rule, the proteic concentration of the preparation is of 5 to 2.5 μg/ml.
The same proteic concentration is used for the control antigen.
The plates are closed with a plastic lid and are incubated overnight at 4° C.
Then they are put once in distilled water and centrifuged. The wells are then filled with 300 μl of non fetal calf serum at 20% in PBS buffer.
The incubation lasts 2 hours at 37° C. (covered plates).
The plates are washed 3 times in PBS buffer with TWEEN 20, 0.05% (PBS-tw buffer):
• first washing 300 μl
• second and third washing 200 μl/well.
The plates are carefully dried and sealed with an adhesive plastic film. They can be stored at -80° C.
ELISA Reaction: Antibody Titer Assay
After defreezing, the plates are washed 3 times in PBS-TWEEN. They are carefully dried.
The positive and negative control sera as well as the tested sera are diluted first in the tube, with PBS-TWEEN containing 0.5% bovine albumin.
The chosen dilution is 1/40.
100 μl of each sera are deposited in duplicate on the viral antigen and in duplicate on the control antigen.
The same is carried out for the positive and negative diluted sera.
100 μl of PBS+TWEEN+bovine serum albumin are introduced in two wells ⊕ and in two wells ⊖ to form the conjugated controls.
The plates equipped with their lids are incubated for 1.5 h at 37° C.
They are washed 4 times in PBS+TWEEN 0.05%.
100 μl of human anti-IgG (labelled with peroxidase) at the chosen dilution are deposited in each well and incubated at 37° C.
The plates are again washed 5 times with the (PBS+TWEEN) buffer. They are carefully dried.
Revealing the enzymatic reaction is carried out by means of a orthophenylene-diamine substrate (0.05% in citrate buffer pH 5.6 containing 0.03% of H 2 O 2 ).
100 μl of substrate are distributed in each well.
The plates are left in a dark room 20 minutes at the laboratory temperature.
Reading is carried out on a spectrophotometer (for microplates) at 492 nm.
Sera deemed as containing antibodies against the virus are those which give a ODD (optical density difference=optical density of viral antigen less optical density of control antigen) equal to or higher than 0.30.
This technique enables a qualitative titration as well as a quantitative one. For this purpose, it is possible either to use several dilutions of the serum to be assayed, or to compare a dilution of the serum with a range of controls tested under the same conditions.
The table hereafter provides first results of serological investigations for LAV antibodies carried out by using the above exemplified ELISA assay.
__________________________________________________________________________FIRST RESULTS OF SEROLOGICAL INVESTIGATIONS FOR LAVANTIBODIES IN FRANCE ELISA-HTLV1** ELISA-LAV (Biotech) Total examined positive % positive positive % positive__________________________________________________________________________Lymphadenopathy patients* 35 22 (63) 5*** (14)Healthy homosexuals 40 7 (17) 1 (3)Control population 54 1 (1,9) 0 (<2,6)__________________________________________________________________________ *28 homosexuals 3 Haitians (1 woman) 4 toxicomans (2 women) **The number of positive sera is probably overestimated in this test, since no control of unspecific binding could be done. ***Out of the 5 LAS HTLV1 positive, 3 were born in Haiti, 1 had stayed in for a long time in Haiti and 1 had made several travels to USA. All of them had also antibodies against LAV.
The table shows clearly high prevalence of LAV antibodies in the homosexual patients with LAS, the very low incidence in the normal population and also a moderate spread of virus infection in still healthy homosexuals. In the latter group, all the positive individuals had a high number of partners (>50 per year). The incidence of HTLV antibodies was very low in all three groups (determined by using a commercial ELISA test (Biotech)). The groups of AIDS patients gave less interpretable results. Approximately 20% had LAV antibodies, but some of the sera were taken at a very late stage of the disease, with a possible negativation of the humoral response.
It should further be mentioned that lymphocytes of all LAS patients do not produce detectable amounts of LAV-type virus. More particularly cells of lymph nodes from 6 more LAS patients were put in culture and tested for virus production as described for patient 1. No virus release could be detected by RT activity. However, a p25 protein recognized by the serum of the first patient could be detected in cytoplasmic extracts of the T-cells labelled with 35 S-methionine in 3 other cases. This suggests partial expression of a similar virus in such cases. Moreover, all (6/6) of these patients had antibodies against LAV p25 proteins, indicating that they all had been infected with a similar or identical virus.
Interestingly, in lymphocytes of one of the patients (patient 2), there was a weak but definite immunoprecipitation of a band of similar size (p24-p25) with goat antiserum raised against HTLV-1. Similarly, the patient's serum had antibodies against both HTLV and LAV, suggesting a double infection by both viruses. Such cases seem rather infrequent.
The invention finally also relates to the biological reagents that can be formed by the LAV extracts containing the p25 protein or by the purified p25 protein, particularly for the production of antibodies directed against p25 in animals or of monoclonal antibodies. These antibodies are liable of forming useful tools in the further study of antigenic determinants of LAV viruses or LAV-related viruses.
It is acknowledged that the OKT designations which have been used with respect to the designation of some sub-sets of lymphocytes or related monoclonal antibodies by way of ease of language, should in no way be opposed to the validity of any corresponding trademark, whether registered or not by its owner.
It should further be mentioned that the viral extracts, particularly viral lysates or enriched fractions can also be defined by reference to their immunological relationship or similitude with the extracts or enriched fractions containing a p25 protein as obtainable from the strain LAV1, IDAV1 or IDAV2. Thus any protein fraction which is capable of giving similar patterns of immunological reaction as do the protein extracts of LAV1, IDAV1 or IDAV2 with the same sera, must be considered as equivalent thereof and, accordingly, be deemed as encompassed by the scope of the claims which follow. A similar conclusion extends of course to the diagnostic means (process and kits) which may make use of such equivalent protein extracts.
The LAV1 virus has been deposited at the "Collection Nationale des Cultures de Micro-organismes" (C.N.C.M.) under n° I-232 on July 15, 1983 and IDAV1 and IDAV 2 viruses have been deposited at the C.N.C.M. on September 15, 1983 under n° I-240 and I-241, respectively. The invention encompasses as well the extracts of mutants or variants of the above deposited strains as long as they possess substantially the same immunological properties.
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Retroviruses associated with Acquired Immune Deficiency Syndrome (AIDS), including Lymphadenopathy Associated Virus (LAV), are isolated from the sera of patients afflicted with Lymphadenopathy Syndrome (LAS) or AIDS. LAV is a Human Immunodeficiency Virus (HIV). Viral extract, structural proteins and other fractions of the retrovirus immunologically recognize the sera of such patients. Immunological reaction is used to detect antibodies that specifically bind to antigenic sites of the retrovirus in samples of body fluids from patients with AIDS or risk of AIDS. A kit for in vitro assay of LAS or AIDS is provided.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a file management program, and more particularly to a file management program which manages image files.
2. Description of the Related Art
In general, image data taken with a digital camera is incorporated into a personal computer and managed with the personal computer. However, a problem has existed in that the management of image data becomes more difficult as the amount thereof that is incorporated into the personal computer increases, and thus users are no longer able to readily find the image they wish to view.
To solve this problem, Japanese Patent Application Publication No. 2003-199028 discloses an electronic album device that, when managing image data, stores the image data after automatically classifying the data by predetermined categories (such as time stamp, date, image taking conditions, resolution, form, etc.) that are based on fundamental attributes of the image data. However, since the electronic album device merely classifies image data by categories such as time stamp, the problem arises that there may be little difference among images in the classification categories, or the images in the same classification may be irrelevant to each other. For example, the relation between classification by time and classification by date is that the classification by time subdivides the classification by date into smaller categories, constituting a drawback in that the classification becomes merely an inclusion relation of a set. Further, for classification by file volume or resolution, images taken at completely different dates or events are classified into the same category, constituting a drawback in that the relationship among images in the respective categories is reduced.
SUMMARY OF THE INVENTION
The present invention has been made in view of the foregoing circumstances, and it is an object of the invention to provide a file management program that enables simple file management.
In order to attain the aforementioned object, a first aspect of the present invention is directed to a computer readable medium having embodied thereon a file management program for processing by a computer, the file management program comprising: a first code segment for, when an icon of a first folder displayed on a display apparatus is dragged and dropped onto another icon of a second folder displayed on the display apparatus, creating a third folder at the same level as the second folder; and a second code segment for copying a file stored in the first folder and a file stored in the second folder into the third folder.
According to the present invention, when an icon of a folder displayed on a display apparatus is dragged and dropped onto an icon of another folder displayed thereon, a new folder is created at the same level as the latter folder. Then, files stored in the former folder and files stored in the latter folder are copied to the new folder.
In order to attain the aforementioned object, a second aspect of the present invention is directed to a computer readable medium having embodied thereon a file management program for processing by a computer, the file management program comprising: a first code segment for, when an icon of a first folder displayed on a display apparatus is dragged and dropped onto another icon of a second folder displayed on the display apparatus, creating a third folder at the same level as the second folder; and a second code segment for copying a shortcut file to a file stored in the first folder and a shortcut file to a file stored in the second folder into the third folder.
According to the present invention, when an icon of a folder displayed on a display apparatus is dragged and dropped onto an icon of another folder displayed thereon, a new folder is created at the same level as the latter folder. Then, shortcut files to files stored in the former folder and shortcut files to files stored in the latter folder are copied to the new folder.
In order to attain the aforementioned object, a third aspect of the present invention is directed to a computer readable medium having embodied thereon a file management program for processing by a computer, the file management program comprising: a first code segment for, when an icon of a first folder displayed on a display apparatus is dragged and dropped onto another icon of a second folder displayed on the display apparatus, creating a third folder at the same level as the second folder; and a second code segment for copying a file that is commonly stored in the first folder and the second folder into the third folder.
According to the present invention, when an icon of a folder displayed on a display apparatus is dragged and dropped onto an icon of another folder displayed thereon, a new folder is created at the same level as the latter folder. Then, files commonly stored in the former folder and in the latter folder are copied to the new folder.
In order to attain the aforementioned object, a fourth aspect of the present invention is directed to a computer readable medium having embodied thereon a file management program for processing by a computer, the file management program comprising: a first code segment for, when an icon of a first folder displayed on a display apparatus is dragged and dropped onto another icon of a second folder displayed on the display apparatus, creating a third folder at the same level as the second folder; and a second code segment for copying a shortcut file to a file that is commonly stored in the first folder and the second folder into the third folder.
According to the present invention, when an icon of a folder displayed on a display apparatus is dragged and dropped onto an icon of another folder displayed thereon, a new folder is created at the same level as the latter folder. Then, shortcut files to files commonly stored in the former folder and in the latter folder are copied to the new folder.
A fifth aspect of the present invention is directed to the medium of the second or fourth aspect, wherein the file management program further comprises a fourth code segment for, when the shortcut file is deleted, deleting the file that is linked to by the shortcut file.
According to the present invention, when shortcut files are deleted, files that are linked to the shortcut files are all deleted.
A sixth aspect of the present invention is directed to the medium of any of the first to the fifth aspects, wherein the file management program further comprises a third code segment for giving to the third folder a folder name made by combining a folder name of the first folder an a folder name of the second folder.
According to the present invention, a folder name in which the folder name of the former folder and the folder name of the latter folder are combined is allocated to the new folder. For example, if the folder name of the former is “A” and the folder name of the latter folder is “B”, the folder name “BA” is allocated to the new folder.
The medium may be a propagated signal, and the propagated signal may be a carrier wave.
According to the present invention, files can be arranged to good efficiency to enable easy management of files.
BRIEF DESCRIPTION OF THE DRAWINGS
The nature of the present invention, as well as other objects and advantages thereof, will be explained in the following with reference to the accompanying drawings, in which like reference characters designate the same or similar parts throughout the figures and wherein:
FIG. 1 is a block diagram showing an example of the hardware configuration of a personal computer;
FIG. 2 is a view showing the main window display of an image viewing program;
FIG. 3 is a view showing a display example of a window display when conducting file operations;
FIG. 4 is a flowchart showing processing procedures when conducting a drag and drop operation for a folder;
FIG. 5 is an explanatory drawing that illustrates a drag and drop operation for a folder;
FIG. 6 is a view showing a display example of a window display after dragging and dropping a folder;
FIG. 7 is a conceptual diagram of file processing caused by dragging and dropping a folder;
FIG. 8 is a conceptual diagram of file processing caused by dragging and dropping a folder;
FIG. 9 is a conceptual diagram of file processing caused by dragging and dropping a folder;
FIG. 10 is a conceptual diagram of file processing caused by dragging and dropping a folder;
FIG. 11 is a flowchart showing processing procedures when conducting a drag and drop operation for a folder;
FIG. 12 is a view showing a display example of a window display when dragging and dropping a folder; and
FIG. 13 is a view showing a display example of a window display when dragging and dropping a folder.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereunder, preferred embodiments for implementing the file management program of the present invention are described referring to the attached drawings.
FIG. 1 is a block diagram showing an example of the hardware configuration of a computer (personal computer) that implements the file management program according to an embodiment of the present invention.
A personal computer (PC) 10 is a commonly used type of computer, and comprises a central processing unit (CPU) 12 for executing an image classification program according to an embodiment of the present invention; a random access memory (RAM) 14 for temporarily storing results of operations in the CPU 12 , image data and the like; a hard disk drive (HDD) 16 for storing an operating system (OS), the image classification program, various application programs, image files and the like; a CD-ROM drive 18 for reading data that is stored on a CD-ROM; a display apparatus 20 for displaying results of operations in the CPU 12 , image data and the like; an input device 22 such as a keyboard and mouse for inputting commands and numerical values and the like; a memory card slot 26 for connecting a memory card 24 on which an image file is stored; an input/output terminal (for example, a USB terminal) 30 for connecting with a digital camera 28 or the like through a communication cable; and a modem 32 for communicating with a server through a network. These components are connected with each other by a bus 34 .
The file management program according to the embodiment of the present invention is incorporated into an image viewing program (viewer) that views image files, and is provided as one function of the image viewing program. The program may be contained in any computer readable medium including a volatile memory in a computer, a nonvolatile memory for a computer such as a floppy diskette or CD-ROM, as well as the propagated signals such as the stream of bits that represent Interne transmissions of packets or the carrier waves that are transmitted to satellites.
The image viewing program is installed onto the HDD 16 of the PC 10 , and is loaded from the HDD 16 into the RAM 14 to be subject to execution control by the CPU 12 . The program may also be executed after a program stored on a CD-ROM or the like is read by the CD-ROM drive 18 or the like, or may be executed after being downloaded through a network.
When the image viewing program is initiated, as shown in FIG. 2 , the main window of the image viewing program is displayed on the display apparatus 20 .
The main window is composed of a folder tree display area, which is displayed on the left-hand side of the screen, and a thumbnail display area, which displayed on the right-hand side of the screen.
The folders in the personal computer 10 are displayed hierarchically in the folder tree display area. When a folder displayed in the folder tree display area is selected, as shown in FIG. 3 , the image files stored in the selected folder are displayed in thumbnail form in the thumbnail display area.
When there are no image files in the selected folder, nothing is displayed in the thumbnail display area, and when there is another folder in the selected folder, the folder icon thereof is displayed. FIG. 2 shows an example of the display when folders (in this case “2003”, “December”, “Flash Lighting” and “Christmas”) are stored in the selected folder (in this case “Folder D”).
When an image file is selected (by double clicking thereon) from among the image files displayed in thumbnail form in the thumbnail display area as shown in FIG. 3 , an enlarged view of the selected image file is displayed in a separate window.
Further, when a slideshow function is executed, the image files stored in the selected folder are sequentially displayed while being advanced frame by frame at fixed time intervals to carry out a slide show.
In this image viewing program, file operations can be conducted to perform processing such as cutting, copying, deleting, renaming, and short cut creation for files displayed in the thumbnail display area. For example, as shown in FIG. 3 , when the mouse pointer is moved onto a file displayed in the thumbnail display area and the right button on the mouse is clicked, the pull-down menu for file operations is displayed, and when the mouse pointer is moved onto a desired processing item in the pull-down menu and the left button on the mouse is clicked, the selected processing is executed. Further, when a file displayed in the thumbnail display area is dragged and dropped (operation in which the mouse pointer is pointed at a target object and the mouse is then moved while keeping the left button on the mouse pressed down, and the left button on the mouse is then released at the target position) onto a folder displayed in the thumbnail display area or the folder tree display area, the file is moved to the folder onto which the file has been dragged and dropped.
The same operations can also be conducted for folders, and processing such as cutting, copying, deleting, renaming and short cut creation can be conducted for folders displayed in the thumbnail display area or folder tree display area.
However, the following processing is conducted with respect to a drag and drop operation for a folder. That is, when a folder (hereinafter referred to as the former folder) displayed in the thumbnail display area or folder tree display area is dragged and dropped onto another folder (hereinafter referred to as the latter folder) displayed in the thumbnail display area or folder tree display area, a new folder is created at the same level as the latter folder onto which the former folder has been dragged and dropped, and shortcut files to files stored in both of the former and latter folders are stored in the newly created folder.
FIG. 4 is a flowchart showing processing procedures when a folder is dragged and dropped onto another folder.
As shown in FIG. 4 , judgment is made as to whether or not a folder has been dragged and dropped onto another folder based on operation information of the mouse (step S 10 ). When it is judged as a result that a folder (the former folder) has been dragged and dropped onto another folder (the latter folder), a folder (the new folder) is newly created at the same level as the latter folder onto which the former folder has been dragged and dropped (step S 11 ). Then, shortcut files to files stored in both of the former and latter folders are created, and the created shortcut files are stored in the newly created folder (step S 112 ).
For example, as shown in FIG. 5 , when a folder named “Christmas” that is stored in a folder named “Folder D” is dragged and dropped onto a folder named “2003” that is also stored in the folder “Folder D”, as shown in FIG. 6 , a folder is newly created at the same level as the folder “2003.”
In this case, the newly created folder is given a name made by combining the folder names of the former and latter folders (“folder name of the latter folder onto which the former folder has been dragged and dropped”+“folder name of the former folder that has been dragged and dropped”). For example, in the above example, since the folder named “Christmas” has been dragged and dropped onto the folder named “2003,” as shown in FIG. 6 , a new folder name “2003 Christmas” is allocated to the newly created folder.
Then, shortcut files to files stored in both of the folders are stored in the thus newly created folder (“2003 Christmas”). For example, as shown in FIG. 7 , in a case where three image files named “DSCF0001”, “DSCF0002” and “DSCF0003” are stored in the folder named “2003” and three image files named “DSCF0100”, “DSCF101” and “DSCF0102” are stored in the folder named “Christmas”, shortcut files to the three image files named “DSCF0001”, “DSCF0002” and “DSCF0003” that are stored in the folder “2003” and shortcut files to the three image files named “DSCF0100”, “DSCF0101” and “DSCF0102” that are stored in the folder “Christmas” are stored in the newly created folder “2003 Christmas.”
Thus, in the image viewing program of the present embodiment, when a folder displayed in the thumbnail display area or folder tree display area is dragged and dropped onto another folder displayed in the thumbnail display area or folder tree display area, a new folder is created at the same level as the latter folder onto which the former folder has been dragged and dropped, and shortcut files to files stored in both the former and latter folders are stored in the newly created folder. Thereby, classification of image files can be carried out in accordance with the preferences of the user, and management of image files is simplified.
Further, since the folder name that is allocated to the newly created folder combines the folder names of both the folder onto which the folder has been dragged and dropped and the folder that has been dragged and dropped, the history of folder operations can be readily known, facilitating management of the image files. More specifically, the user can infer from a folder name which folder was dragged and dropped onto which other folder, enabling the user to easily grasp the folder arrangement.
Shortcut files are stored in the newly created folder in the present embodiment; however, other processing may be adopted whereby files stored in both of the folders are copied to the newly created folder.
Further, other processing may be adopted whereby the user can select between an operation to copy files and an operation to store shortcut files. Thus, usability is improved.
In this connection, by storing shortcut files as in the above-described embodiment, the operation can be conducted by employing only a small file volume, thereby enabling effective utilization of the hard disk drive.
While an example has been described in the above embodiment for a case in which one folder is dragged and dropped onto a different folder, it is also possible to select a plurality of folders and drag and drop the plurality of folders onto a different folder. In this case, shortcut files are created for the files stored in the plurality of folders, and the shortcut files are stored in the newly created folder. A folder name that combines the folder names of the plurality of folders is allocated to the newly created folder.
For example, as shown in FIG. 8 , when the folder named “2003” and the folder named “Christmas” are selected and then dragged and dropped onto a folder named “Flash Lighting”, a folder named “Flash Lighting 2003 Christmas” is newly created, and shortcut files to all files stored in both the folders are stored in the new folder.
It is also possible to drag and drop a folder that has already been created by a dragging and dropping operation. In this case, copies of shortcut files are stored in the newly created folder.
For example, as shown in FIG. 9 , when a folder named “2003 Christmas” that was created by dragging and dropping a folder named “Christmas” onto a folder named “2003” is dragged and dropped onto a folder named “Flash Lighting”, a folder named “Flash Lighting 2003 Christmas” is newly created. Then, copies of the shortcut files that are stored in the folder “2003 Christmas” are stored in the newly created folder and, further, shortcut files to files stored in the folder “Flash Lighting” are also stored in the newly created folder.
According to this embodiment, when one folder is dragged and dropped onto another folder, a new folder is created at the same level as the latter folder onto which the former folder has been dragged and dropped and shortcut files to all the files stored in both of the former and latter folders are stored in the newly created folder; however, other processing may be adopted whereby shortcut files to only files that are commonly stored in both of the former and latter folders are stored in the newly created folder.
More specifically, for example as shown in FIG. 10 , in a case where three image files named “DSCF0001”, “DSCF0002” and “DSCF0003” are stored in a folder named “2003” and three image files named “DSCF0003”, “DSCF0100” and “DSCF0101” are stored in a folder named “Christmas”, when the folder “Christmas” is dragged and dropped onto the folder “2003”, a new folder named “2003 Christmas” is created at the same level as the folder “2003” onto which the folder “Christmas” has been dragged and dropped, and a shortcut file to only the file (in this case, the image file named “DSCF0003”) that is commonly stored in both of the folders is created in the newly created folder.
FIG. 11 is a flowchart showing processing procedures when shortcut files to only files that are commonly stored in two folders are stored in a new folder.
First, the CPU 12 judges whether or not a folder has been dragged and dropped onto another folder based on operation information of the mouse (step S 20 ). When it is judged as a result that a folder has been dragged and dropped onto another folder, the CPU 12 determines whether or not at least one image file is commonly stored in both of the former and latter folders (step S 21 ). When it is determined as a result that an image file is commonly stored in both of the former and latter folders, a folder is newly created at the same level as the latter folder onto which the former folder has been dragged and dropped (step S 22 ). Then, a shortcut file is created for the file that is commonly stored in both of the former and latter folders, and the created shortcut file is stored in the newly created folder (step S 23 ).
Thus, processing may be adopted whereby shortcut files to image files commonly stored in both of the folders involved in the drag and drop operation are stored in the newly created folder. When files are processed in this manner, management of image files can be simplified similarly to the embodiment previously described.
Shortcut files to image files commonly stored in both of the folders involved in the drag and drop operation are stored in the newly created folder in the above-described embodiment; however, other processing may be adopted whereby copies of image files commonly stored in both of the folders involved in the drag and drop operation are stored in the newly created folder.
When dragging and dropping, it is preferable that the user can select between processing which stores in the newly created folder the shortcut files to only the image files that are commonly stored in both of the folders, as in the present embodiment, and processing which stores in the newly created folder the shortcut files to all the image files stored in both of the folders, as in the foregoing embodiment. This processing selection can be conducted, for example, in the following manner.
That is, as shown in FIG. 12 , when a folder is dragged and dropped onto another folder, a dialog box for selecting processing is displayed as a pop-up box, and the processing to be conducted is selected from the dialog box. Selection can be made by checking the check box of the processing to be executed (pointing the mouse pointer at the check box of the processing to be executed and then clicking), and when the mouse pointer is pointed at the “OK” button and the mouse is clicked, the selected processing is executed.
Further, for example, as shown in FIG. 13 , when a folder is dragged and dropped onto another folder while keeping the right button on the mouse pressed down, a pull-down menu for selecting processing is displayed and the processing to be executed is selected from the items displayed in the pull-down menu. Selection is made by aligning the mouse pointer with the processing item to be executed, and when the mouse is clicked the selected processing is executed.
By enabling selection of the processing to be executed in this manner, usability is improved and management of image files is simplified further.
When dragging and dropping, other processing may be adopted whereby the user can select between processing that stores in a newly created folder copies of only image files that are commonly stored in both folders, and processing that stores in a newly created folder copies of all image files stored in both folders.
In the above-described embodiments, shortcut files are stored in a folder newly created by dragging and dropping, and when these shortcut files are deleted, all the files that are linked to by the shortcut files are also deleted. Thus, it is no longer necessary to process files individually, making the management of files easier.
In this connection, other processing may be adopted whereby the user can select between processing which deletes only the shortcut files and processing which also deletes the files that are linked to by the shortcut files, thus improving usability.
Although examples have been described for the embodiments in which the file management program according to the present invention is incorporated into an image viewing program that handles image files, the file management program of the present invention can also be used when handling files other than image files (such as text files).
It should be understood, however, that there is no intention to limit the invention to the specific forms disclosed, but on the contrary, the invention is to cover all modifications, alternate constructions and equivalents falling within the spirit and scope of the invention as expressed in the appended claims.
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The computer readable medium has embodied thereon a file management program for processing by a computer, the file management program comprising: a first code segment for, when an icon of a first folder displayed on a display apparatus is dragged and dropped onto another icon of a second folder displayed on the display apparatus, creating a third folder at the same level as the second folder; and a second code segment for copying a file stored in the first folder and a file stored in the second folder into the third folder.
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BACKGROUND OF THE INVENTION
The present invention relates to a speed control circuit for the motor of an electric power tool, particularly a hand-held electric drill with an adjustable drilling speed. Various types of drilling machines are already known in which the fixed drilling speed is maintained independent of the load by means of an electronic regulating circuit. In a second switch position such circuits switch the motor over to the full operating speed. With such switches, a sudden variation or change in rotational speed is possible, perhaps resulting in a sudden reversal of the rotation force, occurring while the user is completely unaware and unprepared for any change, and consequently the machine could even be torn from his hands by the counter-rotational moment. Such a sudden reaction of the drilling machine to a change in direction could result in a high risk of damage or breakage to the mechanism, or even of injury to the user.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a drilling machine which overcomes the disadvantages of the prior art.
Another object of the invention is to provide an electric drill in which the drilling speed is variable by the user in a simple manner without hampering the operation.
Another object of the invention is to provide a control circuit for an electric drill which permits the drilling speed to be adjusted stepwise from zero up to a preselected operating speed by means of a control potentiometer, with the drilling speed being controlled by a pressure-sensitive switch. Thus whenever the motor is turned on, for every selected operating speed, full operating speed could be reached by a gentle increase in speed of the motor, so that the sudden, full impact of the counter-rotational moment would be avoided when the drill is first switched on.
The invention provides that the drilling speed may be adjustable from zero up to a predetermined operating speed by means of a pressure switch. The predetermined operating speed is set on a control potentiometer. Thus with the switching on of the motor, a gradual increase of speed is possible, without encountering the large counter-rotational reaction force characteristic of prior-art devices when the motor is started at its full operational speed. Preferably the drilling speed can be continuously adjustable by means of the pressure switch being connected to a slidable wiper of a potentiometer.
According to the present invention, the voltage to the motor of the drilling machine is controlled by an electrical circuit including a thyristor and two field coils. The thyristor is connected in series with the rotor of the motor in the primary circuit, which is in turn connected to the wiper of the control potentiometer in a voltage divider circuit. It is expedient if the wiper of the control potentiometer is connected to a second potentiometer whose wiper in turn is connected to the control electrode of the thyristor.
The construction of the circuit is particularly simple if the voltage divider circuit is a series connection of a diode with a first fixed resistor, the control potentiometer, and a second fixed resistor. Parallel to the first fixed resistor and the control potentiometer is a condenser. Furthermore, parallel to the first fixed resistor and the control potentiometer through the slide of the control potentiometer is the slide or wiper of the second potentiometer is then connected to the thyristor as noted above. An accurate speed control of the motor is achieved if this slide of the potentiometer is connected through two diodes with the control electrode of the thyristor. Between both diodes a condenser is connected with the output, or the cathode, of the thyristor.
For full high-speed operation, the control potentiometer is shifted to its end position, thereby short-circuiting the thyristor. Thus the full voltage, without any phase change, will flow through the motor. Through the arrangement of a short-circuiting contact on the control potentiometer the motor will reach the highest operating speed without preselection on the control potentiometer, so that operational error is largely prevented. At the same time the predetermined position of the control potentiometer is easily usable, so that the usually provided on-off switch for controlling operation of the motor may be eliminated.
Using an impulse or spring-free pressure switch, one may preferably provide a switch having three contacts which may be connected by means of a bridge. The bridge operates by means of the pressure switch so that in the first or off position all three contacts are seperated from each other, in the second position the first and the middle contact are connected with one another, and in the last position all three contacts are connected with one another. The first contact is electrically connected to a field coil, and, in turn, to one of the poles of the voltage source; the middle contact is connected with a voltage divider circuit, and the end contact is connected to a switch for short-circuiting the thyristor. In a simple manner it is possible to connect the pressure switch with the wiper of the potentiometer in a mechanical coupling, so that the moving of the wiper to the end position will correspond to the closing of the short-circuiting switch.
BRIEF DESCRIPTION OF THE DRAWINGS
The single FIGURE shows a highly simplified schematic diagram of the control circuit for an electric drill according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The single FIGURE indicates poles 1 and 2 of a voltage source (not shown) connected to field coils 3 and 4 respectively, and thereby to a pressure switch 5 which connects to a primary circuit 6 and a potentiometer circuit 7. The pressure switch 5 comprises a first contact 8, a middle contact 9, and an end contact 10, which are connected together by means of a conducting bridge 11. In the first position of the pressure switch 5 the contacts 8, 9 and 10 are disconnected from one another; in the second position the first contact 8 and the middle contact 9 are connected to one another; and in the third position all three contacts 8, 9 and 10 are connected with one another. The pressure switch 5 is operated by means of pressure switch in the conventional pistol grip of the hand-held electric drill. (not shown).
In the primary circuit 6, the middle contact 9 of the pressure switch is connected through a thyristor 12 to a brush 13, which in turn contacts the rotor 14, and thereby another brush 15 of the operational motor of the drill. The brush 15 is in turn connected to the field coil 4. At the same time the third contact 10 of the pressure switch 5 is connected to a normally open switch 16, which is in turn connected to the output 17 of the thyristor 12, so that in the third position of the pressure switch 5 the contact 8 is connected with the control 10, the switch 16 is closed, the thyrister 12 is short circuited, and the circuit is completed from pole 1 through the field coil 3, the brush 13, the rotor 14, the brush 15 and field coil 4 directly to the other pole 2, so that the motor is driven at maximum power.
The regulation of the rotational speed is controlled by a potentiometer 7 which is connected with the control electrode 18 of the thyristor 12. The phase angle control of the thyristor 12 results from the equalization of the back electromotive force of the rotor 14. The potentiometer circuit 7 comprises a diode 19 in series connection with a first fixed resistor 20, a variable resistor 21, and a second fixed resistor 22, connected between the field coil 4 and the middle contact 9. Between the first fixed resistor 20 and the potentiometer 21 a condenser 23 is connected in parallel. Between the wiper or tap 24 of the potentiometer 21 and the diode 19 another potentiometer 25 is connected, whose tap 26 is connected via two diodes 27 and 28 with the control electrode 18 of the thyristor 12. Between the two diodes 27 and 28 a condenser 29 is connected to the output 17 of the thyristor 12.
The control potentiometer 21 is mechanically coupled with the switch 16, so that in one end position of the wiper 24 the switch 16 is open, and in the other end position of the wiper 24 of the potentiometer 21 the switch 16 is closed, and the thyristor 12 is short circuited. Likewise the wiper 26 of the potentiometer 25 is mechanically connected with the bridge 11 of the pressure switch 5, so that the third position of the pressure switch 5 corresponds to the end position of the wiper 26 of the potentiometer 25.
By sliding the bridge 11 of the pressure switch 5 the contacts 8 and 9 will be connected with one another, so that the current can flow both through the potentiometer circuit 7 and the primary circuit 6. The firing voltage for the control electrode 18 of the thyristor 12 will therefore in a known manner equalize the reference voltage from the potentiometer circuit 7 with the back electromotive force from the rotor 14. With increasing pressure on the pressure switch 5 the potentiometer 25 will increase the reference voltage according to the position of the bridge 11, adjustable up to the end position of the full voltage range of the potentiometer 25, and therefore finally attaining the full voltage at the end position. From this it follows that an increase in rotational speed of the rotor 14 is gradual and is not abrupt as the pressure switch 5 gradually increases the voltage through the potentiometer 25. The wiper 26 of the potentiometer 25 is ajustable for every point of the control potentiometer 21 which may be selected. The control potentiometer 21 is especially sensitive and may be adjusted to low operating speeds, and may be controlled by the position or pressure on the pressure switch 5, so that the rotational speed is adjustable between zero and the desired operating speed.
With switch 16 closed, the shaft rotation will result according to the position of the pressure trigger of the pressure switch 5, with a slow increase of rotational speed. In the end position of switch 5, with all three contacts 8 through 10 connected with one another, the thyristor 12 is short-circuited and a direct connection to the motor is made, so that no sudden changes in rotational speed and therefore sudden and unavoidable reactive rotational forces can occur.
It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of controrl circuits for electric drills differing from the types described above.
While the invention has been illustrated and described as embodied in electric drill speed control, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.
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In a hand-held electric power tool, a combination including an electromotor, and an electric circuit for controlling the speed of the motor, including a pressure switch for controlling the motor speed, a first control potentiometer operatively associated with said pressure switch for adjusting the motor speed from zero up to a predetermined motor operating speed.
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BACKGROUND OF THE INVENTION
The present invention concerns post-treated titanium dioxide (TiO 2 ) having pigmentary morphological and granulometric characteristics, as well as a process for producing said product.
One object of this invention is to provide a TiO 2 particle with pigmentary morphological and granulometric characteristics and endowed with a new property: i.e.; to have a chemically reactive coating.
Still another object of this invention is that of conferring to such a coating a strong adherence to the TiO 2 particles.
Yet another object of this invention is that of imparting to such a coating the property of being uniform and compact.
A further object of the invention is that of conferring to the TiO 2 particles thus coated, a specific surface controllable at will.
Another object still, is that of providing a process for obtaining the above said chemically reactive coating.
Still another object of the invention is that of preparing a pigment superfically coated with organic molecules which impart to it an affinity for the organic substances of the vehicles, for example, paint vehicles, starting from the TiO 2 with a chemically reactive coating.
All these objects and others still are achieved by the new product object of this invention, which consists of TiO 2 particles with pigmentary morphological and granulometric characteristics and is characterized in that said product has a chemically reactive coating consisting of a mixture of oxides and oxychlorides selected from the group consisting of Al 2 O 3 and AlOCl; SiO 2 and SiOCl 2 ; and ZrO 2 and ZrOCl 2 .
The chemical reactivity of these new products is due to the presence of the oxychlorides.
As a result of these reactive groups, one may, for example, fix onto the particles substances containing amine, carboxylic, or hydroxylic groups, thereby obtaining pigments with an affinity for organic vehicles, for example, vehicles for paints based on alkyd, polyester, melaminic, acrylic and phenolic resins.
In general, the atomic ratio between Cl and Al, Si or Zr, present in these new products, is between 0.10 and 0.90.
Still another object of this invention is a process for preparing TiO 2 particles with pigmentary morphological and granulometric characteristics having the above mentioned chemically reactive coating, this process being characterized in that the surface of the particles is activated in a moving bed by thermal treatment with an anhydrous gas at temperatures comprised between 400° and 600° C., and that the particles are then reacted in a moving bed with an inorganic chloride chosen out of a group consisting of: AlCl 3 , SiCl 4 and ZrCl 4 , in the presence of a carrier gas, at temperatures between 350° an 600° C.
SUMMARY OF THE INVENTION
This invention concerns a new product consisting of TiO 2 particles having pigmentary granulometric and morphological characteristics. It includes a chemically reactive coating consisting of a mixture of oxides and oxychlorides selected from the group consisting of Al 2 O 3 and AlOCl; SiO 2 and SiOCl 2 ; and ZrO 2 and ZrOCl 2 .
The particles of reactive TiO 2 product are prepared as follows: the surface of the TiO 2 particles is activated by thermally treating the particles in a moving bed with an anhydrous gas at 400°-600° C. The particles are then made to react in a moving bed at 350° C. to 600° C., in the presence of a carrier gas, with an inorganic chloride selected from the group consisting of AlCl 3 , SiCl 4 and ZrCl 4 .
This new product is useful, for instance, in TiO 2 pigments coated with organic molecules which provide an affinity for the vehicles of paints.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the reaction stage there actually occurs with the chlorides a true and real corrosion reaction of the TiO 2 particles by the action of the chlorides themselves, according to the following reactions:
(x+y)TiO.sub.2 +(2y+4/3 x)AlCl.sub.3 →(x+y)TiCl.sub.4 +2y AlOCl+2/3xAl.sub.2 O.sub.3 ( 1)
(x+y)TiO.sub.2 +(2y+x)SiCl.sub.4 →(x+y)TiCl.sub.4 +2y SiOCl.sub.2 +xSiO.sub.2 ( 2)
(x+y)TiO.sub.2 +(2y+x)ZrCl.sub.4 →(x+y)TiCl.sub.4 +2y ZrOCl.sub.2 +x ZrO.sub.2 ( 3).
In these reactions, the value of y tends to drop when the temperature rises. In other terms the quantity of the oxychlorides with respect to the corresponding oxides tends to decrease with the rise of the temperature.
The corrosion reaction of the TiO 2 is made possible by the preceding activation stage which, among others, has the effect of eliminating the superficial TiO 2 hydroxyls, hindering their reaction with AlCl 3 , etc., with the formation of Al 2 O 3 , etc., which would cause the formation of a slight superficial "passivating" layer of Al 2 O 3 , etc., which would block any further reaction of TiO 2 with AlCl 3 , etc.
The product obtained at the end of the chlorination stage stands out for the high adhesion of the coating to the particles.
This coating is compact and has a very uniform thickness wherefore the elementary particles of the pigment, especially in the case of Al 2 O 3 and AlOCl, practically retain their original shape. Further, the specific surface of the pigment does not suffer any substantial increment, especially in the case of Al 2 O 3 and AlOCl, unless one wishes to increase it within limits controllable at will, just following the procedures that will be explained in further detail.
In the activation and reaction stages there is used a moving bed, that is, a bed in which particles of TiO 2 are put in motion and into close contact with a gas going through the activation or reaction zone. Preferably one operates in a fluidized bed.
It has now been found, according to this invention that it is not necessary to disaggregate the elementary particles of pigment by grinding before treatment in order to obtain a good coating on the single particles.
This is quite convenient in as much as the TiO 2 particles often show up in form of aggregates having dimensions quite suited for their use in a moving bed, and more particularly in a fluidized bed.
Such is the case of TiO 2 via sulphate coming from a calcining furnace; it is quite sufficient to carry out a screening in order to eliminate the fraction exceeding about 500 microns.
If the available particles are too small for being used in a moving bed, they may be granulated according to the usual granulating techniques, for instance in a Heinrich type granulator.
If it is wished to reduce or increase the particle size of the available TiO 2 particles, it is preferable to bring their size to values comprised between 45 and 500 microns which are the sizes most suited for fluidized beds.
These values are referred to the minimum and maximum size of the particles, and do not refer to their mean diameter which may, for instance, be comprised between 80 to 130 micron.
As already explained, the activation phase is carried out at temperatures comprised between 400° and 600° C. Under 400° C., the activation reaction is too slow. Above 600° C. there are obtained end products of an inferior quality. Preferably it is operated at temperatures comprised between 500° and 600° C.
The anhydrous gas used for the activation may be, for example, nitrogen or air. The duration of the activation reaction increases as the treating temperature decreases and humidity of the starting product increases. Usually the activation times range is between about 15 minutes and 3 hours.
The activation must be carried out on an equipment that will ensure a good contact between the anhydrous gas and the TiO 2 particles; moving beds, and more particularly, fluidized beds are preferred. Pneumatic conveyors, rotary kilns, etc. may also be used.
The reaction stage with the chlorides takes place at temperatures comprised between 350° and 600° C. At temperatures below 350° C., the reaction tends to slow down too much, while, at temperatures above 600° C., the formation of oxichlorides becomes too limited; that is, the products that are obtained tend to become chemically less reactive.
Preferably one operates at temperatures between 400° and 500° C.
As a carrier gas, an anhydrous gas which is inert relative to TiO 2 and the chlorides themselves is preferred, unless one wishes to increase in a controllable way the specific surface of the particles, as will be explained further on.
The inert gas may be, for instance, nitrogen or a noble gas; but preferably nitrogen is used. The chloride vapors are introduced into the carrier gas.
A degree of conversion may be defined as consisting of the ratio between the TiO 2 that has reacted in the corrosion reaction and the TiO 2 of the starting pigment. Thus, the degree of conversion is a measure of the intensity of the corrosion as well as of the quantity of coating present on the particles.
By the process according to this invention, it is possible to control the degree of conversion by controlling both the reaction temperature (the higher the temperature, the faster the reaction) as well as the duration of the reaction stage itself. The degree of conversion may vary, for instance, from 0.1% to 5% and more.
The partial pressure of the chloride in the reaction medium is, in general, comprised between 0.005 and 0.15 atm.
The reaction shall be conducted in an apparatus suited for ensuring intimate contact between the solid and the gaseous phase. For such a purpose it is preferred that a moving bed and, more particularly, a fluidized bed be utilized.
The duration of the chlorination stage is a function of the temperature and the conversion degree on wishes to achieve. Suitable reaction times may be, for example, between 20 minutes and 2 hours.
In the case of the reaction with AlCl 3 , the specific surface of the TiO 2 particles remains practically unchanged, while it slightly grows in the case of the reaction with SiCl 4 or ZrCl 4 .
Whenever one wishes to obtain a greater specific surface of the particles, depending on the use to which they are directed according to this invention, contemporaneously with the reaction of the chloride with TiO 2 , there may be carried out an oxidation reaction of the chloride itself with oxygen, such reaction causing the formation of the corresponding oxides according to equations (4), (5) and (6) and their deposit on the TiO 2 particles.
4AlCl.sub.3 +3O.sub.2 →2Al.sub.2 O.sub.3 +6Cl.sub.2 ( 4)
SiCl.sub.4 +O.sub.2 →SiO.sub.2 +2Cl.sub.2 ( 5)
ZrCl.sub.4 +O.sub.2 →ZrO.sub.2 +2Cl.sub.2 ( 6)
Since the oxides that have been formed according to the above reactions deposit themselves onto the TiO 2 particles instead of being produced by a reaction with them, they will form, for the part pertaining to them, a less uniform coating than the one that is obtained by the corrosion reaction alone, wherefore one will obtain an increase in specific surface.
Carrying out a mixed TiO 2 - corrosion and chloride-oxidation reaction, the coating that will be formed will contain oxides coming from both reactions and the increase in specific surface must be ascribed, in the case of AlCl 3 , almost exclusively to the oxidation reaction, while in the case of SiCl 4 and ZrCl 4 it will be due to both reactions.
If one wishes to carry out the oxidation reaction, it will be necessary to operate at at least 400° C. Below this temperature, the reaction occurs in fact in a much too limited way. As the temperature is increased above 400° C., the oxidation reaction takes place with increasing intensity, wherefore there contemporaneously will grow both the specific surface of the particles as well as the quantity of oxide in the coating coming from the oxidation reaction.
The mixed TiO 2 chlorination and chloride-oxidation reaction is preferably carried out at 400°-500° C.
When both reactions are conducted contemporaneously, it is preferred to use air as carrier gas. The specific surface of the coating may be controlled at will by playing on the use or omission of the oxidation reaction and on its intensity which, in its turn, depends on the temperature used.
The product obtained at the end of the corrosion reaction or of the mixed corrosion and oxidation reaction, is an acid product, given the presence of the oxychlorides. Its pH varies, for instance, between 4.4 and 6.3. Also an object of this invention is a process for the preparation of the titanium dioxide pigment coated with organic substances containing aminic, carboxylic or hydroxylic groups capable of imparting to the pigment an affinity for organic vehicles, for instance in paints.
For this purpose there are prepared TiO 2 particles having a chemically reactive coating, and these particles are then made to react with organic substances having --NH 2 , --COOH or --OH groups. The reaction preferably takes place at temperatures between 20° and 200° C. Preferably the reaction is to be conducted in an aprotic organic solvent. Suitable solvents include, for example, tetrahydrofurane and n-hexane.
Among the suitable organic substances which may be used are: lactic acid, isopropanolamine, monopropyletherethylene glycol, monomethylether-ethylene glycol and trimethylolpropane.
The end product will thus consist of TiO 2 particles coated with a first layer of oxide of Al, Si or Zr and a second layer of an organic substance chemically bound to the first layer.
The following set of examples are given in order to further illustrate the inventive idea of this invention.
EXAMPLE 1
There was used a discontinuous fluid-bed reactor consisting of a quartz pipe having an inside diameter of 4.5 cm.
The disengaging height of the bed amounted to 50 cm. This reactor was loaded with 60 g of TiO 2 at a 99.9% concentration and of rutile crystalline structure, and with an elementary granulometry characterized by a mean geometrical diameter d g equal to 0.185 micron, by a standard geometrical deviation σg=1.37 and by a specific surface of 5.5 sq. mt/g.
The TiO 2 was obtained from the sulphate process and was drawn off at the outlet of the calcining furnace. The product presented itself in the form of aggregates with a mean diameter of 110 microns.
The activation stage was conducted maintaining the reactor at 600° C. and by subjecting the titanium dioxide to a 50 Nl/hr flow of nitrogen for 120 minutes.
The corrosion reaction was conducted at 500° C. with a 100 Nl/hr flow of a gaseous mixture consisting of N 2 and AlCl 3 , in which mixture the partial pressure of AlCl 3 was 1.46.10 -2 atm. which corresponds to 5.97.10 -7 mols/cc.
The corrosion treatment lasted 127 minutes and yielded a deposit of Al 2 O 3 and AlOCl which, calculated as Al 2 O 3 , corresponded to 1.4% on the total weight of the particles (i.e.: on the weight of TiO 2 and its coating).
The quantity of Cl and Al in the coating was determined by fluorescence X-ray examination. The atomic ratio Cl/Al proved to be equal to 0.41. The product showed a pH of 4.4 and a specific surface of 5.6 sq.mt/g.
The photostability of the product was measured in a Resial 1180 based enamel baked at 135° C. Resial 1180, produced by Montedison SpA, is an alkydic resin. The pigment specimen in the enamel was subjected, in an accelerated exposure test, to the UV radiation of a carbon-arc lamp, produced by a Fade-Ometer of the Atlas Electric Devices Co. The duration of the exposure was 17 hrs. On the basis of the reflectance loss with the blue filter after exposure, there was calculated a photoinstability index F i which is so much the lower, the greater the photostability of the product.
The photoinstability index F i of the product proved lower than or equal to 0.1, while that of the starting TiO 2 was 1.65.
EXAMPLE 2
The activation stage was repeated as described in Example 1. Thereupon, there was carried out a corrosion stage with AlCl 3 with a contemporaneous oxidation at 400° C., by means of a 100 Nl/hr. flow of a gaseous mixture consisting of air and AlCl 3 , wherein the partial pressure of the AlCl 3 was equal to 1.46.10 -2 atm. The treatment time amounted to 360 minutes.
The product that was thus obtained, displayed an Al 2 O 3 and AlOCl coating equivalent to 1.08% by weight of Al 2 O 3 on the total weight of the particles. The atomic ratio Cl/Al was equal to 0.80. The product showed a pH of 4.4 and a specific surface of 6.5 sq.mt/g.
EXAMPLE 3
The activation as described in Example 1 was repeated. Thereupon there was carried out a corrosion reaction in nitrogen with AlCl 3 .
The reaction was conducted at 600° C. with a 100 Nl/hr flow of a gaseous mixture containing N 2 and AlCl 3 , wherein the partial pressure of AlCl 3 amounted to 1.46.10 -2 atm. The duration of the reaction was 60 minutes. The product obtained had a coating of Al 2 O 3 and AlOCl equivalent to 1.3% by weight of Al 2 O 3 on the total weight of the particles. The atomic ratio Cl/Al was equal to 0.25.
The product displayed a pH equal to 4.8, an F i index lower than or equal to 0.1 and a specific surface of 5.3 sq.mt/g.
EXAMPLE 4
The activation stage according to the procedures of Example 1 was repeated. Thereupon, there was carried out a corrosion stage with AlCl 3 and contemporaneously an oxidation at 600° C., by means of a 100 Nl/hr flow of a gaseous mixture of air and AlCl 3 , wherein the partial pressure of the AlCl 3 amounted to 1.46.10 -2 atm. The treatment time amounted to 90 minutes.
The product obtained showed a coating of Al 2 O 3 and AlOCl equivalent to 1.61% by weight of Al 2 O 3 on the total weight of the particles. The atomic ratio Cl/Al proved to be lower than or equal to 0.10. The product showed a pH value of 5.2, an F i index lower than or equal to 0.1 and a specific surface of 8.5 sq.mt/g.
EXAMPLE 5
The activation stage of Example 1 was repeated. Thereupon there was carried out a corrosion stage in nitrogen with SiCl 4 . The reaction was conducted at 400° C. with a 100 Nl/hr flow of a gaseous mixture consisting of N 2 and SiCl 4 , wherein the partial pressure of the SiCl 4 was equal to 1.7.10 -2 atm. The duration of the reaction amounted to 120 minutes.
The product thus obtained has a SiO 2 and SiOCl 2 coating equivalent to 1.1% by weight of SiO 2 on the total weight of the particles. The atomic ratio Cl/Si was equal to 0.89. The product obtained showed a pH value equal to 5.1 and a specific surface of 9.15 sq.mt/g.
EXAMPLE 6
The activation stage was carried out as described in Example 1. Thereupon there was carried out a corrosion stage with SiCl 4 and a contemporaneous oxidation at 600° C., by means of a 100 Nl/hr flow of a gaseous mixture of air and SiCl 4 , in which the SiCl 4 pressure amounted to 1.4.10 -2 atm. The time of treatment was equal to 180 minutes.
The product thus obtained showed a coating of SiO 2 and SiOCl 2 equivalent to 2.1% by weight of SiO 2 on the total weight of the particles. The atomic ratio Cl/Si amounted to 0.10. The product thus obtained showed a pH value of 6.3 and a specific surface of 9.0 sq.mt/g.
EXAMPLE 7
The activation stage was carried out following the procedures described in Example 1. Thereupon there was carried out a corrosion stage with SiCl 4 in nitrogen. The reaction was conducted at 500° C. in a 100 Nl/hr. flow of a gaseous mixture of N 2 and SiCl 4 , wherein the partial pressure of SiCl 4 amounted to 1.4.10 -2 atm. The duration of the reaction amounted to 180 minutes.
The product thus obtained has a SiO 2 and SiOCl 2 coating equivalent to 1.1% by weight of the SiO 2 on the total weight of the particles. The atomic ratio Cl/Si was equal to 0.45. The product showed a pH value of 5.85 and a specific surface of 8.4 sq.mt/g.
EXAMPLE 8
The activation stage was carried out according to the procedures of Example 1. Thereupon there was carried out a corrosion stage with SiCl 4 nitrogen. The reaction was conducted at 600° C. by means of a 100 Nl/hr flow of a gaseous mixture of N 2 and SiCl 4 , wherein the partial pressure of the SiCl 4 amounted to 1.4.10 -2 atm. The duration of the reaction amount to 180 minutes.
The product thus obtained showed a SiO 2 and SiOCl 2 coating equivalent to 1.6% by weight of SiO 2 on the total weight of the particles. The atomic ratio Cl/Si amounted to 0.15. The product showed a specific surface of 8.3 sq.mt/g.
EXAMPLE 9
The activation stage was carried out according to the procedures of Example 1. Thereupon, there was carried out a corrosion stage with ZrCl 4 in nitrogen. The reaction was conducted at a temperature of 600° C. with a 100 Nl/hr flow of a gaseous mixture consisting of nitrogen and ZrCl 4 , with a partial pressure of ZrCl 4 equal to 40 mmHg corresponding to 5.3.10 -2 atm. The duration of the operation amounted to 75 minutes and yielded a deposit of zirconium compounds equal to 2.6% by weight of ZrO 2 on the total weight of the particles. The atomic Cl/Zr ratio was equal to 0.10. The product coming from the corrosion stage showed a pH value equal to 5.3 and a specific surface of 8.4 sq.mt/g.
EXAMPLE 10
The activation stage was carried out following the same procedures as those of Example 1. Thereupon there was carried out a corrosion stage in nitrogen with ZrCl 4 . The reaction was conducted at a temperature of 400° C. with a 100 Nl/hr flow of a gaseous mixture of N 2 and ZrCl 4 , wherein the partial pressure of ZrCl 4 amounted to 5.3.10 -2 atm. The duration of the reaction amounted to 120 minutes and the product thus obtained had a ZrO 2 and ZrOCl 2 coating equivalent to 1.2% by weight of ZrO 2 on the total weight of the particles. The product showed a pH value of 2.5 and a specific surface of 9.0 sq.mt/g. The atomic Cl/Zr ratio amounted to 0.65.
EXAMPLE 11
Using the same reactor as that described in Example 1, an activation stage was carried out at 450° C. subjecting the titanium dioxide to a 50 Nl/hr flow of nitrogen for 120 minutes.
Thereupon there was carried out a corrosion stage at 450° C. with SiCl 4 , by means of a 100 Nl/hr flow of a gaseous mixture of nitrogen and SiCl 4 , wherein the partial pressure of SiCl 4 amounted to 1.4.10 -2 atm. The treatment time amounted to 180 minutes. At the end of the corrosion stage there was obtained a coating of silicon compounds equivalent to 1.3% by weight of SiO 2 on the total weight of the particles. The product thus obtained showed an atomic ratio Cl/Si of 0.7, a pH value of 2.5 and a specific surface of 8.7 sq.mt/g.
EXAMPLE 12
Using the same reactor as in Example 1, there was carried out at 450° C. an activation stage, subjecting the titanium dioxide to a flow of 50 Nl/hr of air for 120 minutes.
Thereupon there was carried out a corrosion stage with AlCl 3 and an oxidation stage at 500° C. by means of a 100 Nl/hr flow of a gaseous mixture of air and AlCl 3 , wherein the partial pressure of AlCl 3 amounted to 3.7.10 -2 atm. The treatment time amounted to 120 minutes.
At the end of the corrosion-oxidation stages there was obtained a coating of aluminum compounds equivalent to 1.48% by weight of Al 2 O 3 on the total weight of the particles. The product thus obtained showed an atomic ratio Cl/Al of 0.20, a pH value of 4.6 and a specific surface of 6.1 sq.mt/g.
EXAMPLE 13
In this example a coated TiO 2 pigment was treated with monomethylether-ethylene glycol. To one part by weight of reactive TiO 2 coated with SiO 2 and SiOCl 2 , and prepared according to the procedures of example No. 11, there were added 0.1 part of the above indicated glycol and 2.5 parts of n-hexane which serves as a solvent.
The reaction was conducted in a grinding jar at room temperature for 60 minutes. At the end of the reaction the phases were separated by filtering, and the solid product obtained was washed with n-hexane and then dried under vacuum at 60° C. for 18 hours.
In order to evaluate the affinity for organic substances of the end product, the oil absorption was determined according to the ASTM D 1483-60 method, the only difference being that instead of linseed oil dioctylphtalate was used as wetting agent. The oil absorption is expressed as the wetting point and corresponds to the number of cubic centimeters of dioctylphtalate required for obtaining a compact mix starting from 10 g of a TiO 2 sample.
The wetting point has been recorded on the attached table. For comparative purposes, there has been reported the wetting point for TiO 2 free of treatment, and for a TiO 2 subjected to a common wet post-treatment with a silica coating.
______________________________________Sample: Wetting point:______________________________________TiO.sub.2 of example 2.85TiO.sub.2 wet post-treated with SiO.sub.2 2.82TiO.sub.2 not post-treated 3.90______________________________________
From the examination of the table there can be seen that the wetting point of the sample, according to this invention, is practically identical with that obtained with the post-treatment of the prior art.
EXAMPLE 14
In the present example a reactive pigment of TiO 2 , coated with AlCl 3 and AlOCl was prepared according to the procedures of Example 12, and was treated with monomethylether-ethylene glycol following the procedures indicated in Example 13.
On the dried end product there was evidenced the formation of a chemical bond between the glycol and the TiO 2 particles through thermal stability tests in explorative differential calorimetry.
In fact there was ascertained a heat absorption both at 130°-132° C. as well as at 200°-240° C. On the contrary, carrying out tests on non-reactive TiO 2 samples, treated with the glycol according to the procedures of example 13, there occurred a heat absorption only at 130°-132° C., which clearly corresponds to the desorption of the glycol which has a boiling temperature of 124° C. The heat absorption at 200° C. to 240° C. is thus connected with a rupture of chemical bonds of the glycol chemically fixed onto the surface of the TiO 2 particles.
The wetting point was determined by the procedures described in Example 13, on the product according to this invention and, just for comparative purposes, on a TiO 2 free of treatment as well as on a TiO 2 subjected to a common wet post-treatment with an alumina coating. The results thus obtained have been recorded on the table.
______________________________________Sample: Wetting point:______________________________________TiO.sub.2 of example 2.90TiO.sub.2 wet post-treated with alumina 2.80TiO.sub.2 not post-treated 3.90______________________________________
From the examination of the Table it will be seen that the TiO 2 post-treated according to the invention, has a wetting point near that obtained with a post-treatment of the prior art.
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This invention concerns a new product consisting of TiO 2 particles having pigmentary granulometric and morphological characteristics. It includes a chemically reactive coating consisting of a mixture of oxides and oxychlorides selected from the group consisting of Al 2 O 3 and AlOCl; SiO 2 and SiOCl 2 ; and ZrO 2 and ZrOCl 2 .
The particles of reactive TiO 2 product are prepared as follows: the surface of the TiO 2 particles is activated by thermally treating the particles in a moving bed with an anhydrous gas at 400°-600° C. The particles are then made to react in a moving bed at 350° C. to 600° C., in the presence of a carrier gas, with an inorganic chloride selected from the group consisting of AlCl 3 , SiCl 4 and ZrCl 4 .
This new product is useful, for instance, in TiO 2 pigments coated with organic molecules which provide an affinity for the vehicles of paints.
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BACKGROUND OF THE INVENTION
(a) Field of the Invention
The invention relates to cyclic compounds having a 3-dimensional structure which binds to neurotrophin receptors, their uses for the treatment or prevention of peripheral and central nervous system diseases, neuromas at the end of an amputated limb and neoplastic diseases which express neurotrophin receptors.
(b) Description of Prior Art
Nerve Growth Factor (NGF) is a protein which has prominent effects on developing sensory and sympathetic neurons of the peripheral nervous system and cholinergic neurons of the CNS. NGF is a polypeptide growth factor member of the neurotrophin family, which includes Brain Derived Neurotrophic Factor (BDNF), Neurotrophin-3 (NT3) and Neurotrophin-4/5 (NT-4/5). NGF controls the survival and development of certain neuronal populations and has been reported to be a mitogen for other cell types. Two cell surface NGF receptors have been characterized on the basis of binding affinity and signal transduction properties, namely the p75 low affinity NGF receptor (LNGFR) and p140 trkA.
The p75 receptor (Kd=10 -9 M; Johnson, D. et al. (1986) Cell, 47: 545-554) is a 75 kDa glycoprotein member of the TNFR/Fas/CD40 family of receptors (Itoh et al., (1991) Cell, 66:233-243). p75 contains no intrinsic catalytic activity but can associate with the ERK family of soluble kinases (Volonte C. et al. (1993) J. Biol. Chem., 268:21410-21415), and plays a role in protection from neuronal apoptotic death (Rabizadeh, S. et al. (1993) Science, 261:345-348). p75 is also the low affinity binding receptor for BDNF and NT-3 (Ibanez, C. F. et al. (1991) Eur. Mol. Biol. Org. J., 10:2105-2110) but these latter growth factors each have distinct trk receptors.
The p140 trkA receptor is a 140 kDa glycoprotein encoded by the trk proto-oncogene (Klein, R. et al. (1991) Cell, 65:189-197). Scatchard analysis of cells expressing only trkA receptors showed a curvilinear plot with Kd .sup.˜ 10 -11 M and 10 -9 M (Jing, S. et al. (1992) Neuron, 9: 1067-1079). The trkA receptor has intrinsic tyrosine kinase activity and is capable of evoking cellular neurotrophic responses in vitro in the absence of p75 LNGFR (Hempstead, B. L. et al. (1991) Nature, 350: 678-683).
The co-expression of both p75 and p140 allows detection of a higher affinity NGF receptor and affords a Kd .sup.˜ 10 -12 M (Jing, S. et al. (1992) Neuron, 9: 1067-1079). Hence, p75 can associate with different trk-receptors to form high affinity binding sites but neurotrophin binding specificity is mediated by distinct trk-receptors (Ip, N.Y. et al. (1993) Neuron, 10:137-149). The molecular nature of the functional receptor remains unknown.
The NGF protein has been purified, cloned and sequenced (Angeletti, R. H. et al. (1973) Biochemistry, 12: 100-115). Cloning of NGF from different species has shown high amino acid sequence homology, and cross-species biological reactivity.
The structure of mouse NGF has been resolved from crystallographic data at 2.3 Å resolution (McDonald, N. Q. et al. (1991) Nature, 345: 411-414). In the crystals, the NGF molecule is a tightly associated dimer made up of parallel protomers of 118 amino acids. Each protomer has seven β-strands forming three antiparallel pairs. The β-strands are linked by four exposed regions: three β-turns (termed A'-A", A'"-B, and C-D) and one series of three contiguous reverse-turns (termed B-C).
The β-turn and reverse-turn regions had been noted for their hydrophilic nature and unlike the mostly conserved buried residues of the β-strands the β-turns have little conservation between different neurotrophins (Hallbook, F. et al. (1991) Neuron, 6: 845-858). The variability and hydrophilicity of these β-turn regions has prompted the hypothesis that they may be involved in determining neurotrophin receptor specificity because several dimeric molecules use β-turns for critical binding surface(s). Similarly, antibodies and other members of the immunoglobulin gene superfamily (Chothia, C. et al. (1987) J. Mol. Biol., 196:901-917) and other globular proteins (Sibanda, B. L. et al. (1989) J. Mol. Biol., 206: 759-777) use β-turns to interact with complementary sequences with high affinity and specificity.
Experimental evidence using mutagenesis and chimeric molecules has sustained this early hypothesis concerning β-turns of NGF. For example, a chimeric BDNF molecule expressing two β-turns regions of NGF was able to induce neurite outgrowth in NGF responsive sympathetic neurons to the same extent as wild type NGF (Ibanez, C. F. et al. (1991) Eur. Mol. Biol. Org. J., 10:2105-2110).
In spite of the structural information obtained, attempts to create analogs which mimic the activity of NGF β-turns have not been equally successful. Longo et al (Longo, F. et al. (1990) Cell Reg., 1:189-195), found a peptide with sequences from NGF residues 23-35 which inhibited NGF activity. However, this linear peptide did not adopt the β-turn structure from which it was derived in NGF and did not affect the binding of radiolabeled NGF to receptor expressing cells. The peptides were sequence analogs rather than structural analogs of NGF. Furthermore, the concentration of peptide at which inhibition of NGF biological activity occurred (2 mM) was well within concentrations at which non-specific effects can also occur.
Murphy et al (Murphy, R. A. et al. (1993) J. Neuroscience, 13(7): 2853-2862) have used a similar approach to study linear peptides derived from NGF comprising amino acids 23-35, 59-67, 69-79, and 91-100. Some limited biological effects were seen for peptides (59-67) and (91-100) in the in vitro assays of neurite survival when suboptimal concentrations of NGF and a 1,000 fold excess of peptide with respect to NGF were used. However, these peptides did not appear to bind the receptors with high affinity and did not compete with radioactive NGF for binding. In addition, antisera raised against the linear peptides did not effectively cross-react with native NGF, further suggesting that the peptides are simply sequence analogs but not true structural analogs of NGF.
The above-mentioned prior studies have contributed to defining important regions of the NGF molecule. However, the exact combination of amino acids of NGF and the 3-dimensional structure(s) that participate in binding to p75 or trkA receptors and cause biological effects remains to be determined.
Frank M. Longo et al. (European Patent Application published under No. EP-A-335,637 on Oct. 4, 1989) have disclosed what are purported to be agonist and antagonist nerve growth factors peptides. These NGF blocking peptides, which are in fact sequence analogs, can be used to inhibit the expression of mRNA and their encoded proteins whose expression is stimulated by NGF. Again, there is no teachings or suggestions of 3-dimensional structures of native NGF or of NGF blocking peptides that participate in binding to p75 or trkA receptors. The linear peptide sequences described by Longo et al. represent synthesized fragments of NGF without teachings or concern with structural motifs, architecture, folding, or bioavailability. The inhibitory activity of these non-structural, linear peptide sequence analogs of NGF was observed at very high, non-pharmacological doses of analog (2 mM), tested versus suboptimal doses of NGF. Further, the inhibitory activity reported did not include an ability to affect either NGF binding, specific receptor binding by NGF, receptor dimerization, neurite extension by NGF responsive cells, or other physiological events associated with NGF function or receptor physiology.
It would be highly desirable to be provided with a cyclic compound having a 3-dimensional structure which binds to neurotrophin receptors, which would mimic the neurotrophin 3-D conformation.
SUMMARY OF THE INVENTION
One aim of the present invention is to provide cyclic compounds having a particular 3-dimensional structure which allows them to be capable of binding to the receptor for neurotrophins, such as NGF, BDNF, NT3 and NT-4/5.
Another aim of the present invention is to provide NGF structural analogs which bind to the NGF receptor.
In accordance with the present invention there is provided a cyclic compound having a 3-dimensional structure which binds to neurotrophin receptors under physiological conditions in vitro or in vivo, and wherein said binding to said receptor at least partially mimics or inhibits said neurotrophins biological activity. The cyclic compound of the present invention may be a structural analogs of NGF or small monomeric, dimeric or polymeric cyclic compounds that mimic the β-turn regions of NGF. Such a cyclic compound includes at least one 3-D conformation selected from a β-turn at region 28-36(A'-A"), 43-49 (A'"-B) and 91-98 (C-D) and three consecutive reserve turns at region 59-65(B-C). The 3-dimensional conformation of those cyclic compounds may be stabilized by oxidation of cysteine residues to disulfide bridge or by other means of cyclization that do not require Cys, including ionic bonds, salt bridges, Lys-Glu or any chemical bonding.
Also in accordante with the present inventation, the cyclic compounds may be used in vivo as a neurotrophin antagonist to inhibit the neurotrophin binding to its receptor, or to induce the neurotrophin receptor internalization or downmodulation from the surface of cells. Such inhibitions may be used for the treatment of central or peripheral nervous system diseases or for the inhibition or neurite outgrowth in situ in cases of neuromas or for targeting the neurotrophin receptor-expressing tumors.
Also in accordance with the present invention, the cyclic compounds may be used in vivo as neurotrophin agonist to mimic the neurotrophin binding to more then one neurotrophin receptor. Such agonists may be used for the treatment of central nervous system diseases or for peripheral nervous system diseases, or for inducing re-innervation, accelerating cellular differentiation, or inducing terminal differentiation of receptor-expressing tumors.
The following list provides the cyclic compounds in accordance with the present invention, and this is intended to be made without limitation,
Z-X C K G K E C X; SEQ ID NO:1
Z-X C D I K G K E C X; SEQ ID NO:2
Z-X C T A I K G K E C X; SEQ ID NO:3
Z-X C I K G K E C X; SEQ ID NO:4
A T D I K G K E V; SEQ ID NO:5
T I G E A D K K V; SEQ ID NO:6
Z-X C I N N S V C X; SEQ ID NO:7
Z-X C N I N N S V C X; SEQ ID NO:8
Z-X C N I N N S C X; SEQ ID NO:9
V N I N N S V F; SEQ ID NO:10
N N S F V I N V; SEQ ID NO:11
Z-X C S N P V E S C X; SEQ ID NO:12
Z-X C A S N P V E S C X; SEQ ID NO:13
X C A S N P V E C; SEQ ID NO:;14
X C A S N P V E C X; SEQ ID NO:15
R A S N P V E S G; SEQ ID NO:16
A N V S R S P E G; SEQ ID NO:17
Z-X C T D E K Q C X; SEQ ID NO:18
Z-X C T D E K Q A C X; SEQ ID NO:19
T T D E K Q A A W; SEQ ID NO:20, and
T E Q A T D K A W; SEQ ID NO:21
wherein,
X is any uncharged amino acid or hydropathic amino acid; and
Z is a absent or a protective group selected from the group consisting of Fmoc group and acetyl groups.
The following list provides the preferred cyclic compounds in accordance with the present invention,
X C K G K E C X; SEQ ID NO:1
X C D I X G E C X; SEQ ID NO:2
X C I K G K E C X; SEQ ID NO:4
X C I N N S V C X; SEQ ID NO:7
X C N I N N S V C X; SEQ ID NO:8
X C N I N N S C X; SEQ ID NO:9
X C S N P V E S C X; SEQ ID NO:12
X C A S N P V E S C X; SEQ ID NO:13
X C A S N P V E C X; SEQ ID NO:15
X C T D E K Q C X; SEQ ID NO:18; and
X C T D E K Q A C X; SEQ ID NO:19.
The cyclic compounds of the present invention are active in various forms, as follows:
(i) N-terminus can be acetylated or Fmoc protected;
(ii) next to Cys(C), a Tyr(Y), Phe(F), His(H) or Gly(G) can be added, for example:
YCTDEKQCY SEQ ID NO:22
HCTDEKQCH; SEQ ID NO:23
(iii) some substitutions of the following amino acid side chains are allowed, Asp (D) for Glu (Q) or Glu (Q) for Asp (D) in A'-A" and C-D turns;
(iv) racemization of amino acids during synthesis or purification is allowed.
Also in accordance with the present invention, the cyclic compounds can be linked to a tracer (metal chelator, radiolabel, biotin or other chemical groups) to follow the fate of the analog in vivo. Also this is useful for imaging or for cytotoxicity of trkA expressing tumors in vivo especially if toxins are linked, or if other therapies are combined.
Also in accordance with the present invention, there in provided a method for the treatment of central nervous system or peripheral nervous systern diseases and neuromas in a patient, which comprises administering an effective amount of a cyclic compound of the present invention to a patient.
Also in accordance with the present invention, there is provided a method for immunization of a mammal against the cyclic compounds of the present invention, which comprises administering by systemic injection an immunizing amount of at least one of the compounds in an immunogenic form in association with a pharmaceutically acceptable carrier.
Also in accordance with the present invention, there is provided a pharmaceutical composition for the treatment of central nervous system diseases and neuromas, which comprises an effective amount of a cyclic compound of the present invention in association with a pharmaceutically acceptable carrier.
Also in accordance with the present invention, there is provided a method for immunization against the structural analogs of the present invention by systemic injection of these compositions in an immunogenic form.
For the purpose of the present invention the following terms are defined below.
The term "neurotrophin" refers to any neurotrophins, such as NGF, BDNF, NT3 and NT-4/5 among others.
The term "neurotrophin receptors" refers to trkA, trkB, trkc, trkE and p75 among others.
"Agonist" refers to a NGF structural analog in accordance with the present invention which binds to a NGF receptor and mimic NGF in that it is capable of at least one biological activity normally associated with NGF.
"Antagonist" refers to a NGF structural analog in accordance with the present invention which binds to a NGF receptor and inhibits at least one biological activity normally associated with NGF.
"Substantial homology" as used herein refers to substantial correspondence between the identity and the sequence of amino acid residues of the native NGF protein and the NGF structural analogs.
The term "effective amount" refers to the amount of NGF structural analogs required to produce a desired agonist or antagonist effect of the neurotrophin biological activity. The precise effective amount will vary with the nature of NGF structural analogs used and may be determined by one of ordinary skill in the art with only routine experimentation.
As used herein, the terms "neurotrophin-mediated activity" or "neurotrophin-associated activity" refers to cellular events triggered by neurotrophin, being of either biochemical or biophysical nature. The following list is provided, without limitation, which discloses some of the known activities associated with neurotrophins, such as NGF: ion flux, phospholipid metabolism, activation of cyclic AMP-dependent protein kinase, activation of cyclic AMP-independent protein kinase and other protein kinases, protein phosphorylation, activation of oncogenic proteins, activation of RNA transcription, stabilization of mRNA species, and enhancement of protein synthesis, receptor stabilization, receptor dimerization or oligomerization, receptor internalization, and eventual protection from cellular apoposis, induction of growth, and differentiation.
The term "central nervous system diseases" as used herein refer to a disease state in a mammal which includes degenerative growth, development disorders and disorders of the nervous system. Thus diseases characterized by the loss of function and/or degeneration of neurons and nerves. In addition, any disease that can respond to treatment of NGF-responsive or NGF-synthesizing cells with the peptides of the present invention is within the scope of the invention. Exemplary disorders include without limitation, Alzheimer's disease, Down's syndrome, Creutzfeldt-Jacob disease, kuru, Gerstman-Straussler syndrome, scrapie, transmissible mink encephalopathy, Huntington's disease, Riley-Day familial dysautonomia, multiple system atrophy, ALS (amyotropic lateral sclerosis) or Lou Gehrig's disease, Parkinson's disease and the like.
The term "neuromas" as used herein refer to a disease state in a mammal which includes neurite outgrowth or other neural growth of an abnormal sort which causes pain at the end of an amputated limb.
The terms "neoplasmas or tumors" as used herein refer to a disease state in a mammal which includes tumors of neural origin such as neuroblastomas, or non-neural origin such as melanomas, or hematopoietic tumors.
In general, the abbreviations used herein for designating the amino acids are based on the conventional one-letter abbreviations as indicated below:
Alanine A
Arginine R
Asparagine N
Aspartic Acid D
Cysteine C
Glutamine Q
Glutamic Acid E
Glycine G
Histidine H
Isoleucine I
Leucine L
Lysine K
Methionine M
Phenylalanine F
Proline p
Serine S
Threonine T
Tryptophane w
Tyrosine Y
Valine V
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the antagonistic bioactivity of the NGF structural analogs in accordance with the present invention;
FIGS. 2A-B illustrates the competitive inhibition of 125 I-NGF binding to trka by designed NGF structural analogs in accordance with the present invention;
FIG. 3 is a graph which illustrates the inhibition of NGF-induced cell growth or survival by structural analogs;
FIGS. 4A-B illustrates FACScan profiles of surface p14 trkA using an anti-trkA specific monoclonal antibody, after binding of structural analogs under different conditions; and
FIG. 4C is a graph of the analysis of the % reduction of cell surface mean fluorescence channel after receptor internalization.
DETAILED DESCRIPTION OF THE INVENTION
The cyclic compounds in accordance with one embodiment of the present invention are derived from 3-dimensional domains of NGF which are identified as binding to neurotrophin receptors, such as NGF receptor. Such neurotrophin receptor binding interactions by these compounds cause or prevent neurotrophin biological effects in vivo.
The cyclic compounds in accordance with one embodiment of the present invention include a different β-turn or reverse turn mimic of the NGF. These compounds can be combined dimers or oligomers in any desired combination of the same or different structures to obtain improved affinities and biological effects.
It would be clear to those skilled in the art that this approach can be used to derive neurotrophin receptor binding structures from molecules other than neurotrophins themselves, such as the complementary determining region of antibodies directed against the neurotrophin receptors, or from anti-idiotypic antibodies raised against anti-neurotrophin antibodies (Williams et al. (1989) Proc. Natl. Acad. Sci. USA, 86:5537; Saragovi, H. U. et al. (1991) Science, 253: 792-795).
In accordance with the present invention, structural NGF analogs were produced by designing structural constraints in the analogs in order to maintain the desired conformation (Saragovi, H. U. et al. (1991) Science, 253: 792-795, Saragovi, H. U. et al. (1992) Biotechnology, 10: 773-778).
It is demonstrated that cyclic analogs which conserve and closely mimic the three-dimensional structure of the β-turn regions bind to NGF receptors. In contrast, their linear counterparts would seldom adopt the appropriate configuration required to fit the ligand docking site.
Small (average molecular weight .sup.˜ 1,500) structural analogs of β-turns or reverse turns of NGF were designed, synthesized and constrained by cyclization, whereas linear and randomized analogs served as controls. Conformationally constrained analogs had significant NGF antagonistic activity and inhibited NGF mediated neurite outgrowth in p75 LNGFR-p140 trkA expressing PC12 cells grown under optimal conditions. Control linear (not constrained) and randomized sequence analogs did not evidence antagonistic activities at the concentrations tested in the neurite outgrowth assay. Furthermore, some biologically active antagonists were also effective in blocking 125 I-NGF binding to PC12 cells. Furthermore, specific receptor-ligand interactions were mapped by testing the ability of the analogs to inhibit 125 I-NGF binding to p140 trkA receptor expressing fibroblast transfectants.
These data further supports the hypothesis that β-turns are critical in NGF binding to the NGF receptors, and elucidates novel features of receptor-NGF interactions. These data demonstrate that a large macromolecule such as NGF can be reduced to small functional units if the 3-dimensional structure of the native molecule is retained or constrained.
The antagonistic property of the analogs suggests that for agonistic binding the ligand must either engage more than one site on a given receptor, or possess the ability to induce receptor dimerization.
Peptide Synthesis and Characterization
Mouse NGF analogs were synthesized using standard FMOC synthetic procedures. In order to synthesize the large number of analogs required, the Multipin Cleavable Peptide Synthesis System™ (Chiron Mimotopes, Australia) was used. This method allows simultaneous peptide synthesis of 96 peptides on diketopiperazine-linker-derivatized polyethylene pins. Cleavage is performed under mild base conditions using 0.15 M Ammonium bicarbonate pH 8.4. All peptides were synthesized and tested with the amino-termini acetylated and with the Fmoc group intact, and with the diketopiperazine linker present at the carboxy terminus. For cyclization, NH 3 --X--Cys and Cys--X--COO - were added to the termini of the indicated peptides, where X can represent any uncharged or hydropathic amino acid (e.g. Gly when Fmoc-amino termini were present, or Tyr or His when it was absent (see Table I)). Following cleavage the peptides were cyclized by oxidation of the Cysteine residues as described by Saragovi et al. (Saragovi, H. U. et al. (1992) Biotechnology, 10: 773-778). Cyclization efficiency was determined by the Ellman's procedure to be greater than 70%. Peptides were lyophilized, resuspended in water and purified to greater than 85% in a Waters™ HPLC (0.1% trifluoroacetic acid, 40 min 10-40% acetonitrile (ACN) gradient) using a Vydac™ 218TP C18 (1×25 cm) column. Peptides were characterized by aminoacid analysis (Beckman Model 6300 Analyzer™) and by Mass Spectrometry (SCIEX API III™).
Cell Cultures
All cells were cultured as described. PC12 pheochromocytoma cells expressing rat p140 trkA and p75 LNGFR (American Type Culture Collection, 7th edition, 1992, Catalog of cell lines and hybridomas, R. Hay Editor, accession No. CRL 1721) were grown in DMEM supplemented with 20% Fetal Bovine Serum (FBS), 10% Horse serum, and antibiotics. PC12 cells used for experiments were grown on collagen coated dishes. The NIH-3T3 fibroblast transfectants R7 (p75 and trkA double transfectant) and E25 (trkA transfectant) (Jing, S. et al. (1992) Neuron, 9: 1067-1079; kindly provided by Dr. Mariano Barbacid, Bristol-Meyers-Squibb, NJ) were grown in RPMI media supplemented with 5% FBS and antibiotics and the appropriate drug selection.
Neurite Outgrowth Assay
Analogs were tested for their ability to affect NGF induced neurite outgrowth in PC12 cells. PC12 cells were incubated in complete media containing optimal concentrations of NGF (50 ng/ml; approximately 2.0 nM) or basic Fibroblast Growth Factor (bFGF) (50 ng/ml) (Prince Labs, Toronto). NGF analogs or control analogs were then added to a final concentration of 10 μM, cells were incubated and neurite outgrowth was measured every 24 hrs. for three days. Cells without growth factor added served as baseline, whereas cells with growth factor but without analog added were used for maximum neurite outgrowth determination. All analogs were tested in at least three separate assays from three different synthesis. Samples were coded and analysis were performed blind.
NGF Binding Studies
Analogs were tested for their ability to affect binding of 125 I-NGF (73.1 μCi/μg NEN, DuPont). 0.4-1×10 6 cells were incubated in binding buffer (HBSS, 1% BSA, 0.05% Na Azide, pH 7.4) at 4° C. with the indicated concentration of cyclic NGF analogs, control analogs, a titration of unlabeled NGF, or nothing. After 15 min, 125 I-NGF was added to a final concentration of 0.4-2 nM (.sup.˜ 40,000 cpm) and the mixtures were further incubated for 40 min at 4° C. Cells were then washed in binding buffer, pelleted, and cell-associated 125 I-NGF was determined. Background binding was measured by the addition of .sup.˜ 2000 fold excess unlabeled NGF, which resulted in less than 10% of maximum binding; or by measuring binding to NGF receptor negative NIH3T3 cells (.sup.˜ 5%). Assays were performed >4 times, each from at least three different synthesis (inhibitory analogs) or 1-3 times each from 2 different synthesis (non-inhibitory analogs). Receptor saturation experiments were similarly performed with increasing concentrations of 125 I-NGF ligand and a constant dose of inhibitor.
Design and Synthesis of NGF Analogs.
Four regions of the NGF primary sequence were defined which differ significantly from the primary sequence of other neurotrophins, corresponding to amino acid numbers 28-36 (β-turn A'-A"), 42-49 (β-turn A'"-B), 59-67 (turn B-C), and 91-99 (β-turn C-D) of mouse NGF (Table I). Cyclic peptides (C) were synthesized, and for each a linear (unconstrained sequence) (L) control and a scrambled (randomized sequences) (R) control were also made.
TABLE I__________________________________________________________________________NGF Derived Structural Analogs ORIGINAL STRUCTURE/REGIONNFG SEQUENCE AMINO ACID RESIDUES ANALOG CODE__________________________________________________________________________A'-A"Fmoc-X C K G K E C X β turn 32-35 C(32-35) (SEQ ID NO: 1)Fmoc-X C D I K G K E C X β turn 30-35 C(30-35) (SEQ ID NO: 2)Fmoc-X C T A I K G K E C X β turn 29-35 C(29-35ΔD30A) (SEQ ID NO: 3) (ΔD30A)Fmoc-X C I K G K E C X β turn 31-35 C(31-35) (SEQ ID NO: 4)A T D I K G K E V linear 28-36 L(28-36) (SEQ ID NO: 5)T I G E A D K K V randomized 28-36 R(28-36) (SEQ ID NO: 6A'"-BFmoc-X C I N N S V C X β turn 44-48 C(44-48) (SEQ ID NO: 7)Fmoc-X C N I N N S V C X β turn 43-48 C(43-48) (SEQ ID NO: 8)Fmoc-X C N I N N S C X β turn 43-47 C(43-47) (SEQ ID NO: 9)V N I N N S V F linear 42-49 L(42-49) (SEQ ID NO: 10)N N S F V I N V randomized 42-49 R(42-49) (SEQ ID NO: 11)B-C Fmoc-X C S N P V E S C X reverse turn 61-66 C(61-66) (SEQ ID NO: 12)Fmoc-X C A S N P V E S C X reverse turn 60-66 C(60-66) (SEQ ID NO: 13)X C A S N P V E C reverse turn 60-65 C(60-65) (SEQ ID NO: 14)R A S N P V E S G linear 59-67 L(59-67) (SEQ ID NO: 16)A N V S R S P E G randomized 59-67 R(59-67) (SEQ ID NO: 17)C-D Fmoc-X C T D E K Q C X β turn 92-96 C(92-96) (SEQ ID NO: 18)Fmoc-X C T D E K Q A C X β turn 92-97 C(92-97) (SEQ ID NO: 19)T T D E K Q A A W linear 91-99 L(91-99) (SEQ ID NO: 20)T E Q A T D K A W randomized 91-99 R(91-99) (SEQ ID NO: 21)__________________________________________________________________________
X is any uncharged amino acid or hydropathic amino acid and Fmoc in the protective group used during synthesis.
The indicated sequences (shown from amino to carboxy ends) were synthesized and purified. Cysteine residues not found in the NGF sequences selected were incoporated in the peptides to constrain their conformation by intramolecular disulfide bridging. In some cases other designed modifications of the original NGF sequences were necessary to improve analog solubility and to prevent intermolecular disulfide bridging. For cyclic analogs other designed modifications of the original NGF sequences were done. C=cyclic, L=linear, R=randomized. ΔD30A is an Alanine substitution for Aspartic acid at position 30.
Crystallographic data and modeling of NGF has shown that the conformation of regions 28-36, 43-49, and 91-98 is a β-turns while that of region 59-65 are 3 consecutive reverse turns. In some of our peptides the conformation predicted to exist in NGF was preserved by cyclization, which forces the peptide into a β-turn mimic (Williams et al. (1989) Proc. Natl. Acad. Sci. USA, 86:5537). Cyclization was achieved by introducing Cysteine (Cys) residues in the appropriate positions and subjecting the analogs to oxidation. Oxidation of Cys results in a covalent disulfide bridge which stabilizes the desired conformation. All active peptides were purified by HPLC and characterized by ion spray mass spectrophotometry and amino acid analysis.
Inhibition of NGF Function in Biological Assays
Rat PC12 pheochromocytoma cells in culture can differentiate and produce neurites in response to NGF or bFGF. None of the analogs were able to induce neurite projections when added to PC12 cell cultures, suggesting that by themselves they lacked NGF agonistic activity at the concentrations used in these assays.
The effect of the analogs on NGF dependent neurite outgrowth were determined. Cells were incubated with 50 ng/ml NGF (A, C, E, G) or with 50 ng/ml bFGF (B, D, F, H). The indicated NGF analogs were added at ˜10 μM. Representative results for 3 different analogs are shown. For a summary and complete list of the results from these biological tests see Table II.
Two of the inhibitory cyclic analogs, C(32-35), and C(44-48) caused enlargement of the cell size and clumping (Table II). However, non-inhibitory analogs L(42-49), and R(59-67) caused a similar effect, suggesting that this was unrelated to activity.
TABLE II______________________________________Bioactivity Of NGF Structural Analogs TURN INHIBITION CHANGES INNGF REGION OF NEURITE CELL SIZE ORANALOG OF NGF OUTGROWTH (1) APPEARANCE______________________________________C(32-35) A'-A" ++ LARGER SIZEC(30-35) +± NONEC(31-35) ++ NONEL(28-36) ± NONER(28-36) ± NONEC(44-48) A'"-B +++ LARGER/ROUNDINGC(43-48) +++ NONEC(43-47) + NONEL(42-49) +± LARGER/ROUNDINGR(42-49) + NONEC(60-66) B-C ++ NONEC(60-65) ++ NONEL(59-67) + NONER(59-67) + LARGER SIZEC(92-96) C-D +++± NONEC(92-97) +++ NONEL(91-99) + NONER(91-99) ± NONE______________________________________ ++++ equivalent to 0 ng/ml NGF (complete inhibition) +++ equivalent to 6.25 ng/ml NGF ++ equivalent to 12.5 ng/ml NGF + equivalent to 25 ng/ml NGF - equivalent to 50 ng/ml NGF (no inhibition).
The analogs were assayed as described for FIG. 1, and NGF mediated PC12 neurite outgrowth measured. The arbitrary units indicating antagonistic activity are the result of direct comparisons with NGF dose response curves done in parallel. Significant inhibition is indicated by +++.
Cyclic analogs C(92-96) and C(92-97) derived from β-turn C-D, and C(43-48) and C(44-48) derived from β-turn A'"-B of NGF demonstrated antagonistic activity and significantly inhibited NGF mediated PC12 cell neurite projections (FIG. 1, C, E), but did not affect bFGF mediated responses (FIG. 1, D, F). In contrast, other cyclic analogs (e.g. β-turn A'-A" analog C(30-35); FIG. 1, G and H) and the linear or randomized analogs did not affect either NGF or bFGF mediated neurite outgrowth (for a summary see Table II).
Controls ruled out toxicity and demonstrated the specificity of the analogs as antagonists of NGF. First, no cell death was observed after culture with the compounds (exceptions which did cause necrosis were C(29-35ΔD30A) from β-turn A'-A" and C(61-66) from β-turn B-C, and were not used further). Second, when the analogs were removed PC12 cells responded normally to NGF. Third, and most importantly, the NGF analogs did not affect PC12 cell neurite outgrowth in response to bFGF suggesting that the analogs were specific for NGF receptors.
The data presented is the first direct demonstration of the involvement of a defined β-turn region of a polypeptide ligand in binding to a defined neurotrophin receptor. Overall, these data provide support for the notion that β-turn regions are crucial for certain ligand-receptor interactions and this concept may now be applied to other members of the neurotrophin family.
This concept is acceptable to the family of neurotrophins because they are highly related in primary sequence and in structure, and their receptors are also highly related. The neurotrophin ligands differ mostly in their β-turns suggesting that specificity of receptor binding is mediated by β-turns. Replication of this invention with the structure of other neurotrophins would be evident to those skilled in the art.
Direct Inhibition of NGF Binding
To determine the mechanism of biological antagonistic activity by the cyclic analogs, 125 I-NGF binding measurements were performed with cell lines expressing both p75 and trkA receptors (PC12 cells and R7 transfectants) or only trkA receptors (E25 transfectants) (Table III). Analogs were used at a concentration of .sup.˜ 40 μM.
Analogs from the C-D β-turn region were effective in inhibiting 125 I-NGF binding to E25, R7 and PC12 cells. Inhibition of binding was roughly comparable to that obtained with 0.1 μM unlabeled NGF (Table III). These analogs were more efficient at inhibiting NGF binding to E25 cells than to R7 cells. Furthermore, while analogs C(92-96) and C(92-97) inhibited NGF binding to E25 cells to a similar degree (71.3% and 64.9% respectively); C(92-96) was more effective than C(92-97) in blocking NGF binding to R7 cells (51.1% versus 24.3% respectively).
TABLE III______________________________________INHIBITION OF .sup.125 I-NGF BINDING TO NGFRECEPTORS BY NGF STRUCTURAL ANALOGS % INHIBITION PC12 R7 E25INHIBITOR (trkA-p75) (trkA-p75) (trkA)______________________________________0.1 uM NGF 69.5 ± 4.5 80.0 ± 18.9 93.3 ± 8.1C(92-96) 86.4 ± 10.4 51.1 ± 0.7 71.3 ± 13.5C(92-97) N.T. 24.3 ± 9.2 64.9 ± 12.4C(30-35) N.T. 0.44 ± 0.6 51.1 ± 0.7C(32-45) 9.0 (*) -4.5 ± 6.5 30.7 ± 10.5C(44-48) N.T. N.T. -12.5 ± 5.4C(43-48) N.T. 5.0 (*) -2.7 ± 8.5L(91-99) N.T. 3.8 ± 1.0 2.1 ± 8.5L(28-36) 5.0 (*) .sup. -11.3 (*) 6.4 ± 12.4L(42-49) N.T. 8.0 (*) -16.0 ± 15.1L(59-67) N.T. N.T. -9.5 ± 7.5______________________________________
The NGF analogs (.sup.˜ 40 μM) were tested singly for their ability to inhibit 125 I-NGF binding to NGF receptor expressing cells. Data shown represents an average percent inhibition of binding ±2 standard errors of the mean (2 SEM). Background binding was determined by adding 2000 fold excess unlabelled NGF. n=>4 (inhibitory analogs), or 1-3 (non-inhibitory analogs). NT=not tested. (*) assayed only once.
Percent inhibition was determined by applying the following formula: ##EQU1##
Analogs C(30-35) and C(32-35) derived from β-turn A'-A" region inhibited NGF binding to E25 cells (albeit less efficiently than the C-D region analogs), but did not affect NGF binding to R7 cells. This may suggest that the A'-A" region binds to trkA receptors which are not in association with p75, or that p75 association to trkA changes the conformation of trkA such that the binding site for the analog is not available or stable.
None of the other cyclic, linear or randomized analogs had significant effects in 125 I-NGF binding (e.g. C(43-48) or L(91-99), Table III). Note that two biologically active cyclic analogs (A'"-B region analogs C(43-48) and C(44-48), Table II) did not inhibit 125 I-NGF binding in these assays and they may function through a different mechanism.
Analogs derived from β-turn A'-A" region also inhibited NGF binding to trkA-expressing E25 cells, albeit with lower potency than the C-D region β-turn analogs. We have not yet measured the IC50 of A'-A" region analogs, but we expect them to be of lower affinity. A'-A" region analogs did not affect NGF binding to p75/trkA expressing cells at all, suggesting that they only bind trkA receptors which are not in association with p75.
Lack of inhibition by A'-A" region analogs on cells expressing both p75 and trkA can be the result of higher receptor affinity for the ligand. Additionally, a receptor conformational change or masking of the docking site can occur upon heterodimerization of p75 and trkA (Verdi, J. M. et al. (1994) Neuron, 12: 733-745). Theoretical models of functional NGF receptors (Chao, M. V. (1992) Neuron, 9:583-593; Klein, R. et al. (1991) Cell, 65:189-197; Jing, S. et al. (1992) Neuron, 9: 1067-1079) are consistent with the possibility that the trk-docking site of the analogs may be masked upon association of p75 and trkA, but concomitant p75 binding by the analogs could not be formally ruled out.
Analogs C(43-48) and C(44-48) derived from NGF β-turn A'"-B were effective in inhibiting biological assays in PC12 cells without being effective at all in binding assays in E25 cells. The biological effects of C(43-48) must be mediated by the NGF receptor because bFGF was not affected. Perhaps this analog can prevent trkA receptor dimerization, trkA receptor internalization or NGF stability without actually affecting NGF binding. Another explanation is that this inconsistency reflects differences between rat and human trkA receptors which are expressed in neuronal or fibroblastoid cell lines respectively. Inconsistencies between biological and binding responses in transfected fibroblasts versus PC12 cells have been reported (Ip, N.Y. et al. (1993) Neuron, 10:137-149). The mechanism of inhibition by NGF β-turn A'"-B analogs will be resolved by further studies.
C-D Region Analogs are Competitive Inhibitors of NGF by Binding trkA Receptors
In order to determine the nature of the inhibition of 125 I-NGF binding to trkA receptors by the C-D region analogs, dose response and saturation studies were performed.
Dose response studies using increasing amounts of analogs (0.4 μM to 200 μM) or unlabeled NGF (4 nM to 2 μM) were performed in the presence of constant 200 pM concentration of 125 I-NGF (FIG. 2A). Averages of similar experiments showed for analog C(92-96) an IC 50 =23.5±16 μM compared to unlabeled NGF IC 50 =2.65±0.35 nM (FIG. 2B).
Saturation binding assays were performed with trkA receptor expressing E25 cells as described above.
Increasing concentration of inhibitors were tested for their ability to inhibit a constant amount of 125 I-NGF (200 pM)(FIG. 2A). A constant amount of inhibitors (.sup.˜ 45 μM of C(92-96) analog, or 2000 fold excess unlabeled NGF) were added to increasing concentrations of 125 I-NGF.
Saturation analysis using increasing concentrations of 125 I-NGF (0-1.13 nM) versus a constant concentration of analog (C(92-96); 45 μM) or a 2,000 fold excess of unlabeled NGF were performed (FIG. 2B). NGF receptor saturation by 125 I-NGF was displaced by both the analog and unlabeled NGF by reducing receptor availability rather than receptor affinity, suggesting that the inhibition is of a competitive nature.
Taken together, these data demonstrate that cyclic sequence analogs of NGF β-turns C-D and A'-A" likely mimic the native architecture and are therefore able to bind to trkA receptors. Secondary structure requirements for antagonistic activity proved to be absolute because linear and random compounds with primary sequences from all β-turns had no effect at the concentrations tested. Thus, the conformation of the analog must retain some if not many of the features found in the original ligand. This experience is emphasized by previous reports of low affinity or inactive linear analogs of NGF (Longo, F. et al. (1990) Cell Reg., 1:189-195; Murphy, R. A. et al. (1993) J. Neuroscience, 13(7): 2853-2862).
Analogs derived from β-turn C-D, inhibited neurite outgrowth induced by NGF in PC12 cells, and inhibited NGF binding to several receptor expressing cells. Since all neurotrophins (except NGF) have an extra amino acid in β-turn C-D, binding specificity of NGF for trkA may be partly explained (Ibanez, C. F. et al. (1993) Eur. Mol. Biol. Org. J., 12:2281-2293). This region is likely to confer added specificity to NGF in binding to trkA and perhaps to other neurotrophins in binding to their specific high affinity receptors.
It is unlikely that the mechanism of biological antagonism was to hinder NGF but not bFGF signal transduction because transduction is ras-dependent for both ligands (Kremer, N. E. et al. (1991) J. Cell Biol., 115:809-819). Therefore, the analogs mediate their action by directly binding to the extracellular domain of NGF receptors and in this regard they are different than K252 molecules which mediate their action by inhibition of the kinase activity of trkA (Berg, M. M. et al. (1992) J. Biol. Chem., 267:13-16).
NGF analogs did not behave as agonists of PC12 cells. For agonistic activity the ligand must either engage more than one site on a given receptor, or possess the ability to induce receptor dimerization. Since the analogs are structurally equivalent to only one β-turn region of NGF they would not induce receptor dimerization and would be expected to behave as antagonists in biological assays. Preliminary studies testing combined analogs from NGF β-turns A'-A" and C-D showed additive (but not synergistic) effects in NGF binding assays. It is expected in accordance with the present invention that appropriate coupling of these analogs as homodimers or heterodimers will likely reveal synergy or agonistic function.
Previous studies have implicated the amino terminus of NGF comprising amino acids 1-9 was also implicated in binding to trkA receptors (Kahle, P. et al. (1992) J. Biol. Chem., 267:22707-22710; Ibanez, C. F. et al. (1993) Eur. Mol. Biol. Org. J., 12:2281-2293). However, the amino termini was not resolved crystallographically but is not a β-turn (McDonald, N. Q. et al. (1991) Nature, 345: 411-414).
The study of the mechanism of binding by the analogs to trkA only expressing cells versus p75-trkA expressing cells will provide.-more information concerning receptor-ligand interactions. Furthermore, by creating homodimeric and heterodimeric forms of the analogs in accordance with the present invention we will be generating agonistic ligands that permit receptor dimerization.
The present invention will be more readily understood by referring to the following examples which are given to illustrate the invention rather than to limit its scope.
EXAMPLE I
Effect of NGF Analogs in E25 Cell Survival
The inhibitory activity of the compounds of the present invention was tested in more sensitive assays of apoptosis. Cells are dependent on the presence of serum for growth and survival. In the absence of serum (i.e. serum-free media) these cells die (apoptosis) but can be rescued from death with NGF. The peptide analogs can specifically prevent NGF rescue of these cells from death, indicating that they are true NGF antagonists.
NGF responsive mouse fibroblasts transfected with human trkA cDNA (E25 cells) were studied. 5,000 E25 cells/well in serum-free media (SFM) were added to 96 well plates (Costar) containing either serum (final concentration 5% FBS), or SFM with serial dilutions of NGF (Prince Labs, Toronto), or the indicated analogs (final concentration 40 ug/ml) in the presence of optimal concentrations of NGF. The proliferative/survival profile of the cells was quantitated using the MTT assay as described over a 36-72 hour period (FIG. 3).
Serum and NGF can rescue SFM induced apoptosis. Addition of certain NGF analogs of the present invention can prevent NGF-mediated rescue, but not serum-mediated rescue an listed in Table IV. Proliferation was calculated as a percent of maximum (serum-induced-100%).
TABLE IV______________________________________Sequence Code SEQ ID NO:______________________________________Peptide 1 = Fmoc-YCTDEKQCY-OH C(92-95) SEQ ID NO: 22Peptide 2 = Acetyl-YCTDEKQCY-OH C(92-96) SEQ ID NO: 22Peptide 3 = Fmoc-YCDIKGKECY-OH C(30-35) SEQ ID NO: 2Peptide 4 = Acetyl-YCDIKGKECY-OH C(30-35) SEQ ID NO: 2______________________________________
FIG. 3 is a graph which illustrates the assays results indicated significant differances from NGF treated cells.
The NGF antagonistic activity of the analogs further indicates that they are structural analogs of NGF. The importance of these assays is two fold. First, the analogs were effective in bioassays using cells other than PC12 cells, expanding the types of tissues tested. Second, it is shown that lack of NGF availability, due to antagonistic activity of the analogs, can induce an active process of cell death (apoptosis). This antagonism may be desired in cases of neuromas at the end of an amputated limb.
Effect of NGF Analogs on trkA Receptor Internalization
Some of the peptide analogs are shown to induce internalization of the trkA receptor, which may be one mechanism of downmodulation of receptor.
E25 single cell suspensions were first treated with NGF analog C(92-97) (Fmoc-YCTDEKQACY-OH) (10 μM) or with NGF (2 nM) using conditions which allow ligand-induced induced internalization of surface receptors (37° C., in culture media), or conditions which do not allow internalization (4° C., 0.05% sodium azide) for 30 min. Expression of surface trkA receptors was quantified by FACScan analysis.
FIG. 4A illustrates FACScan profiles using an anti-trkA specific monoclonal antibody versus control mouse IgG.
FIG. 4B is a graph of the analysis of the % reduction of cell surface mean fluorescence channel (MFC, using the Lysis (B.D.) software) after receptor internalization.
NGF and the structural NGF analog C(92-97) induced the disappearance of surface trkA receptors at the permissive conditions only, indicating ligand-induced receptor internalization.
Induced internalization of receptors by their ligands at 37° C. (permissive conditions) is a well-known process. Internalization requires receptor association with cytoskeletal structures, and clathrin-coated vesicles upon ligand binding (Corvera, S. et al. (1989) J. Biol. Chem., 264:12568-12572). The ability of the analogs to induce internalization is strong evidence of their binding to NGF receptors and inducing biophysical changes in the receptor and biological changes in the cell.
Ligands are internalized together with the receptors. This knowledge is useful two fold. First, analogs which are coupled to a toxin can be internalized into a receptor-expressing tumor cell whereby the toxin would then destroy the tumor cell. Second, receptor internalization is a means to temporarily downmodulate receptor expression or responses to a ligand.
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.
__________________________________________________________________________# SEQUENCE LISTING- (1) GENERAL INFORMATION:- (iii) NUMBER OF SEQUENCES: 23- (2) INFORMATION FOR SEQ ID NO: 1:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 8 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: one-of (1 - #, 8)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#1: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Lys Gly Lys Glu Cys Xaa1 5- (2) INFORMATION FOR SEQ ID NO: 2:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 10 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: one-of (1 - #, 10)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#2: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Asp Ile Lys Gly Lys Glu Cys Xaa# 10- (2) INFORMATION FOR SEQ ID NO: 3:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 11 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - 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#e (B) LOCATION: one-of (1 - #, 10)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#12: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Ser Asn Pro Val Glu Ser Cys Xaa# 10- (2) INFORMATION FOR SEQ ID NO: 13:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 11 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: one-of (1 - #, 11)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#13: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Ala Ser Asn Pro Val Glu Ser Cys Xa - #a# 10- (2) INFORMATION FOR SEQ ID NO: 14:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: 1#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#14: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Ala Ser Asn Pro Val Glu Cys1 5- (2) INFORMATION FOR SEQ ID NO: 15:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 10 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: one-of (1 - #, 10)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#15: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Ala Ser Asn Pro Val Glu Cys Xaa# 10- (2) INFORMATION FOR SEQ ID NO: 16:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide#16: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Arg Ala Ser Asn Pro Val Glu Ser Gly1 5- (2) INFORMATION FOR SEQ ID NO: 17:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide#17: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Ala Asn Val Ser Arg Ser Pro Glu Gly1 5- (2) INFORMATION FOR SEQ ID NO: 18:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: one-of (1 - #, 9)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#18: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Thr Asp Glu Lys Gln Cys Xaa1 5- (2) INFORMATION FOR SEQ ID NO: 19:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 10 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: one-of (1 - #, 10)#/note= "Xaa is any uncharged amino acid or hydrop - #athic amino acid"#19: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Xaa Cys Thr Asp Glu Lys Gln Ala Cys Xaa# 10- (2) INFORMATION FOR SEQ ID NO: 20:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide#20: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Thr Thr Asp Glu Lys Gln Ala Ala Trp1 5- (2) INFORMATION FOR SEQ ID NO: 21:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide#21: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Thr Glu Gln Ala Thr Asp Lys Ala Trp1 5- (2) INFORMATION FOR SEQ ID NO: 22:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide#22: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- Tyr Cys Thr Asp Glu Lys Gln Cys Tyr1 5- (2) INFORMATION FOR SEQ ID NO: 23:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (C) STRANDEDNESS: single (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide#23: (xi) SEQUENCE DESCRIPTION: SEQ ID NO:- His Cys Thr Asp Glu Lys Gln Cys His1 5__________________________________________________________________________
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Cyclic compounds with a 3-dimensional structure that bind at least one neurotrophin receptor (NTR) under physiologic conditions in vitro or in vivo are new. Binding to NTR at least partially mimics or inhibits NT biological activity.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 07/871,651, filed on Apr. 21, 1992, now U.S. Pat. No. 5,340,646.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a porous film, and particularly relates to a hydrolyzable, porous film which comprises a polylactic acid-based resin composition essentially consisting of a lactic acid-based polymer having hydrolyzability in the natural environment and a finely-powdered filler.
The porous film of the invention has high moisture permeability and breathability and is also excellent in flexibility, and is hence suitable for uses such as leak-proof films for a disposable paper diaper and other sanitary materials, packaging materials and filter media. Additionally the porous film is prepared from the polylactic acid-based resin composition and has hydrolyzability. Consequently, the porous film is expected for a countermeasure of waste disposal which has recently been a serious problem.
2. Description of the Related Art
Porous films have already been prepared by blending a specific proportion of an organic or inorganic incompatible matter with polyolefine-based resin, melting, film-forming and stretching the resultant film as disclosed in Japanese Patent Publication Sho 53-2542 and Japanese Laid-Open Patent Sho 56-99242, 57-59727, 60-129240 and 62-138541.
These porous films are mainly used for leakproof films for sanitary materials such as a disposable paper diaper and packaging materials, and are generally applied to so-called throw away uses where the films are abandoned immediately after use.
However, the porous films prepared from polyolefine-based resin cannot be hydrolyzed or have a very slow rate of hydrolysis in the natural environment. As a result, these films remain semipermanently when buried under the ground after use. Disposal of these films in the ocean causes aesthetic damage or destruction of the living environment of marine organisms. Thus, disposal of wastes has become a social problem with expansion in consumption.
On the other hand, polylactic acid and its copolymer have been known as a thermoplastic and hydrolyzable polymer. For example, U.S. Pat. No. 1,995,970 discloses a preparation process of a lactic acid-based polymer by polymerization of lactic acid, lactide or a mixture of these compounds.
These lactic acid-based polymers can be obtained by fermentation of inexpensive materials such as corn starch and corn syrup and can also be prepared from petrochemicals such as ethylene. The lactic acid-based polymer, however, is generally high in hardness and hence has a disadvantage of having low flexibility when used in the form of a film. Consequently, the lactic acid-based polymer has been thought to have many restrictions in use and a porous film of the lactic acid-based polymer has not yet been known.
That is, a porous film consisting of polylactic acid or its copolymer which has hydrolyzability in the natural environment has not yet been known and is a material for providing useful goods in view of the above market demand and protection of the natural environment. Thus, the development of the lactic acid-based porous films has been strongly desired.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a porous film which is plasticized, if desired, and has hydrolyzability.
Another object of the present invention is to provide a porous film which is plasticized and has hydrolizability and moreover which is excellent in long-term stability of mechanical properties such as tensile strength and so on.
As a result of an intensive investigation in order to accomplish the above object, the present inventors have found that a porous film having suitable flexibility and hydrolyzability can be obtained by adding a specific amount of a finely-powdered filler to a specific amount of a polylactic acid-based resin composition comprising a specific amount of a lactic acid-based polymer and a specific amount of a plasticizer, melting and film-forming the resultant mixture, and stretching the thus-obtained film. Thus, the present invention has been completed.
One aspect of the present invention is a porous film obtained by the process comprising adding from 40 to 250 parts by weight of a finely-powdered filler having an average particle size of from 0.3 to 4 μm 100 parts by weight of a polylactic acid-based resin composition comprising from 80 to 100% by weight of polylactic acid or a lactic acid-hydroxycarboxylic acid copolymer and from 0 to 20% by weight of a plasticizer, melting and film-forming the resultant mixture, and successively stretching the thus-obtained film 1.1 times or more at least in the one direction of the axis. The hydrolyzable, porous film of the invention is characterized by hydrolyzability and is prepared by adding the finely-powdered filler having a specific particle size to the polylactic acid-based resin composition having a specific composition, mixing with a Henschel mixer, successively melt-kneading after pelletizing or as intact with a single- or twin-screw extruder, delivering through a ring or flat die to form a film, and stretching to provide porosity for the thus-obtained film.
The porous film of the invention has breathability, can provide various grades of flexibility and stiffness, and additionally is hydrolyzable. Consequently, the film is useful as a material for leakproof films of sanitary materials such as a paper diaper and packaging materials. The film is hydrolyzed in the natural environment in the case of discarding after use and hence does not accumulate in the form of industrial wastes.
DETAILED DESCRIPTION OF THE INVENTION
The lactic acid-based polymer of the present invention is polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid. Exemplary hydroxycarboxylic acid includes glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid and hydroxyheptanoic acid. Preferred hydroxycarboxylic acid is glycolic acid and hydroxycaproic acid.
Preferred molecular structure of polylactic acid is composed of from 85 to 100% by mole of an L-lactic acid unit or D-lactic acid unit and from 0 to 15% by mole of the antipode unit of each lactic acid. The copolymer of lactic acid and hydroxycarboxylic acid is composed of from 85 to less than 100% by mole of an L-lactic acid unit or D-lactic acid unit and less than 15% by mole of a hydroxycarboxylic acid unit.
The lactic acid-based polymer can be prepared by selecting the raw material monomer required for obtaining a desired polymer structure from L-lactic acid, D-lactic acid and hydroxycarboxylic acid and carrying out dehydrating polycondensation. The polymer can be preferably prepared by using lactide which is a cyclic dimer of lactic acid, glycolide which is a cyclic dimer of glycolic acid, and caprolactone and carrying out ring-opening polymerization.
The lactide includes L-lactide which is a cyclic dimer of L-lactic acid, D-lactide which is a cyclic dimer of D-lactic acid, meso-lactide obtained by cyclizing dimerization of D-lactic acid and L-lactic acid, and DL-lactide which is a racemic mixture of D-lactide and L-lactide. Any of these compounds can be used for the invention. However, preferred main materials are D-lactide and L-lactide.
The lactic acid-based polymer which can be preferably, used for the invention is a lactic acid-based polymer essentially consisting of from 85 to 100% by mole of an L-lactic acid unit or D-lactic acid unit and from 0 to 15% by mole of the antipode lactic acid unit and/or glycolic acid unit.
The lactic acid-based polymer can be prepared by the following processes 1 to 6.
1 About 85% by mole or more of L-lactide is copolymerized with about 15% by mole or less of D-lactide and/or glycolide.
2 About 85% by mole or more of D-lactide is copolymerized with about 15% by mole or less of L-lactide and/or glycolide.
3 About 70% by mole or more of L-lactide is copolymerized with about 30% by mole or less of DL-lactide and/or glycolide.
4 About 70% by mole or more of L-lactide is copolymerized with about 30% by mole or less of meso-lactide and/or glycolide.
5 About 70% by mole or more of D-lactide is copolymerized with about 30% by mole or less of DL-lactide and/or glycolide.
6 About 70% by mole or more of D-lactide is copolymerized with about 30% by mole or less of meso-lactide and/or glycolide.
The lactic acid-based polymer has preferably a high molecular weight. The inherent viscosity of the polymer at 25° C. in a chloroform solution having a concentration of 0.5 g/dl is preferably 1˜10, more preferably 3˜7.
When the inherent viscosity is less than 1, melt viscosity is too low, the polymer causes drooling from the die slit of the extruder and thus processing becomes difficult. Additionally, the product thus obtained is very brittle and difficult to handle. On the other hand, an inherent viscosity exceeding 10 causes too high melt viscosity and unfavorably gives adverse effect on the melt extrudability of the polymer.
Catalysts are preferably used in order to obtain a high molecular weight polymer within a short time by the polymerization of lactide or copolymerization of lactide and glycolide.
The polymerization catalysts which can be used are various compounds capable of exhibiting catalytic effect on the polymerization reaction. Exemplary catalysts include stannous octoate, tin tetrachloride, zinc chloride, titanium tetrachloride, iron chloride, boron trifluoride ether complex, aluminum chloride, antimony trifluoride, lead oxide and other polyvalent metal compounds. Tin compounds and zinc compounds are preferably used. Stannous octoate is particularly preferred in these tin compounds. The amount is preferably in the range of from 0.001 to 0.1% by weight for the weight of lactide or the total weight of lactide and glycolide.
Known chain extenders can be used for the polymerization. Preferred chain extenders are higher alcohols such as lauryl alcohol and hydroxy acids such as lactic acid and glycolic acid. Polymerization rate increases in the presence of a chain extender and polymer can be obtained within a short time.
Molecular weight of the polymer can also be controlled by varying the amount of the chain extender. However, too much amount of the chain extender tends .to decrease molecular weight of polymer formed. Hence, the amount of the chain extender is preferably 0.1% by weight or less for lactide or for the total weight of lactide and glycolide.
Polymerization or copolymerization can be carried out in the presence or absence of a solvent. Bulk polymerization in a molten state of lactide or glycolide is preferably carried out in order to obtain high molecular weight polymer.
In the case of molten polymerization, polymerization temperature may be generally above the melting point (around 90° C.) of the monomer, lactide or glycolide. In the case of solution polymerization which uses solvents such as chloroform, polymerization can be carried out at temperature below the melting point of lactide or glycolide. In any case, polymerization temperature above 250° C. is unfavorable because decomposition of formed polymer develops.
The polylactic acid-based resin composition of the invention comprises from 80 to 100% by weight of the above lactic acid-based polymer and from 0 to 20% by weight of a plasticizer.
The plasticizers which can be used include, for example, di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, di-iso-octyl phthalate and other phthalic acid derivatives; di-n-butyl adipate, dioctyl adipate and other adipic acid derivatives; di-n-butyl maleate and other maleic acid derivatives; tri-n-butyl citrate and other citric acid derivatives; monobutyl itaconate and other itaconic acid derivatives; butyl oleate and other oleic acid derivatives; glycerol monoricinolate and other ricinoleic acid derivatives; tricresyl phosphate, trixylenyl phosphate and other phosphoric acid esters; lactic acid, straight chain lactic acid oligomer, cyclic lactic acid oligomer and lactide. These plasticizers can be used singly or as a mixture. In these plasticizers, lactic acid, straight chain lactic acid oligomer, cyclic lactic acid oligomer and lactide are preferably used in view of their plasticizing effect. Lactic acid oligomers used for the plasticizer can be prepared with ease by hot-dehydrating condensation of lactic acid at 50° to 280° C.
The oligomer thus obtained usually has a polymerization degree in the range of from 1 to 30. The oligomer can also be prepared by heating glycolide or lactide at 50° to 280° C. in the presence of water and glycolic acid or lactic acid. The oligomer also includes lactide, i.e., cyclic dimer of lactic acid which is used as a monomer in the preparation of lactic acid-based polymer.
The lactic acid-based polymer is effectively plasticized by the addition of the plasticizer and resulting resin composition becomes flexible. When the amount of the plasticizer is 5% by weight or more, flexibility can be clearly observed. However, an amount exceeding 20% by weight gives adverse effect on the melt-extension and stretching of the resin composition and unfavorably decreases mechanical strength of the porous film obtained.
The plasticizer is blended with the lactic acid-based polymer by dissolving the polymer in a solvent such as chloroform, methylene chloride, toluene or xylene, or heat-melting the polymer at 100° to 280° C., and thereafter adding and mixing a prescribed amount of the plasticizer.
Lactic acid or lactic acid oligomer including lactide which is a preferred plasticizer is mixed, for example, by the following methods:
(a) Polymerization of lactide or copolymerization of lactide and glycolide is stopped before completion to leave unreacted lactide.
(b) After completing polymerization of lactide or copolymerization of lactide and glycolide, a prescribed amount of lactic acid or a lactic acid oligomer including lactide is added and mixed. Methods (a) and (b) can be incorporated.
In the method (a), unreacted lactide is uniformly mixed with the lactic acid-based polymer on microscopic observations and exhibits good plasticizing performance. Reaction of monomer (lactide) is started by heating in the presence of a catalyst, in the coexistence of a chain extender, if desired, and stopped by finishing the heating at the time when the residual monomer concentration reaches to a prescribed level. The amount of residual monomer in the resulting lactic acid-based polymer can be determined by gas chromatographic analysis or thermogravimetric analysis.
In the method (b), after finishing polymerization, the resulting lactic acid-based polymer is dissolved in a solvent such as chloroform, methylene chloride, toluene and xylene, or heat-melted at temperature of 100° to 280° C. and successively a prescribed amount of lactic acid or the lactic acid oligomer is added and mixed. The method has an advantage of readily controlling the amount of lactic acid or the lactic acid oligomer in the resin composition.
The polylactic acid-based resin composition obtained above is compression-molded or melt-extruded at temperature of 180° to 280° C. into films, sheets or bars. These molded articles are cooled to about -20° C. with dry ice-methanol and crushed with a hammer mill. Alternatively, the resin composition can also be melt-extruded into a strand and cut into pellets.
The polylactic acid-based resin composition thus crushed or pelletized is then mixed with a finely-powdered filler. The finely-powdered filler may be mixed with the lactic acid-based polymer simultaneously with blending of the plasticizer.
The plasticizer affects long-term stability of mechanical properties such as tensile strength and so on of the porous film obtained. When it is considered, especially preferable plasticizers are citric acid derivatives among the above plasticizers. More preferable plasticizers are acetyl tributyl citrate and acetyl triethyl citrate. The decreasing trend in tensile strength of the porous film containing the above plasticizer is little even after 2 years.
Lactic acid, lactic acid oligomer and lactide are excellent in plasticizing effect, and hence, a flexible porous film is obtained with ease. However, a porous film which contains 10% by weight or more of plasticizers such as lactic acid, lactic acid oligomer and lactide is not necessarily sufficient in the long-term stability of mechanical properties such as tensile strength and so on. To disclose more concretely, while the above porous film does not show a decreasing trend in tensile strength for half a year after production, it does gradually show a decreasing trend in tensile strength after a year or more.
On the other hand, a porous film plasticized by a citric acid derivative does not show a decreasing trend in tensile strength even after a year or more. Therefore, use of the citric acid derivative as a plasticizer is preferable, when it is desired to obtain a porous film of a lactic acid-based polymer which has low hydrolyzability and excellent long-term stability of mechanical properties such as tensile strength and so on.
Exemplary citric acid derivative as a plasticizer includes triethyl citrate, tributyl citrate, monoisopropyl citrate, monostearyl citrate, distearyl citrate, tristearyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl tri-2-ethylhexyl citrate and the like. Preferred citric acid derivative is acetyl tributyl citrate, acetyl triethyl citrate and tributyl citrate.
The finely-powdered filler which can be used for the invention is inorganic or organic fine powder.
Exemplary inorganic fine powder includes calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, barium oxide, aluminum oxide, aluminium hydroxide, hydroxyapatite, silica, mica, talc, kaolin, clay, glass powder, asbestos powder, zeolite and acid clay. Particularly preferred inorganic fillers are calcium carbonate, magnesium oxide, barium sulfate, silica and acid clay.
The organic fine powder includes, for example, wood flour, pulp powder and other cellulosic powder.
The finely-powdered filler preferably has an average particle size of from 0.3 to 4 μm, and more preferably has a specific surface area of 15 m 2 /g or less in addition to this range of the average particle size. The most preferred filler has a specific surface area in the range of from 0.5 to 5 m 2 /g.
An average particle size exceeding 4 μm gives adverse effect on the stretching ability of the film and sometimes leads to film breakage prior to uniform whitening. Consequently, stability of operation becomes poor and uniform porosity of the film is difficult to obtain. When the average particle size is less than 0.3 μm, high filling of the inorganic fine particle becomes difficult and it is impossible to make the film porous. On the other hand, when the specific surface area exceeds 15 m 2 /g, the form of the inorganic finely-powdered filler becomes amorphous, needle or plate. Consequently, particle size distribution becomes broad, stretching ability of the film decreases, and processing ability for making the porous film is unfavorably impaired.
The amount of the finely-powdered filler for use in the invention is from 40 to 250 parts by weight, preferably from 60 to 150 parts by weight per 100 parts by weight of the polylactic acid-based resin composition. An amount less than 40 parts by weight leads to insufficient porosity and low percentage of open cells, and hence satisfactory breathability and moisture permeability cannot be obtained. On the other hand, an amount exceeding 250 parts by weight gives adverse effect on the melt-extendability, film-forming ability and stretching ability.
Next, preparation process of the porous film of the invention will be illustrated.
The finely-powdered filler is added to the polylactic acid-based resin composition, mixed for 5 to 30 minutes at room temperature with a blender such as Henschel mixer, super mixer and tumbling mixer, followed by melt-kneading with a common single- or twin-screw extruder and pelletizing the extrudate.
The pellets thus-obtained are successively processed into a film by an inflation method or T-die extrusion method. The film can also be obtained directly from the extruder without pelletizing.
Extrusion temperature is preferably in the range of from 100° to 270° C., more preferably in the range of from 130° to 250° C. When the temperature is lower than 100° C., extrusion stability is difficult to obtain and overload is liable to occur. On the other hand, a temperature exceeding 270° C. is unfavorable because decomposition of the lactic acid-based polymer becomes violent.
The die of the extruder used in the invention is a ring or flat die. Temperature range of the die is about the same as extruding temperature.
Successively, the extrudate is stretched from 1.1 to 10 times, preferably from 1.1 to 7 times at least in the direction of the axis. Stretching can be carried out in multi-steps or conducted biaxially. When the degree of stretching is less than 1.1 times, the porosity of the film is unsatisfactory. The degree of stretching exceeding 10 times often leads to unfavorable breakage of the film.
Preferred stretching temperature is in the range of from the glass transition temperature (Tg) of the lactic acid-based polymer to Tg+50° C. After stretching, heat setting can be carried out in order to enhance form stability of the pores.
Thickness of the porous film differs depending upon uses and is generally in the range of from 10 to 300 μm.
Colorants, reinforcements and other types of fillers can also be added unless the object of the invention is impaired.
The present invention will hereinafter be illustrated further in detail by way of examples.
Following evaluation methods were used in the examples.
1 Amount of residual monomer
After finishing the polymerization reaction, the reaction mixture was dissolved in hexafluoroisopropanol (hereinafter referred to as HFIP) or methylene chloride to obtain a solution having known concentration. Residual monomer was determined by gas chromatography.
2 Inherent viscosity
A lactic acid-based polymer is dissolved in chloroform (concentration; 0.5 g/dl), viscosity of the resulting solution was measured at 25°±0.5° C. with a Ubbelohde viscometer, and inherent viscosity η was calculated from the following equation.
η=log(T.sub.1 /T.sub.0)/C
wherein
To: Measuring time of the solvent (sec)
T 1 : Measuring time of the solution (sec)
C: Concentration of the sample solution (g/dl)
3 Specific surface area
Measured by the BET absorption method
4 Average particle size
A powder specific surface area tester (permeation method) Model SS-100 (manufactured by Shimadzu Seisaku-sho Co.) was used. To a sample cylinder having a sectional area of 2 cm 2 and a height of 1 cm, 3 g of the sample was filled, and the average particle size was calculated from the time required for permeating 50 cc of the air through the filled layer under the pressure of 500 mmH 2 O.
5 Permeability
Measured in accordance with ASTM-E-96-66
6 Polymerization degree of oligomer
An oligomer was dissolved in tetrahydrofuran or chloroform, distribution of the polymerization degree was measured by gel permeation chromatography (GPC) to calculate polymerization degree of the oligomer.
7 Tensile strength
A tensile strength tester Model Universal Material Tester UCT (manufactured by Orientec Co. Ltd.) was used. Film samples just produced and film samples left for a year under the conditions of 60% of relative humidity at 23° C. were measured in the longitudinal direction by the tester in accordance with JIS Z-1702.
Preparation Example
To a reaction vessel, 1.8 kg of L-lactide and 1.0 kg of an aqueous lactic acid solution having a concentration of 87% by weight were charged and heated for 2 hours at 100° C. The reaction mixture was cooled to the room temperature. A viscous transparent liquid was obtained. As a result of GPC analysis, the liquid contained lactic acid and a lactic acid oligomer. An average polymerization degree was 2.8. The product was hereinafter referred to as LA-oligomer.
Examples 1˜14, and Comparative Examples 1˜3
Marketed L-lactide (hereinafter referred to as L-LTD), D-lactide (hereinafter referred to as D-LTD), DL-lactide (hereinafter referred to as DL-LTD) and glycolide (hereinafter referred to as GLD) were individually recrystallized 4 times from ethyl acetate.
ε-Caprolactone (hereinafter referred to as CL) was dried over calcium hydride and distilled.
To a glass reaction vessel having a silane-treated internal surface, the above-purified L-LTD, D-LTD, DL-LTD, GLD, CL and a catalyst stannous octoate were respectively charged in an amount illustrated in Table 1. Then the resulting mixture was dried for 24 hours by evacuating the reaction vessel.
The reaction vessel was heated to the prescribed temperature illustrated in Table 1 and polymerization was carried out for the prescribed time. After finishing the reaction, the reaction mixture was discharged from the vessel. The lactic acid-based polymers thus-obtained were referred to as P1˜P6.
The inherent viscosity and residual monomer content were measured and results are illustrated in Table 1.
TABLE 1______________________________________Lactic acid-based polymer P1 P2 P3 P4 P5 P6______________________________________L-LTD (wt. parts) 100 70 95 75 50 80DL-LTD (wt. parts) -- 30 -- 30 50 --D-LTD (wt. parts) -- -- 5 -- -- --GLD (wt. parts) -- -- -- 5 --CL (wt. parts) -- -- -- -- -- 20Catalyst (wt. %) 0.015 0.015 0.015 0.015 0.015 0.015Polymerization 110 120 110 120 125 120temperature (°C.)Polymerization 160 120 40 120 100 140time (hr)Inherent 4.2 6.1 3.8 5.1 5.4 4.3viscosityResidual 1.3 0.9 13.1 1.1 1.5 1.9monomer (wt. %)______________________________________
Next, L-LTD or LA-oligomer obtained in the Preparation Example was added to these lactic acid-based polymers in a proportion illustrated in Table 2, mixed with a plastomill at temperature illustrated in Table 2 to obtain polylactic acid-based resin compositions C1 to C7.
These resin compositions were pressed under the pressure of 100 kg/cm 2 at the temperature illustrated in Table 2 to obtain a sheet having a thickness of 1 mm.
TABLE 2__________________________________________________________________________Composition C1 C2 C3 C4 C5 C6 C7__________________________________________________________________________Lactic acid- P1 P2 P2 P2 P4 P5 P6base polymer 80 90 80 90 80 90 90(wt. %)Additive LA LA LA LTD LA LA LA(wt. %) oligomer oligomer oligomer monomer oligomer oligomer oligomer 20 10 20 10 20 10 10Melt-mixing 210 150 150 150 150 130 130temperature(°C.)Press 210 150 150 150 150 130 130temperature(°C.)__________________________________________________________________________
The polylactic acid-based resin composition illustrated in Table 3 was cooled with liquid nitrogen, crushed with a hammer mill, and followed by adding a finely-powdered filler having an average particle size illustrated in Table 3 in an amount illustrated in Table 3 for 100 parts by weight of the polylactic acid-based resin composition and mixing with a Henschel mixer at the room temperature.
The resulting mixture was pelletized with a twin-screw extruder.
TABLE 3______________________________________Polylactic Finely-powdered filleracid-based Averageresin particlecomposi- size Amounttion Compound (μm) (wt part)______________________________________Example1 P1 Precipitated BaSO.sub.4 0.8 2002 P2 ↑ 0.8 1203 P3 ↑ 0.5 504 P5 MgO 1.1 805 P6 Precipitated BaSO.sub.4 1.1 1206 C1 ↑ 1.1 1207 C2 ↑ 1.1 1208 C2 Precipitated CaCO.sub.3 0.8 1209 C2 ↑ 0.5 8010 C3 ↑ 0.5 5011 C4 Heavy CaCO.sub.3 2.6 12012 C5 Precipitated BaSO.sub.4 3.0 12013 C5 ↑ 3.5 12014 C7 ↑ 3.5 120Compar-ativeExample1 P1 -- -- 02 P1 Precipitated BaSO.sub.4 0.8 303 C2 ↑ 0.8 300______________________________________
The pellets obtained were melted with a single-screw extruder and delivered through a T-die at 230° C. The extruded film was formed so as to give, after stretching, a porous film having a thickness illustrated in Table 4.
Successively, the film was stretched with rolls at 60° C. to the uniaxial or biaxial direction with a degree of stretching illustrated in Table 4 to obtain a porous film.
Properties of the porous film thus-obtained were evaluated and results are illustrated in Table 4.
TABLE 4__________________________________________________________________________Stretch- Tensile strength*ing Thick- Moisture kg/cm.sup.2degree ness permeability 0 0.5 1 2(times) (μm) (g/m.sup.2 /24 hr) year year year years Remark__________________________________________________________________________Example1 2 36 1500 175 172 170 1602 7 35 2500 167 163 160 1483 3 × 3 35 5500 130 120 90 424 5 34 1800 154 150 145 1315 4 36 2100 170 166 163 1506 7 36 2400 155 138 118 647 5 35 2200 128 122 90 458 5 36 2100 147 137 102 519 5 34 1900 119 112 88 5610 5 35 1700 126 121 94 3511 5 36 2400 144 137 110 3012 5 35 2500 132 126 101 4913 5 35 2800 170 161 131 6214 5 35 2500 140 134 104 38Compar-ativeExample1 1 34 220 -- -- -- -- *12 7 36 <400 -- -- -- -- *23 -- -- -- -- -- -- -- *3__________________________________________________________________________ *tensile strength in the direction of MD, wherein 0, 0.5 year and a year mean just produced time, 0.5 year after production and 1 year after production, respectively. *1: unstretched; *2: fluctuated permeability; *3: extrusion impossible
As illustrated in Table 4, the porous films obtained in Examples 3 and 6-14, which contained 10% or more by weight of lactide or a lactic acid oligomer as plasticizers, did not show a decreasing trend in tensile strength for half a year after production, but it gradually showed decreasing trends in tensile strength after a year or more. Further, decreasing trends in tensile strength of porous films obtained in Examples 15˜18, 20 and 21 were little even after 2 years. On the other hand, the porous films obtained in Examples 1, 2, 4, and 5, which contained less than 10% by weight of lactide or a lactic acid oligomer, did not almost show a decreasing trend in tensile strength even after a year.
Next, the porous film obtained in Examples 1, 2 and 5 and a porous film of polyolefine resin (Espoal N; Trade Mark of Mitsui Toatsu Chemicals Inc.) were respectively immersed in distilled water at 37° C. After 120 days, weight loss was 7%, 13%, 21% and 0%, respectively.
Examples 15˜21
Polylactic acid-based resin compositions C8 to C11 were obtained by the same procedures as Example 1 except that lactic acid-based polymers P-1, P-2 or P-4 and acetyl tributyl citrate, acetyl triethyl citrate or tributyl citrate as a plasticizer were mixed in a proportion as illustrated in Table 5. Results are illustrated in Table 5.
Next, the polylactic acid-based resin composition was added with precipitated BASO 4 or precipitated CaCO 3 as a finely-powdered filler in a proportion as illustrated in Table 6 and mixed by a Henschel mixer at room temperature. The resulting mixture was pelletized with a twin-screw extruder. The pellets obtained were melted with a single-screw extruder and delivered through a T-die at 230° C. Thus, the polylactic acid-based film containing a plasticizer and a finely-powdered filler was obtained.
Successively, the film was uniaxially stretched with 5 times stretching in the longitudinal direction of the film so as to form a porous film. Thickness, moisture permeability and tensile strength were evaluated by the prescribed methods and results are illustrated in Table 7.
As set forth in Table 7, the porous films obtained in Examples 15-21, which contained citric acid derivatives as plasticizers, did not almost show a decreasing trend in tensile strength even after a year or more.
TABLE 5______________________________________Composition C8 C9 C10 C11______________________________________Lactic acid-based P1 P2 P2 P4polymer (wt %) 80 90 80 80Additive Acetyl Acetyl Tributyl Acetyl(wt %) tributyl tributyl citrate triethyl citrate citrate 20 citrate 20 10 20Melt-mixing 140 140 130 140temperature (°C.)Press 140 140 130 140temperature (°C.)______________________________________
TABLE 6______________________________________Polylacticacid-based Finely-powdered filler resin Average composi- particle AmountExample tion Compound size (μm) (wt part)______________________________________15 C8 Precipitated BaSO.sub.4 1.1 12016 C9 ↑ 1.1 12017 C9 ↑ 0.8 12018 C9 ↑ 0.5 8019 C10 Precipitated CaCO.sub.3 0.5 5020 C11 Precipitated BaSO.sub.4 3.0 12021 C11 ↑ 3.5 120______________________________________
TABLE 7__________________________________________________________________________Stretch- Tensile strength*ing Thick- Moisture kg/cm.sup.2degree ness permeability 0 0.5 1 2Example(times) (μm) (g/m.sup.2 /24 hr) year year year years__________________________________________________________________________15 5 35 2400 128 125 122 11016 5 37 2700 130 128 125 11517 5 34 2400 175 171 169 15518 5 33 2800 154 151 150 14219 5 35 2200 138 137 134 7020 5 36 2100 143 141 141 13121 5 35 2600 130 128 123 113__________________________________________________________________________ *tensile strength in the direction of MD, wherein 0, 0.5 year and 1 year mean just produced time, 0.5 year after production and 1 year after production, respectively.
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A breathable, hydrolyzable, porous film having long-term stability in mechanical properties which is obtained by the process comprising adding from 40 to 250 parts by weight of a finely-powdered filler having an average particle size of from 0.3 to 4 μm to 100 parts by weight of a polylactic acid-based resin composition comprising from 80 to 95% by weight of polylactic acid or a lactic acid-hydroxycarboxylic acid copolymer and from 5 to 20% by weight of a plasticizer comprising a citric acid ester, melting and film-forming the resultant mixture, and successively stretching the thus-obtained film 1.1 times or more at least in the direction of the axis; and which is consequently useful as a material for leakproof films of sanitary materials such as a paper diaper and packaging materials, and does not accumulate as wastes because of hydrolyzability in the natural environment in the case of being abandoned after use.
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PRIORITY NOTICE
The present application claims priority under 35 U.S.C. §119(e) and under 35 USC §120, to U.S. patent application with Ser. No. 13/854,795, filed on Apr. 1, 2013, which claims priority to U.S. Provisional Patent Application Serial No. 61/650,179, filed on May 22, 2012, the disclosures of which are incorporated herein by reference in their entirety.
TECHNICAL FIELD OF THE INVENTION
The present apparatus and method relates in general to a plug that is used to repair and restore holes that a tenant drilled in the floor of the space that the tenant occupied during a tenancy.
COPYRIGHT & TRADEMARK NOTICE
A portion of the disclosure of this patent application may contain material that is subject to copyright protection. The owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent file or records, but otherwise reserves all copyrights whatsoever.
Certain marks referenced herein may be common law or registered trademarks of third parties affiliated or unaffiliated with the applicant or the assignee. Use of these marks is by way of example and should not be construed as descriptive or to limit the scope of this invention to material associated only with such marks.
BACKGROUND OF THE INVENTION
Typically, a condition in a lease contract between a commercial building owner and a tenant is that at the end of the lease the tenant must return the leased premises in the same condition that it was in at the time the tenant took possession, save for normal wear and tear. During the course of a tenancy, a lessee will typically cause numerous holes to be drilled into the concrete floor and/or ceiling of his suite to accommodate the routing of electrical wires, plumbing pipes, voice cables, and other such items that run through the floors. In the great majority of mid and high rise office buildings, these floors are constructed of a lightweight aggregate poured on a metal underlayment or pan. This flooring assembly provides a fire break between floors. When the tenant vacates the premises, the drilled holes during the tenancy are left wide open as a result of the removal of the wiring, plumbing, etc. that had been previously installed. This is potentially a breach of the fire control properties of the flooring assembly. These holes are typically three to four inches in diameter, but can range up to twelve inches or larger. Until recently, most property owners did not recognize this as a problem, and as a result did not require the vacating tenant to repair and restore these holes. More recently, it has been recognized, however, as an issue that must be remedied before a new tenant can take possession of the property.
There are several products on the market that can be used to restore the fire break properties of the flooring assembly. Most utilize a mechanical closure of the hole by installing an expandable metal plug or cap, and require that they be installed through the bottom of the hole. This solution often requires that access to the underside of the floor be granted by another tenant or the owner. Such access may be disruptive, cause security and liability issues, necessitate that the repair work be performed after normal working hours, and cause possible damage to another tenant's property. The parts and labor associated with these products tend to be rather expensive as well.
Another problem with other products is that the final repair results in a protruding floor surface. This is a design flaw that complicates future use of the floor where the protrusion is located.
Yet another problem related to repairing holes after a lease has expired is shoddy repair work. To honor the lease, a tenant may merely stuff a rag or other such material in the hole and then fill it with a plaster, such as FIX-IT-ALL™. Such a repair is insufficient, as there is nothing to keep the rag and plaster from falling through the floor into the suite below. Moreover, such a repair may be prone to water leaks and likely does not conform to the fire code, and testing these properties would be overly burdensome, defeating the purpose of the repair in the first place.
It is to these ends that the present apparatus and method has been developed.
BRIEF SUMMARY OF THE INVENTION
To minimize the limitations in the prior art, and to minimize other limitations that will be apparent upon reading and understanding the present specification, the present apparatus describes a precast plug for sealing a hole in a floor comprising a concrete housing and at least one rod whereby the distal end of said at least one rod makes at least one protrusion from at least one edge of said concrete housing.
The present method and apparatus also describes a method for repairing a hole in a floor, comprising the steps of preparing a wet cement mixture, pouring said wet cement mixture into a form mold housing, installing into said form mold housing at least one rod whereby the distal end of said at least one rod makes at least one protrusion from at least one edge of said concrete housing, allowing said mixture to cure with said at least one rod in place, thereby creating a precast plug, grinding at least one groove into said floor to house the distal end of said at least one rod, coating said precast plug's edges with a sealant, placing said precast plug into said hole such that the distal end of said at least one rod rests in said at least one groove, and allowing said sealant to cure.
It is an objective of the present apparatus and method to seal a hole in a floor such as to make it fire resistant, water resistant, and structurally sound.
Is another objective of the present apparatus and method to allow for ease of installation, making a repair job quick and efficient.
It is yet another objective of the present apparatus and method to repair a hole in a floor, such that the apparatus is flush with the floor's surface.
These and other advantages and features of the present apparatus and method are described herein with specificity so as to make the present apparatus and method understandable to one of ordinary skill in the art.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
Elements in the FIGS. have not necessarily been drawn to scale in order to enhance their clarity and improve understanding of these various elements and embodiments of the apparatus and method. Furthermore, elements that are known to be common and well understood to those in the industry are not depicted in order to provide a clear view of the various embodiments of the apparatus and method.
FIG. 1 is a three dimensional exploded cross-section view, depicting a precast plug housing one rod above a cutout section of a floor, before it is place in said floor.
FIG. 2 is a three dimensional cross-section view of a precast plug that has been placed in a hole in a cutout section of a floor.
FIG. 3 depicts a plan cross section view with a precast plug fully installed into a hole.
FIG. 4 depicts a front elevation cross section view of FIG. 3 with a precast plug fully installed into a hole.
FIG. 5 is a plan cross section view of a precast plug in a floor depicting an alternative embodiment comprising two rods housed within a precast plug.
FIG. 6 depicts a front elevation cross section view of FIG. 5 with a precast plug fully installed into a hole.
FIG. 7 is a plan cross section view depicting a further alternative embodiment utilizing two rods.
FIG. 8 depicts a front elevation cross section view of FIG. 7 .
FIG. 9 is a plan cross section view depicting an alternative embodiment of the system and method whereby a rectangular like rod is housed within a precast plug.
FIG. 10 depicts a front elevation cross section view of FIG. 9 .
DETAILED DESCRIPTION OF THE INVENTION
In the following discussion that addresses a number of embodiments and applications of the present apparatus and method, reference is made to the accompanying drawings that form a part thereof, where depictions are made, by way of illustration, of specific embodiments in which the apparatus and method may be practiced. It is to be understood that other embodiments may be utilized and changes may be made without departing from the scope of the apparatus and method.
FIG. 1 is a three dimensional exploded cross-section view, depicting precast plug 101 before it is placed in hole 102 . This embodiment is a basic depiction of how precast plug 101 may function, namely to seal hole 102 . It also depicts the various components of precast plug 101 including rod 104 .
Precast plug 101 may be constructed off site, i.e., from where the hole it intends to repair is located. However, this is not to limit the scope of precast plug 101 . If a particular location required precast plug 101 to be made on site, such as a remote location and time was of the essence, this could be accomplished by making precast plug 101 at the site of hole 102 .
In either case, precast plug 101 may be constructed of the same material as floor 103 , which in the typical scenario will be a lightweight aggregate or other cement, which has fire and water resistant properties in addition to structural integrity, similar to floor 103 . For example, Rapid Set® Cement All™ may be used to construct precast plug 101 , but this is not to limit the scope of the apparatus and method. In another embodiment, precast plug 101 may be constructed of plastic, steel, or any other material suitable for filling a cavity. Where a cement like material is used to prepare precast plug 101 , it may be mixed with the requisite amount of water (and coloring if desired) to form a wet mixture. This mixture may then be poured into a form mold.
The shape and size of form mold, and therefore precast plug 101 , may vary depending upon the type of repair job. The embodiment depicted in FIG. 1 shows precast plug 101 as having a cylindrical shaped housing with a slight inward taper from the top of precast plug 101 where logo 105 is located to the bottom of precast plug 101 . However, a straight cylindrical form mold may also be employed to create precast plug 101 with no taper. Other embodiments of precast plug 101 may be cast in square, rectangular, triangular, and other variable sized and shaped form molds to create variable sized and shaped precast plugs 101 . Precast plug's 101 diameter (or general width) is also variable depending upon the actual size of hole 102 to be repaired. A larger hole may necessitate a larger diameter form mold while a smaller hole may necessitate a smaller diameter form mold. Finally, the height of hole 102 is relevant to the size of the form mold to be used, which in the typical repair job may be three and one/half inches. The embodiment shown in FIG. 1 depicts precast plug 101 to be of substantially the same height as the height of hole 102 , meaning from the top of floor 103 to the bottom of floor 103 , however the actual height of precast plug 101 may vary.
Before the cement mixture cures in the properly sized form mold, an appropriately sized rod 104 may be inserted into the wet cement housing of precast plug 101 . Rod 104 may be comprised of any number of materials, including steel, plastic, multiples of rods, etc., as will be further discussed below. As depicted in FIG. 1 , rod 104 may be constructed of steel and may also be bent or molded such that it forms a “C” like shape in the center of rod 104 . This allows for the “C” portion of rod 104 to be fully embedded within the form mold cement mixture, and the ends of rod 104 to extend from either side of what is soon to become precast plug 101 after curing. The ends, or “wings” of rod 104 , may give precast plug 101 support when resting in hole 102 and prevent precast plug 101 from falling through the floor.
Precast plug 101 may also be embossed as depicted in FIG. 1 with logo 105 before cement mixture cures. However this is not to limit the scope of the apparatus and method. Logo 105 may also be a stamp, painting, etching, or any other mark to indicate who made precast plug 101 . In FIG. 1 , logo 105 consists of a capital “C” and a capital “P” indicating for example, a trademark. However, logo 105 may also consist of other combinations of letters, numbers, symbols, and/or pictures.
Precast plug 101 may also be stamped, as depicted in FIG. 1 , with size indicator 106 . Again, size indicator 106 may also be embossed, painted, etched, or generally engraved in such a way that it clearly communicates information about precast plug's 101 and/or hole's 102 dimensions. In FIG. 1 , it may be noted that size indicator 106 is represented by a “#30”. This may be a shorthand method of indicating that hole 102 is three inches for example. It could also be used to communicate that the width of precast plug 101 is three inches, if that would be a preferable method of measuring. However, other methods of communicating the size of precast plug 101 or the size of hole 102 may be employed such as a size indicator 106 depiction of “(3″)” or “3 In.”.
Logo 105 and size indicator 106 may also be used to communicate other desirable information, such as implied information. Implied information may be apprised from both logo 105 and size indicator 106 to indicate to appropriate authorities, such as a fire marshal, that the plug that is going to be installed or already has been installed into floor 103 is of such a quality and design that it meets appropriate fire codes and/or other safety regulations.
Further depicted in FIG. 1 are grooves 107 on either side of hole 102 . Grooves 107 may not be preexisting. If not, grooves 107 may be ground out, for example, with an angle grinder, chiseled with a chisel, or carved out using some other device or mechanism to accommodate the “wings” of rod 104 . Once the appropriate number of grooves 107 are carved out (and in the proper places), precast plug 101 may be inserted into hole 102 such that each “wing” of rod 104 may rest snugly within its own groove 107 and the top of precast plug 101 may rest flush with floor 103 .
In another embodiment of the apparatus and method, rather than utilizing the technique of grooves 107 , holes may be drilled in either side of the wall of hole 102 , beneath the surface of floor 103 . Similar tools may be employed as may be used to carve out grooves 107 , including a right angle drill. Utilizing this technique, it would be possible not only to repair a hole in a floor below ones feet, but also a floor above one's head, i.e. a ceiling. In such a case, various embodiments of precast plug 101 may include logo 105 and size indicator 106 embossed or otherwise marked on the bottom side of precast plug 101 , or rather on both ends of precast plug 101 to make it visible to one viewing precast plug 101 from above or below. The “wings” of rod 104 may also extend from a more central portion of precast plug 101 rather than being substantially flush with the top of precast plug 101 . To accommodate the “wings” of rod 104 it may be necessary to drill deeper holes on either side of hole 102 . After drilling the holes, one “wing” of rod 104 may be fully inserted into said drilled hole such that the side of precast plug 101 and interior of hole 102 are flush and the other “wing” of rod 104 is fully within hole 102 and extended in the direction of the drilled hole that it is to occupy. The entirety of precast plug 101 may then be laterally moved in that direction such that it is centered in hole 102 and both “wings” of rod 104 come to rest in either drilled hole.
FIG. 2 is a three dimensional cross-section view of precast plug 101 , that has been placed in hole 102 in a cutout section of floor 103 . This embodiment is a basic depiction of how precast plug 101 functions, i.e. to seal hole 102 such that hole 102 is fire resistant, water resistant, and structurally sound. FIG. 2 also depicts how the top portion of precast plug 101 may not protrude from floor 103 , but is relatively flush with floor 103 . FIG. 2 further depicts how the bottom of precast plug 101 may be flush with the bottom side of floor 103 .
Before appropriately sized precast plug 101 is fitted into hole 102 , however, sealant 201 may be beaded around the exterior wall of precast plug 101 and the interior wall of hole 102 , after which precast plug 101 may be fitted into hole 102 . Once the “wings” of rod 104 are snugly within grooves 107 , sealant 201 may be inserted into any voids such that hole 102 is completely full and/or excess sealant 201 may be wiped away from the area of hole 102 . Sealant 201 may also be applied over the top of the “wings” of rod 104 to further secure rod 104 in place. After sealant 201 cures, what is left is a fire resistant, water resistant, and structurally sound repair job, which may be impliedly indicated by logo 105 as discussed above. As an example, 3M™ Fire Barrier Sealant IC 15WB+ may be used as sealant 201 , however, this is not to limit the scope of the apparatus and method. Other products with similar properties may be employed in lieu of said brand.
FIG. 3 depicts a plan cross section view with precast plug 101 fully installed into hole 102 in a cutout section of floor 103 . FIG. 3 also introduces another aspect of the present apparatus and method, videlicet, the various dimensions of the apparatus and method. Before installation of precast plug 101 , it may be necessary to measure the size of hole 102 that is to be repaired. For example, size indicator 106 depicts a “#30”, which may mean that before installation, it was measured that the size of hole 102 to be repaired was three inches. In such a case, whatever the width of hole 102 may be, D 2 represents this dimension. D 1 represents the width of precast plug 101 . Finally, both d's represent the portion of how far rod 104 extends into floor 103 . Depending upon the nature of the repair to be made, any and all of these dimensions may be lengthened or shortened to accommodate the repair.
FIG. 3 also depicts sealant 201 surrounding precast plug 101 . Sealant 201 , however, may also be applied over the top rod 104 to give further stability to the system and method.
FIG. 4 depicts a front elevation cross section view of FIG. 3 with precast plug 101 fully installed into hole 102 in a cutout section of floor 103 . The location of the cross section is indicated in FIG. 3 by the 4 - 4 cross section line. As can be seen in this embodiment, rod 104 has a “C” shaped bend allowing for rod 104 to penetrate into the center of precast plug 101 . This bend into the center of precast plug 101 allows for rod 104 to lend structural support to precast plug 101 . Also seen from this view, the “wings” of rod 104 extend into floor 103 on either side of precast plug 101 , where grooves 107 may have been chiseled to allow for proper installation of precast plug 101 . This embodiment also depicts the slight inward taper of precast plug 101 at an unspecified degree. However, as mentioned above, this taper is not necessary, and in another embodiment, precast plug 101 may have an outward taper, which may make it easier to apply sealant 201 . Another dimension depicted in FIG. 4 is the height h of floor 103 . As mentioned above, precast plug 101 may be adapted to accommodate the varying heights of concrete floors in different buildings.
FIG. 4 also depicts sealant 201 as extending from the bottom edge of floor 103 to the top edge of floor 103 and fully encompassing the space between floor 103 and precast plug 101 . In another embodiment, less sealant 201 may be applied such that enough is applied to fulfill its purpose, which is to seal hole 102 .
FIG. 5 is a plan cross section view depicting an alternative embodiment comprising two rods 104 housed within precast plug 101 rather than one as in previous figures. Two rods 104 may be suitable to lend further support for a larger precast plug 101 to repair a wider diameter hole 102 or a floor 103 of an increased height. FIG. 5 depicts a different sized precast plug 101 as indicated by size indicator 106 . As discussed above, size indicator may refer to the size of precast plug 101 or the size of hole 102 . For example the “#65” in FIG. 5 may indicate that hole 102 has a diameter of six point five inches.
The front elevation cross section view in FIG. 6 of FIG. 5 depicts a similar view as in FIG. 4 . The location of the cross section is indicated in FIG. 5 by the 6 - 6 cross section line. This embodiment generally depicts, however, how rod 104 may be lengthened in order to accommodate a larger precast plug 101 that may be situated in a deeper hole 102 as may be the case with floor 103 of a greater height, such that rod 104 may still penetrate the center of precast plug 104 and lend its full support.
FIG. 7 is a plan cross section view of another embodiment of the apparatus and method utilizing two rods. However, as shown and as clarified further by the 8 - 8 cross section line in FIG. 8 , the two separate rods 104 act as their own “wings” and are not part of a single rod 104 . These separate rods 104 may be inserted into precast plug 101 in a similar fashion as described above, i.e., before the wet cement mixture fully cures within the form mold and such that the “wings” are substantially flush with the top of precast plug 101 . In another embodiment, rods 104 may be positioned such that the “wings” of said rod extend from a central or lower position on either side of precast plug 101 , rather than being flush with the top of precast plug 101 . Utilizing one of these embodiments, precast plug 101 may be inserted into a ceiling as described above.
FIG. 7 further depicts another potential embodiment as represented by size indicator 106 , which shows a “#45”. This may represent that either hole 102 or precast plug 101 has a width of four and one/half inches.
However, the embodiments depicted in FIGS. 7 and 8 are not to be construed as limiting the scope of the present apparatus and method. For example, rods 104 in FIG. 7 need not be within substantially the same plane as one another, but may be cured into precast plug 101 in a staggered fashion such that they are rather substantially parallel to one another. In another embodiment, four separate rods 104 similar to those used in FIGS. 7 and 8 may be cured into a single precast plug 101 and arranged in a fashion such that there are two pairs of rods 104 (see FIG. 7 for an example of an arrangement of one pair of rods) with each pair on substantially the same plane when viewed from above and the first pair being substantially parallel with the second pair.
In yet another embodiment, four separate rods 104 similar to the rods 104 depicted in FIGS. 7 and 8 may be cured into precast plug 101 such that each “wing” when viewed from above would point in a different direction, such as twelve o'clock, six o'clock, three o'clock and nine o'clock substantially bisecting precast plug 101 both vertically and horizontally. With such an embodiment, the method of installation may be modified to account for the requisite number of grooves 107 to house such “wings”.
FIG. 9 is a plan cross section view depicting an alternative embodiment of the apparatus and method. Rather than a tubular shape as discussed above, rod 104 may take on a substantially rectangular shape. In this embodiment, rod 104 may be comprised of a plastic “T” bar with a break away joint at the “T” intersection, as can be seen in the 10 - 10 cross section line in FIG. 10 . The break away joint and base of the “T” of rod 104 may be a cylindrical arrow-like shape. Such an embodiment allows for this breakaway joint and base to grip the housing of precast plug 101 , providing additional support so that precast plug 101 does not fall through hole 102 . Rod 104 in plastic form, is not to limit the scope of the present apparatus and method. Other embodiments may include iron, wood, silicone, or other durable composite materials. Also, as mentioned above sealant 201 may be applied between precast plug 101 and floor 103 , and over the top of rod 104 in the embodiment depicted in FIG. 9 .
Finally, in FIG. 9 , size indicator 106 depicts a “#112”. This may indicate that either hole 102 or precast plug 101 may be eleven point two inches wide for example. FIG. 10 also depicts precast plug 101 with no tapered edge, an alternative embodiment to the present apparatus and method. An even column of sealant 201 fills the space between floor 103 and precast plug 101 . In another embodiment, however, more or less sealant may be applied, e.g., if precast plug 101 were to taper outward or inward, or hole 102 were to taper inward or outward. In yet another embodiment sealant 201 may be applied such that it covers the bottom edge of precast plug 101 and/or the top edge of precast plug 101 , such as to give further protection to precast plug 101 and floor 103 .
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The present apparatus and method relates in general to sealing a hole in a floor with a precast plug. A precast plug is created by pouring a wet aggregate mix into a form mold and thereafter inserting a pre bent rod into the uncured mixture, positioning it such that the center of the rod rests in the center of the form mold and the ends of the rod extend outward near the top of the form mold. The mix is then cured. The precast plug may then be transported to the hole that it is destined to fix. Grooves may be carved on either side of the hole to accommodate the rod's ends. The interior of the hole and the exterior of the plug may then be covered with a sealant, after which the plug may be inserted into the hole. Once the sealant cures, the hole is fully repaired.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority from U.S. Provisional Application Ser. No. 62/045,218 filed on Sep. 3, 2014, and U.S. Provisional Application Ser. No. 61/940,691, filed Feb. 17, 2014. The entire disclosures of each of the above applications are incorporated herein by reference.
FIELD
[0002] The present disclosure relates to submersible pumps used in landfill wells for leachate discharge and well liquid level control, and more particularly to a pneumatically driven, automatic pump that is especially resistant to the buildup contaminants on its moving components.
BACKGROUND
[0003] This section provides background information related to the present disclosure which is not necessarily prior art.
[0004] Present landfill leachate and liquid level control pumps typically have metal end plates with four protrusions on the ID on both ends of the pump float to reduce the contact area and thereby reduce stiction forces hindering free movement of the float. Abrasion of the discharge tube surface from the pump float can lead to corrosion and pitting of the discharge tube which in turn can aid in solids adhesion, which increases stiction forces. Stiction is defined as a static friction that must be overcome to enable relative motion of stationary objects initially in contact with each other. Field reports from landfill well sites describe a downward spiral in the discharge tube surface roughness leads to increased susceptibility to corrosion and greater solids adhesion rate and cleaning difficulty. The present rough surface is also an industry standard pipe manufacturing quality, which includes surface pitting.
[0005] Known pump air control mechanisms include stainless steel “E” clips. The “E” clips' thinness, which is a corrosive attack factor, and susceptibility to subtle damage in disassembly have caused problems requiring replacement in the field.
SUMMARY
[0006] This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
[0007] In one aspect the present disclosure relates to a liquid level control pump adapted to be lowered into contact with a fluid collecting with a wellbore, and being in communication with an external pressurized fluid source. The liquid level control pump may comprise a pump casing, a discharge tube, a first check valve, a second check valve, a float, a control rod, and a pivoting lever assembly. The discharge tube is disposed substantially within the pump casing and has a first end and a second end. The discharge tube is operable to receive fluid collecting within an area between the pump casing and an outer surface of the discharge tube. The discharge tube further includes first and second ends. The first check valve is disposed at the first end for controlling a flow of the fluid within the discharge tube to one direction only, that being out from the first end of the discharge tube. The second check valve is disposed at the second end for limiting the flow of fluid to one direction only, that being from the pump casing into the discharge tube at the second end. The source of pressurized fluid is in communication with the pump casing, and the float is arranged coaxially around the discharge tube and movable along the discharge tube towards the first and second ends. The control rod is disposed adjacent the discharge tube and operably associated with the float so as to be lifted by the float as the float moves toward the first end as the area within the pump casing fills with the fluid. The float moves towards the second end as the fluid within the pump casing is pumped out through the discharge tube using a pressurized fluid from the pressurized fluid source. The pivoting lever assembly is operably associated with the float for controlling the application and interruption of the pressurized fluid into the pump casing, to thus control the pumping of the fluid collecting within the pump casing out from the pump casing and into the second end of the discharge tube, towards the first end of the discharge tube. The float includes a through bore and a through slot in communication with the through bore. The through slot permits passage of a portion of the control rod therethrough and operates to permit fluid flow about an entire periphery of the control rod as the float moves up and down adjacent an outer surface of the discharge tube, and relative to the control rod. This reduces or eliminates a buildup of solids between the control rod and the float that could otherwise affect free sliding movement of the float along the discharge tube.
[0008] In another aspect the present disclosure relates to a liquid level control pump adapted to be lowered into contact with a fluid collecting with a wellbore, and being in communication with an external pressurized fluid source. The liquid level control pump comprises a pump casing, a discharge tube, a first check valve, a second check valve, a control rod, a float, a pivoting lever assembly, and a removable and replaceable discharge tube sleeve. The discharge tube is disposed substantially within the pump casing and has a first end and a second end. The discharge tube is operable to receive fluid collecting within an area between the pump casing and an outer surface of the discharge tube. The discharge tube further includes first and second ends. The first check valve is disposed at the first end for controlling a flow of the fluid within the discharge tube to one direction only, that being out from the first end of the discharge tube. The second check valve is disposed at the second end for limiting the flow of fluid to one direction only, that being from the pump casing into the discharge tube at the second end. The source of pressurized fluid is in communication with the pump casing, and the float is arranged coaxially around the discharge tube and movable parallel to the discharge tube towards and away from the first and second ends. The control rod is disposed adjacent the discharge tube and operably associated with the float so as to be lifted by the float as the float moves toward the first end as the area within the pump casing fills with the fluid. The float then moves towards the second end as the fluid within the pump casing is pumped out through the discharge tube using a pressurized fluid from the pressurized fluid source. The pivoting lever assembly is operably associated with the float for controlling the application and interruption of the pressurized fluid into the pump casing, to thus control the pumping of the fluid collecting within the pump casing out from the pump casing and into the second end of the discharge tube, towards the first end of the discharge tube. The removable and replaceable discharge tube sleeve is disposed over the outer surface of the discharge tube. The float is adapted to move slidably along an outer surface of the discharge tube sleeve.
DRAWINGS
[0009] The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
[0010] FIG. 1 is a partial cross sectional view of a liquid level control pump of the present disclosure positioned in a landfill well at a float lower position;
[0011] FIG. 2 is a partial cross sectional view of the pump of FIG. 1 at a float upper position;
[0012] FIG. 3 is a side elevational view of a pump float of the liquid level control pump of FIG. 1 ;
[0013] FIG. 4 is an end elevational view of the pump float of FIG. 3 ;
[0014] FIG. 5 is a perspective view of a pump end cap of the liquid level control pump of FIG. 1 ;
[0015] FIG. 6 is a front elevational view of the pump end cap of FIG. 5 ;
[0016] FIG. 7 is a cross sectional view taken at section 7 of FIG. 6 ;
[0017] FIG. 8 is a cross sectional view taken at section 8 of FIG. 6 ;
[0018] FIG. 9 is a perspective assembly view of a pivoting lever assembly of the liquid level control pump of FIG. 1 ;
[0019] FIG. 10 is a partial cross sectional front elevational view of a pivoting lever portion of the pivoting lever assembly of FIG. 9 ;
[0020] FIG. 11 is a partial cross sectional front elevational view of the pivoting lever portion of FIG. 10 ;
[0021] FIG. 12 is an end elevational view of a lever poppet bushing of the present disclosure;
[0022] FIG. 13 is a cross sectional view taken at section 13 of FIG. 12 ;
[0023] FIG. 14 is a front elevational view of a housing adapter of the present disclosure;
[0024] FIG. 15 is a bottom plan view of the housing adapter of FIG. 14 ;
[0025] FIG. 16 is a top plan view of the housing adapter of FIG. 14 ;
[0026] FIG. 17 is a front cross sectional view taken at section 17 of
[0027] FIG. 15 ;
[0028] FIG. 18 is a rear cross sectional view taken at section 18 of FIG. 14 ;
[0029] FIG. 19 is an assembly view of a ball check valve and housing adapter of the present disclosure;
[0030] FIG. 20 is an elevational view of a replaceable discharge tube sleeve that may be incorporated into the pump of FIG. 1 by being placed over the discharge tube;
[0031] FIG. 21 is an end view of the sleeve shown in FIG. 20 illustrating a plurality of teeth or ridges that may be formed on the inner surface of the sleeve to eliminate play between the sleeve and the discharge tube;
[0032] FIG. 22 is an enlarged portion of the sleeve of FIG. 21 showing one example of the shape that the ridges may have, in this example the shape being generally triangular;
[0033] FIG. 23 shows an example of the ridges of the sleeve having a rectangular shape; and
[0034] FIG. 24 shows an example of the ridges of the sleeve having a semi-circular shape.
[0035] Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION
[0036] Example embodiments will now be described more fully with reference to the accompanying drawings.
[0037] Referring to FIG. 1 , a liquid level control pump 10 of the present disclosure includes a pump casing 12 which is submerged below an anticipated water level found in a landfill well pipe 14 . Within the pump casing 12 is a discharge tube 16 centrally located in the pump casing 12 . A float 18 is slidably disposed on the outer surface of the discharge tube 16 and can raise and lower as the water level within the landfill well pipe 14 changes. A control rod 20 , positioned external to the discharge tube 16 , is slidably received through the float 18 through each of a first float end cap 22 and a second float end cap 24 positioned at opposite ends of float 18 .
[0038] After operation of the liquid level control pump 10 , liquid level in the landfill well pipe 14 lowers and the float 18 is positioned in direct contact with a lower float stop 26 fixed to the control rod 20 . Contact between the float 18 and the lower float stop 26 thereafter pulls the control rod 20 downward. An upper float stop 28 is also fixed to an upper location of control rod 20 , whose function will be described in greater detail in reference to FIG. 2 . A pivoting lever assembly 30 is connected to the control rod 20 , whose position is changed by contact between float 18 and either the lower float stop 26 (as shown) or the upper float stop 28 . At the lower position of float 18 (shown), the pivoting lever assembly 30 is rotated to an orientation which isolates pressurized air in a pressurized air supply tube 32 from entering pump casing 12 . At this lower position of float 18 , a ball 34 defining a portion of a ball check valve is seated against a threaded end 36 of a check valve ball housing 38 . This seated position of ball 34 prevents fluid which has been discharged by operation of liquid level control pump 10 from returning back down into landfill well pipe 14 . A housing adapter 40 is connected to the check valve ball housing 38 and is used to both retain the ball 34 within check valve ball housing 38 and as an adapter for connection to a tubing connector 42 , where fluid discharged by operation of liquid level control pump 10 exits the pump.
[0039] In the lower position of float 18 (shown), fluid which enters the landfill well pipe 14 flows upward into the pump casing 12 by displacement of a check valve member 44 positioned at a lower end of liquid level control pump 10 . The check valve member 44 displaces away from a valve seat 46 , allowing the inward flow in the direction of flow arrows “A” into pump casing 12 . This inward flow of fluid into pump casing 12 causes the float 18 to upwardly displace in a float upward displacement direction “B”. This upward displacement of float 18 continues until the first float end cap 22 directly contacts the upper float stop 28 and displaces the control rod 20 upward to rotate the pivoting lever assembly 30 .
[0040] Referring to FIG. 2 , at the upward displacement position of float 18 , the first float end cap 22 directly contacts upper float stop 28 . After this direct contact occurs with upper float stop 28 , further upward displacement of the float 18 causes the direct displacement of control rod 20 in the upward displacement direction “B”, which rotates the pivoting lever assembly 30 to an opposite orientation from that disclosed with respect to FIG. 1 . This rotation of pivoting lever assembly 30 displaces a poppet, described in reference to FIG. 9 , which allows entrance of pressurized air from pressurized air supply tube 32 into the pump casing 12 . The entrance of pressurized air into pump casing 12 forces the liquid within pump casing 12 to close the check valve member 44 and thereby open an entrance path for liquid to flow into the discharge tube 16 , thereafter rising up through discharge tube 16 to upwardly displace the ball 34 , providing a discharge path for liquid through housing adapter 40 and tubing connector 42 via a discharge pipe (not shown) for discharge of the liquid out of the landfill well pipe 14 . Air flow into pump casing 12 continues until the position of float 18 shown in reference to FIG. 1 is reached again, which thereby rotates the pivoting lever assembly 30 , isolating the pressurized air in pressurized air supply tube 32 from pump casing 12 . This cyclic operation of liquid level control pump 10 continues as long as the fluid level within landfill well pipe 14 is sufficient to raise float 18 into direct contact with upper float stop 28 and as long as pressurized air is available in pressurized air supply tube 32 . Improvements made to the liquid level control pump 10 include design changes which will be described herein with respect to the clearance provided for displacement of float 18 with respect to control rod 20 , modifications to the pivoting lever assembly 30 , and provision of the modified design of housing adapter 40 .
[0041] Referring to FIG. 3 , float 18 includes a through bore 48 which is sized to slidably contact the outer wall of discharge tube 16 . According to several aspects, the material of float 18 is selected as a polymeric material to provide the upward force required for displacement of control rod 20 .
[0042] Referring to FIG. 4 and again to FIG. 3 , the through bore 48 of float 18 is centered with respect to a float longitudinal axis 50 . To minimize the frictional contact between control rod 20 and material of float 18 , a through slot 52 is provided, which extends all the way from an outer wall of the float 18 into the through bore 48 . The open design of through slot 52 allows free flow of the liquid of landfill well pipe 14 entirely about the perimeter of control rod 20 for the entire upward and downward displacement of float 18 . Clearance is also provided by a width of the through slot 52 which is sized to be approximately two times a diameter of control rod 20 . This further minimizes the potential for buildup of materials present in the liquid from plating out onto control rod 20 or the surfaces of float 18 , which would increase the frictional resistance to displacement of float 18 . It is noted that through slot 52 is aligned with a slot center axis 54 intersecting with the float longitudinal axis 50 .
[0043] Referring to FIG. 5 and again to FIGS. 1 and 2 , each of the first and second float end caps 22 , 24 are identical to each other and are installed in oppositely facing directions on the pump casing 12 . Each of the first and second float end caps 22 , 24 includes a cap body 56 which is washer-like in appearance having a center bore 58 . According to several aspects, a plurality of raised bumpers 60 , each defining a semi-spherical shape, extend inwardly from a bore inner wall 62 of center bore 58 . Each of the raised bumpers 60 are provided to make direct contact with the outer wall of discharge tube 16 . The rounded geometry of the raised bumpers 60 , as well as the use of a minimum quantity of the raised bumpers 60 (according to several aspects four raised bumpers 60 may be provided), minimizes frictional contact with the discharge tube 16 . In addition, a material selected for each of the first and second float end caps 22 , 24 is a
[0044] PEEK polymeric material selected due to its low-friction properties and resistance to the materials present in landfill well liquids. Other engineering plastics in addition to PEEK material, such as improved polyamides (nylons) and glass fiber reinforced polyphenylene sulfide (PPS)0 can also be used, each having desirable characteristics for the float end caps such as strength, chemical resistance and wear/abrasion resistance. A control rod receiving aperture 64 is created through cap body 56 , which closely matches an outer diameter of control rod 20 , allowing for sliding contact between the first and second float end caps 22 , 24 and control rod 20 as the float 18 displaces.
[0045] Referring to FIG. 6 and again to FIGS. 1-2 and 5 , a bumper inner diameter 66 is defined by an innermost rounded surface 68 of each of the multiple raised bumpers 60 . The bumper inner diameter 66 is substantially equal to or larger than a diameter of the discharge tube 16 . According to several aspects, the four raised bumpers 60 a, 60 b, 60 c, 60 d are each located at approximately 90 -degree intervals with respect to each other with one of the raised bumpers 60 b also axially aligned with control rod receiving aperture 64 . In addition to control rod receiving aperture 64 , first and second fastener apertures 70 , 72 are also created through the cap body 56 . The first and second fastener apertures 70 , 72 provide for fastener installation of the first or second float end caps 22 , 24 at their respective end positions on float 18 .
[0046] Referring to FIG. 7 and again to FIGS. 5-6 , a chamfered edge 74 can be provided with each of the first and second fastener apertures 70 , 72 .
[0047] Chamfered edge 74 allows for full recession of a fastener head (not shown) used for installation of the first or second float end caps 22 , 24 .
[0048] Referring to FIG. 8 and again to FIGS. 5-7 , the geometry of control rod receiving aperture 64 aligns a central axis 65 of the control rod receiving aperture 64 substantially parallel with respect to a central axis 67 of the first and second float end caps 22 , 24 .
[0049] Referring to FIG. 9 and again to FIGS. 1 and 2 , the pivoting lever assembly 30 is modified in the design of liquid level control pump 10 to reduce the quantity of parts associated with operation of poppets that control the flow of pressurized air into and out of pump casing 12 . The pivoting lever assembly 30 includes each of a first and a second lever half 76 , 78 , each having a first and second connecting flange 80 , 82 oppositely extending therefrom. A planar end face 84 is created on each of the first and second connecting flanges 80 , 82 which abut with the corresponding faces of the opposite half of the pivoting lever assembly 30 . A slot 86 is created between the first and second connecting flanges 80 , 82 , which provides for the positioning of an insert member 88 which is located substantially at a central position of slot 86 . An elongated slot 90 is provided in each of the first and second lever halves 76 , 78 to allow for liquid flow past the pivoting lever assembly 30 .
[0050] A poppet 92 having a needle end 94 is positioned within at least one of the slots 86 . The needle end 94 can be used, for example, to isolate the flow of pressurized air into pump casing 12 from the pressurized air supply tube 32 when the float 18 is not in direct contact with upper float stop 28 . The poppet 92 is connected to one of the first or second lever halves 76 , 78 using a lever poppet bushing 96 having a bushing rod 98 extending therefrom. The bushing rod 98 is sized to be slidably received through a poppet aperture 100 of poppet 92 and thereafter received in a rod receiving aperture 102 of the insert member 88 , such as insert member 88 ′ (shown).
[0051] Referring to FIG. 10 and again to FIG. 9 , each of the first and second lever halves 76 , 78 includes an insert aperture 104 which extends inwardly (away) from an end face of slot 86 . An insert outer wall 106 of the insert member 88 is sized to be frictionally coupled against the insert aperture 104 such that a friction fit will retain the insert member 88 within one of the first or second lever halves 76 , 78 .
[0052] Referring to FIG. 11 and again to FIG. 10 , after insertion of the insert member 88 into the insert aperture 104 , an end face of the insert member 88 is positioned substantially flush with a slot end wall 108 of the slot 86 .
[0053] Referring to FIG. 12 and again to FIGS. 9-11 , the lever poppet bushing 96 includes the bushing rod 98 which is integrally connected to a bushing sleeve 110 . A through aperture 111 created through the bushing sleeve 110 is oriented axially parallel with respect to a longitudinal axis of the bushing rod 98 . For maximum wear life, the material of lever poppet bushing 96 can be a nitride material.
[0054] Referring to FIG. 13 and again to FIG. 12 , the bushing sleeve 110 can be created as a separate part with respect to bushing rod 98 and the two parts fixed together, for example, by welding, adhesive or molding. According to other aspects, the bushing rod 98 and the bushing sleeve 110 can be integrally provided of a single material by machining the geometry of lever poppet bushing 96 . According to several aspects, an inner bore wall of the through aperture 111 extending through bushing sleeve 110 is aligned coplanar with a lower outer surface of the bushing rod 98 .
[0055] Referring to FIG. 14 and again to FIGS. 1-2 , the housing adapter 40 includes a hex head 112 to provide for tool use during installation of the housing adapter onto pump casing 12 . Housing adapter 40 further includes a male threaded shank 114 from which a blade member 116 integrally extends beyond a shank end face 118 at the end of threaded shank 114 . A tubing connection head 120 is provided at an opposite end with respect to threaded shank 114 to provide for connection of a discharge tube or pipe to discharge fluid during operation of liquid level control pump 10 .
[0056] Referring to FIG. 15 and again to FIG. 14 , housing adapter 40 includes a housing bore 122 which is substantially bisected by the blade member 116 . This creates a first and a second bore portion 124 , 126 of substantially equal size on opposite sides of the blade member 116 . The blade member 116 therefore results in minimal restriction of fluid flow through the housing bore 122 .
[0057] Referring to FIG. 16 and again to FIGS. 14-15 , each of the hex head 112 , tubing connection head 120 , and the housing bore 122 are coaxially aligned with respect to a longitudinal axis of housing adapter 40 .
[0058] Referring to FIG. 17 and again to FIGS. 14-16 , the blade member 116 has a free end defined as a rounded end 128 having, for example, a semispherical shape. Rounded end 128 is provided to minimize the surface area of blade member 116 , which is in direct contact with ball 34 when ball 34 raises to allow discharge of fluid from liquid level control pump 10 . Rounded end 128 increases the service life of ball 34 , while preventing ball 34 from discharging via the housing bore 122 through the discharge pipe. The blade member 116 therefore minimizes fluid flow resistance through the housing bore 122 while simultaneously retaining ball 34 .
[0059] Referring to FIG. 18 and again to FIGS. 14-17 , the blade member 116 is an integral extension of the material of housing adapter 40 outward of the threaded shank 114 . A first and a second blade support leg 130 , 132 integrally connect the blade member 116 to housing adapter 40 . This extension created by the first and second blade support legs 130 , 132 also creates a flow window 134 above the blade member 116 , as viewed in reference to FIG. 18 . Flow window 134 also helps reduce fluid flow resistance through housing adapter 40 .
[0060] Referring to FIG. 19 and again to FIGS. 1-2 and 14-18 , the housing adapter 40 is assembled into the check valve ball housing 38 by threaded insertion of the threaded shank 114 engaging internal threads 136 created in a ball receiving bore 138 of check valve ball housing 38 . The ball 34 is positioned within the ball receiving bore 138 prior to installation of housing adapter 40 such that the blade member 116 prevents release of ball 34 . As previously noted, the rounded end 128 of blade member 116 is provided to minimize the surface area of blade member 116 in direct contact when ball 34 is positioned at its maximum lift location. The check valve ball housing 38 is itself threadably engaged to the pump casing 12 using a housing male thread 140 .
[0061] The PEEK (polyether ether ketone) plastic, bearing grade float end caps 22 , 24 are designed to reduce scraping damage to the surface finish of the pump discharge tube 16 , whether the discharge tube 16 is coated or not. The PEEK end caps 22 , 24 have rounded bumpers 60 extending inwardly from the bore inner wall 62 directed toward the central axis 67 of the end caps 22 , 24 . The bumpers 60 minimize a surface area of the end caps 22 , 24 in direct contact with the discharge tube 16 , and thereby help reduce abrasion of the discharge tube surface. This abrasion if not minimized can lead to corrosion and pitting of the discharge tube 16 which in turn can aid in solids adhesion.
[0062] The pivoting lever assembly 30 on the air control mechanism eliminates the stainless steel “E” clips currently in use for this purpose. The present disclosure pivoting lever assembly 30 design has fewer parts, is easier to assemble and can be retrofitted in the field to existing pumps.
[0063] The float 18 is provided having the open channel 52 for the control rod 20 to pass-through, rather than the current enclosed channel. The open channel 52 reduces the build-up of solids vs. with the conventional bore design, is easier to clean and makes coatings easier to apply.
[0064] The float 18 is coated to reduce the adhesion of solids and make them easier to clean off. An epoxy silicone paint is applied to the float 18 which has been found to be effective in reducing adhesion of solids.
[0065] An improved finish is also provided for the discharge tube 16 to reduce solids adhesion, make cleaning easier and reduce corrosion. The improved surface finish uses centerless grinding followed by electro-polishing for a mirror-bright finish.
[0066] Referring now to FIGS. 20-24 , in another embodiment the liquid level control pump 10 may incorporate a discharge tube sleeve (hereinafter simply “sleeve”) 150 . The sleeve 150 forms a tubular component designed to fit over the discharge tube 16 ( FIGS. 1 and 2 ). The sleeve 150 forms a component that may be easily replaced simply by sliding it off from the discharge tube 16 and sliding a new sleeve 150 on over the discharge tube 16 . By incorporating the sleeve 150 and making it readily replaceable, the situation where a buildup of solids on the exterior of the discharge tube 16 might occur can be avoided. Such a condition could impede the smooth, easy sliding motion of the float 18 up and down the discharge tube 16 and potentially cause the float 18 to “hang up” at some intermediate point along its intended path of travel. The sleeve 150 may have a length that extends virtually the entire length of the discharge tube 16 , or a length which is at least sufficiently long to cover that portion of the discharge tube 16 that the float 18 rides along during normal operation of the pump 10 . The sleeve 150 thus functions to provide an exceptionally smooth, low friction surface for the inner surface of the float 18 to ride on. The sleeve 150 may be formed from a bearing grade thermoplastic polymer, for example, but not limited to, polyether ether ketone (PEEK) or Polyphenylene Sulfide (PPS). Other materials such as graphite and/or other lubricants may also be incorporated into its material composition to further reduce friction and/or to help reduce the likelihood of solids buildup on the external surface of the sleeve 150 .
[0067] An end view of the sleeve 150 is shown in FIG. 21 . The sleeve 150 may be extruded or formed in any other suitable manner. An inner wall 152 of the sleeve 150 may include a plurality of circumferentially spaced apart teeth or ridges 154 . Preferably the ridges 154 are spaced evenly about the entire circumference of the inner wall 152 of the sleeve 150 . FIG. 21 shows the ridges 154 spaced about every 30 degrees around the inner wall 152 , but it will be appreciated that a greater or lesser number of ridges 154 may be used, and either a uniform spacing or non-uniform spacing of the ridges 154 can be used. The ridges 154 in this example project about 0.023 inch radially inward, as indicated by dimensional arrows 153 in FIG. 22 , but again, this dimension could vary significantly. In one example the wall thickness of sleeve 150 is between about 0.030 inch to about 0.060 inch. An inner diameter formed by the ridges 154 , as indicated by dimensional arrow 156 in FIG. 21 , is preferably just slightly less, for example by 0.010 inch or so, than the outer diameter of the discharge tube 16 . The ridges 154 may bend or deflect slightly as the sleeve 150 is slid onto the discharge tube 16 during assembly of the pump 10 , and thus help to take up the play between the discharge tube 16 and the sleeve 150 and help to maintain the sleeve 150 axially centered about the discharge tube 16 . The outer surface of the discharge tube 16 may also be highly polished to further help resist the buildup of solids thereon. Since the sleeve 150 can be quickly and easily slid on and off the discharge tube 16 , this enables convenient periodic replacement of the sleeve 150 without the need for any special tools or disassembly procedures. It is anticipated that users will find that replacement of the sleeve 150 with a new sleeve may even be easily accomplished in the field. Users may find that establishing a schedule for periodic replacement of the sleeve 150 (e.g., once 6-12 months) may help to ensure that no tangible buildup of solids occurs during use of the pump 10 .
[0068] FIGS. 23 and 24 show alternative forms of the ridges 154 . The ridges 154 a in FIG. 23 are shown as being generally square shaped. The ridges 154 b in FIG. 24 are shown as having a rounded, arcuate shape. In both cases the ridges 154 a and 154 b are able to flex or deform slightly as the sleeve 150 is inserted onto the discharge tube 16 to eliminate play between the sleeve 154 and the discharge tube 16 .
[0069] Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
[0070] The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed.
[0071] When an element or layer is referred to as being “on,” “engaged to,” “connected to,” or “coupled to” another element or layer, it may be directly on, engaged, connected or coupled to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly engaged to,” “directly connected to,” or “directly coupled to” another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
[0072] Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
[0073] Spatially relative terms, such as “inner,” “outer,” “beneath,” “below,” “lower,” “above,” “upper,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
[0074] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.
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A liquid level control pump especially well adapted for use in land-fill wells is disclosed. The pump makes use of a pump casing, a discharge tube, a control rod, first and second check valves, a float and a pivoting lever assembly for controlling the application of a pressurized fluid from an external pressurized fluid source. In one aspect the float may include a through slot which allows the control rod to pass therethrough and which helps to reduce the chance of the float hanging due to an accumulation of solids between the control rod and the float. In another aspect a removable and replaceable discharge tube sleeve may be included.
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FIELD OF THE INVENTION
This invention relates to a process for removing tobacco stems from tobacco leaves. More specifically, the present invention pertains to a process in which tobacco leaves are cooled to very low temperatures and then flexed to separate the stems and lamina.
BACKGROUND OF THE INVENTION
Tobacco leaf stems have generally been found to be objectionable in smoking tobacco blends, particularly in blends for cigars and cigarettes. Stems have undesirable burning qualities and their stiffness may lead to deformed or punctured wrappers. In making smoking tobacco products, it is therefore customary to subject tobacco leaf to a threshing operation to separate the stem from the remainder of the leaf.
The stems, after separation, may be processed to produce products useful in smoking products. For example, they may be ground, mixed with fines, and converted into synthetic leaf, or the whole stem may be converted to useable filler material by an enzymatic process. Relatively long pieces of stem are more suitable for processing into a smoking product. In addition, relatively long pieces of stem are easier to remove from the rest of the leaves. Thus, any commercially suitable threshing process must result in the production of relatively long stems.
The remainder of the leaf, the lamina, is the portion that is the most important in production of smoking tobacco products. High grade tobacco products contain little stem and the lamina is by far the most valuable part of the leaf. Consequently, it is desirable to remove the stems with as little attached lamina as possible.
It is also commercially desirable to keep the lamina in relatively large pieces. Large pieces may be handled and shredded more easily during processing into high quality tobacco filler for cigars and cigarettes. Even more importantly, the destemming process must keep the production of fines, the dustlike particles of lamina, to a minimum. Tobacco fines, unless processed into reconstituted tobacco sheets, are not suitable for use in tobacco products. Thus, production of large amounts of fines represents a significant loss of valuable lamina.
In known tobacco leaf destemming processes, the leaf stems are separated from the leaf lamina by first subjecting the leaves to a mechanical threshing action of sufficient duration and intensity to completely detach the lamina from the stems. The resulting stem-lamina mixture is then subjected to a classification step. In typical threshers, lamina is separated from stems or veins by the action of one or more toothed rotors beating against stationary teeth, or by the action of counter-rotating toothed rotors, or by the action of a toothed rotor beating against a perforated cage or basket or by the action of a toothed rotor beating first against stationary teeth and then against a perforated cage or basket.
Because of the relatively ductile nature of the tobacco lamina, it will not easily break away from the stems. Therefore multiple impacts by the rotors are required to tear and rip the lamina and the stem must undergo violent flexing during this phase of the process, if all the lamina is to be removed from the stems and large veins.
The threshing processes currently in use, even if carefully controlled, result in the production of a preponderance of small pieces of lamina. In addition, an unacceptable amount of tobacco fines is produced, because of the pulverizing action of the toothed rotors and the multiple impacts required to completely detach all the lamina. The multiple impacts and violent flexing action also result in the production of broken and undesirably short stems.
In addition, current threshing processes often require, as an initial step, the addition of significant amounts of water, to permit handling of the leafs without causing undue fragmentation of the lamina. This water has to be removed in a drying step, subsequent to classification, before the tobacco lamina can be processed into a marketable product.
The present invention provides a technique whereby the stems can be easily detached from the tobacco leaves and then separated from the lamina. The technique of the present invention results in the production of relatively large pieces of lamina and long stems and veins. Furthermore, the process of the present invention does not require the addition of large amounts of water to prepare the tobacco for the stem separation process.
SUMMARY OF THE INVENTION
The process of the present invention comprises cooling tobacco leaves until they are frozen, subjecting the frozen leaves to flexing whereby the lamina are detached from the stem, and finally separating the detached lamina and stems for subsequent processing.
The leaves should be cooled to a temperature of between about 0°C. and -210°C., preferably between about -30°C and about -60°C. While the moisture content of the leaves is not critical, it is preferably maintained between about 15% and 25% by weight.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of one embodiment of the present invention, in which a spray of cold liquid is employed for freezing the tobacco leaves and an adjustable compression roller acting on a moving conveyor provides means for flexing the frozen leaves.
FIG. 2 is a schematic illustration of another embodiment of the present invention, also employing a spray of cold liquid, but using a mechanical doffer and a vibrating conveyor to provide means for flexing the leaves.
FIG. 3 is a schematic illustration of yet another embodiment of the present invention, in which a spray of cold liquid is used and a tumbler is employed to achieve flexing.
FIG. 4 illustrates a multiple nozzle arrangement which may be employed in the embodiment of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the process of the present invention, the cooling can be accomplished by any suitable means, such as by placing the tobacco leaves inside a suitable enclosure provided with a refrigerator system. Preferably, however, the leaves are cooled directly by contact with a cold liquid, such as liquid nitrogen or a dry ice-ethyl alcohol slurry. Contact with the cold liquid can be accomplished by totally or partially immersing the leaves, or the liquid can be sprayed or splashed on the leaves.
Regardless of the cooling technique employed, it is essential that the leaf be cooled to at least 0°C., and preferably at least -30°C. At higher temperatures, good separation is not achieved and unacceptable levels of fines are generated.
Upon cooling tobacco leaves, stem freezes before lamina. Preferably, to obtain good stem separation, both the lamina and stem are frozen prior to flexing. However, the tobacco leaves can be removed from the cooling stage and subjected to the flexing process with only the stems, and the portion of the lamina immediately adjacent to the stems frozen.
The method of providing the flexing action is not critical. Any means which will mechanically flex or vibrate the leaves is suitable. For example, the flexing can be accomplished by rolling the leaves with adjustable compression rollers. Alternatively, the frozen leaves can be placed in a tumbler. The tumbler preferably contains tumbling elements to impart further flexing, in addition to that provided by the weight of the leaf charge itself. In other embodiments, the flexing can be imparted by direct impact with toothed rotors or other rotating or reciprocating mechanical threshing means.
Flexing also can be accomplished with hydraulic impinging jets employing liquid, gas or two-phase (gas-liquid, gas-solid, or liquid-solid) working fluids, such as sand blasts or water jets. In addition, the lamina can be detached by vibrating the frozen leaves, as by a vibrating conveyor system or shaker. The leaves can be submerged in a coolant during vibration. Combinations of these flexing means, of course, can be employed.
The best results, in terms of large size pieces of lamina and minimum fine production, occur when the controllable parameters of the selected flexing means are chosen to provide a relatively gentle flexing action. The separation of the detached lamina and stems can be carried out by known techniques, such as forced air classification.
In the embodiment shown schematically in FIG. 1, the tobacco leaves are fed onto a moving conveyor 5 and pass under a spray of liquid nitrogen 2. The liquid nitrogen issues from spray head 1, fed from coolant distribution means 3. Conveyor 5 subsequently carries the frozen leaves under compression roller 7. Roller 7 acts upon the frozen leaves to detach the lamina from the stem. From this point the detached, but intermingled, pieces of lamina and stems are fed into separation means 13 to segregate these components. The coolant flow rate, conveyor speed, and leaf feed rate are preferably controlled to produce leaf temperatures of from -30°C. to -60°C. at the position where the compression roller 7 engages the leaves.
The compression roller 7 may have a partially yielding surface, such as a rubber coating on a steel roller. Such a surface tends to avoid pulverizing the stem by conforming to the stem while exerting sufficient force on the immediately adjacent lamina to cause it to detach from the stem at the lamina stem interface. The downward force of the roller is provided by the sum of its own weight plus adjustable spring force means 9. The compression roller 7 is driven by a roller drive means 11 arranged as a counter weight to partially off-set the downward force.
Adjustable spring force means 9 can be regulated to obtain different roller pressure on the leaf. Obviously the pressure is selected to provide optimum operation, in terms of lamina-stem separation and lamina piece size.
In the embodiment shown schematically in FIG. 2, the tobacco leaves are fed onto a vibrating conveyor 19. The leaves pass under a spray of liquid nitrogen 2 issuing from spray head 1 which is supplied by coolant distribution means 3. The frozen leaves are then carried under a mechanical thresher means, such as rotating doffer 15 where the lamina is detached from the stems. The intermingled stems and pieces of lamina are subsequently carried into the separator means 13.
In addition to providing threshing means, doffer 15 serves to keep the tobacco in the liquid nitrogen spray 2 until the desired leaf temperature is reached.
Doffer 15 can be replaced with other threshing means, such as a wire reinforced rubber pipe in contact with the vibrating conveyor or multiple doffers. Multiple doffers rotating at different speeds may be employed.
In the embodiment depicted in FIGS. 3 and 4, the tobacco leaves are fed into a tumbler 17. Liquid nitrogen is sprayed on the leaves from multiple spray heads 1, fed from a coolant distribution means 3. The multiple spray heads 1 are inserted into the tumbler 17 approximately parallel to the rotational axis. After the leaves have become frozen, flexing caused by the tumbling causes the lamina to detach from the stem. Subsequently, the mixture of pieces of lamina and stems are fed into the separation means 13.
As in the embodiments of FIGS. 1 and 2, the liquid nitrogen spray rate and batch spray time are selected to produce the desired leaf temperature prior to flexing. The rotation rate of tumbler 17 is chosen to provide optimum separation, depending on the nature and amount of tobacco employed and the actual temperature used.
It will be apparent to those skilled in the art that various modifications and variations could be made in the process constituting this invention without departing from the spirit and scope of the invention.
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A process is disclosed for separating tobacco stems from tobacco leaves which comprises freezing the leaves, subjecting them to flexing to break the lamina free from the stems, and then separating the stems from the lamina. Generally, it is preferable to freeze the tobacco leaves, at a temperature between about 0°C. and -210°C., and to flex the frozen leaves as gently as possible to leave the stem unbroken.
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TECHNICAL FIELD
[0001] The subject matter disclosed herein generally relates to inlet air treatment systems, and more specifically to systems and methods for bypassing panel or pocket coalescers for gas turbine systems.
BACKGROUND
[0002] Gas turbine systems typically include a compressor for compressing incoming air, a combustor for mixing fuel with the compressed air and igniting a fuel and air mixture to form a high temperature gas stream, and a turbine section driven by the high temperature gas stream.
[0003] The gas turbine system may be a component in a gas turbine plant such as a power plant for the production of electricity. In some cases the gas turbine system may be used in a combined cycle power plant. In a combined cycle power plant, the gas turbine system generates power and electricity from the combustion of the mixture of fuel and air. The heat energy from this combustion is transmitted to a heat recovery steam generator, which converts the heat into steam. The steam is then communicated to a steam turbine engine where additional power and electricity are produced. The gas turbine plant may include a distributed plant control system.
[0004] Some gas turbine systems include inlet air treatment systems that remove moisture and/or particulates and dissolved solids from air channeled to the compressor. Air filtration systems may include pocket or panel coalescers that remove moisture in the air stream, which protects the downstream filters and the turbine. This is essential in environments with high levels of ambient moisture, including humidity, rain, fog and mist. Coalescers also can help to remove liquid phase corrosives, reducing the likelihood of such corrosives reaching the turbine and causing damage. Coalescers remove moisture by agglomerating water droplets, making them larger and heavier, so that they can drain away rather than continue in the airstream.
[0005] During normal operating conditions, it is desired to have the inlet air treatment system channel filtered air to the compressor with minimal air disruption and pressure drop through the inlet air treatment system.
[0006] Over time, the pressure drop across the coalescers may increase resulting in a decrease in the amount of air flow provided to the compressor. This decrease reduces the operating efficiency of the gas turbine. In some instances, the reduced air flow may cause a compressor surge that may damage the compressor. To prevent compressor surges, in at least some known inlet air treatment systems, coalescers have to be removed manually to be cleaned. This removal process may require shutdown of the gas turbine.
BRIEF DESCRIPTION OF THE INVENTION
[0007] The disclosure provides a solution to the problem of high pressure loss due to clogging of a coalescer in a gas turbine system.
[0008] In accordance with one exemplary non-limiting embodiment, the invention relates to a system including an air intake subsystem having a housing and a coalescer that is disposed inside the housing. The system includes a mounting bracket and a release mechanism coupled to the coalescer and the mounting bracket. The release mechanism is adapted to selectively release the frame.
[0009] In another embodiment, the invention relates to a gas turbine system comprising a turbine inlet; a compressor coupled to the turbine inlet; a combustor; a turbine; and an air intake subsystem having a housing. The gas turbine system includes a coalescer that is disposed inside the housing and a mounting bracket attached to the housing. A means for coupling the frame to the mounting bracket is provided. The means for coupling is adapted to selectively release the coalescer.
[0010] In another embodiment, the invention relates to a gas turbine plant having a turbine inlet; a compressor coupled to the turbine inlet; a combustor; a turbine; a mechanical load; a distributed plant control system that operates at least a portion of the gas turbine plant; and an air intake subsystem having a housing. The gas turbine plant includes a coalescer that is disposed inside the housing and a mounting bracket attached to the housing. The gas turbine plant also includes a release mechanism coupled to the frame and the mounting bracket. The release mechanism is adapted to selectively release the coalescer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of certain aspects of the invention.
[0012] FIG. 1 is a schematic of a gas turbine system.
[0013] FIG. 2 is a schematic of an inlet system for a gas turbine.
[0014] FIG. 3 is a cross-sectional view of an embodiment of a coalescer bypass system.
[0015] FIG. 4 is a cross-sectional view of an embodiment of a release mechanism.
[0016] FIG. 5 is a cross-sectional view of an embodiment of a magnet release mechanism.
[0017] FIG. 6 is a cross-sectional view of an embodiment of an electromagnet release mechanism.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Referring now to the drawings, FIG. 1 illustrates a simplified, schematic depiction of one embodiment of a gas turbine system 100 . In general, the gas turbine system 100 may include a compressor 105 , one or more combustor(s) 110 and a turbine 115 drivingly coupled to the compressor 105 . During operation of the gas turbine system 100 , the compressor 105 supplies compressed air to the combustor(s) 110 . The compressed air is mixed with fuel and then burned within the combustor(s) 110 . Hot gases of combustion flow from the combustor(s) 110 to the turbine 115 in order to turn the turbine 115 and generate work, for example, by driving a generator 120 .
[0019] Additionally, the gas turbine system 100 may include an inlet duct 125 configured to feed ambient air and possibly injected water to the compressor 105 . The inlet duct 125 may have ducts, filters, coalescers, screens and/or sound absorbing devices that contribute to a pressure loss of ambient air flowing through the inlet duct 125 and into one or more inlet guide vanes 130 of the compressor 105 . The gas turbine system 100 may include a heat recovery steam generator system (HRSG) 131 . The HRSG 131 is an energy recovery heat exchanger that recovers heat from a hot gas stream. It produces steam that can be used in an external process integrated with the gas turbine system 100 (cogeneration) or used to drive a steam turbine. Moreover, the gas turbine system 100 may include an exhaust duct 135 configured to direct combustion gases from the outlet of the turbine 115 . The exhaust duct 135 may include sound absorbing materials and emission control devices that apply a backpressure to the turbine 115 . The amount of inlet pressure loss and back pressure may vary over time due to the addition of components to the inlet duct 125 , and exhaust duct 135 and/or due to particulates and dissolved solids and/or dirt clogging the inlet duct 125 , and exhaust duct 135 .
[0020] Moreover, the gas turbine system 100 may also include a controller 140 . In general, the controller 140 may comprise any suitable processing unit (e.g., a computer or other computing device) capable of functioning as described herein. For example, in several embodiments, the controller 140 may comprise a General Electric SPEEDTRONIC™ Gas Turbine Control System, such as is described in Rowen, W. I., “SPEEDTRONIC™ Mark V™ Gas Turbine Control System,” GE-3658D, published by GE Industrial & Power Systems of Schenectady, N.Y. The controller 140 may generally include one or more processors that execute programs, such as computer readable instructions stored in the controller's memory, to control the operation of the gas turbine system 100 using sensor inputs and instructions from human operators. For example, the programs executed by the controller 140 may include scheduling algorithms for regulating fuel flow to the combustor(s) 110 . As another example, the commands generated by the controller 140 may cause actuators on the gas turbine system 100 to, for example, adjust valves between the fuel supply and the combustor(s) 110 that regulate the flow, fuel splits and type of fuel flowing to the combustor(s) 110 , adjust the angle of the inlet guide vanes 130 of the compressor 105 and/or to activate other control settings for the gas turbine system 100 .
[0021] The scheduling algorithms may enable the controller 140 to maintain, for example, the NOx and CO emissions in the turbine exhaust to within certain predefined emission limits, and to maintain the combustor firing temperature to within predefined temperature limits. Thus, it should be appreciated that the scheduling algorithms may utilize various operating parameters as inputs. These parameters may be derived from measurements made by a plurality of sensors 150 . The controller 140 may then apply the algorithms to schedule the gas turbine system 100 (e.g., to set desired turbine exhaust temperatures and combustor fuel splits) so as to satisfy performance objectives while complying with operability boundaries of the gas turbine system 100 .
[0022] Referring still to FIG. 1 , a fuel control system 145 may be configured to regulate the fuel flowing from a fuel supply to the combustor(s) 110 , the split between the fuel flowing into primary and secondary fuel nozzles and/or the amount of fuel mixed with secondary air flowing into the combustion chamber of the combustor(s) 110 . The fuel control system 145 may also be adapted to select the type of fuel for the combustor(s) 110 . It should be appreciated that the fuel control system 145 may be configured as a separate unit or may comprise a component of the controller 140 .
[0023] FIG. 2 shows an example of a turbine inlet air system 200 . The turbine inlet air system 200 may be used with a gas turbine system 100 . The turbine inlet air system 200 may include a weather hood 205 . The weather hood 205 may be in communication with the gas turbine system 100 via an inlet duct 210 . A filter house 215 may be positioned about the inlet duct 210 . The filter house 215 may have a number of filters 220 therein. The weather hood 205 also may include a plurality of coalescer assemblies 225 . The incoming flow of air 235 passes through the weather hood and the coalescer assemblies 225 and is conveyed by the inlet duct 210 to the compressor 105 .
[0024] FIG. 3 illustrates one of the plurality of coalescer assemblies 225 . Each of the plurality of coalescer assemblies 225 may include a moisture separator 255 and a coalescer 260 . The moisture separator separates moisture from the stream of air flowing through the coalescer assemblies 225 . Additional components such as a filter (not shown) disposed adjacent to the coalescer 260 may be added to the coalescer assemblies 225 . The coalescer 260 may be a panel or pocket coalescer having a frame 265 . Other types of coalescing materials/forms (tubes, cartridges, sponges, screens, depth media, etc.) may also be used. The weather hood 205 includes a back plate 270 . Each of the plurality of coalescer assemblies 225 may include a gasket 275 . Each of the plurality of coalescer assemblies 225 also includes a release mechanism 280 coupled to a support bracket 285 that is attached to the back plate 270 . The release mechanism 280 is adapted to release the frame 265 when a pressure differential across the coalescer 260 exceeds a predetermined pressure differential. It should be noted that although the coalescer assemblies 225 have been described in association with a hood, other types of housings may be used to support the coalescer assemblies 225 .
[0025] In operation, when the pressure differential across the coalescer 260 exceeds a predetermined pressure differential, release mechanism 280 releases the frame 265 from the support bracket 285 . Upon release of the frame 265 the pressure differential will cause the coalescer 260 to pivot thereby allowing the airflow 290 to bypass the coalescer 260 in a direction denoted by arrow 295 .
[0026] Illustrated in FIG. 4 is an embodiment of a release mechanism 280 which comprises a detachable spacer 300 . The detachable spacer 300 includes a body section 305 a first flange section 310 and a second flange section 315 . The detachable spacer 300 also includes the first notch 320 and a top portion 325 . The detachable spacer 300 also includes a second notch 330 and a bulbous bottom portion 335 .
[0027] During assembly, the top portion 325 is inserted through a hole in the frame 265 of the coalescer 260 until the frame 265 is positioned around the first notch 320 . During insertion, top portion 325 deforms to allow the top portion 325 to be inserted through the hole in the frame 265 . The bottom portion 335 is inserted through a hole in the support bracket 285 until the support bracket 285 is positioned around the second notch 330 of the detachable spacer 300 . During insertion, the bottom portion 335 deforms to allow the bottom portion 335 to be inserted through the hole in the support bracket 285 .
[0028] In operation, the detachable spacer 300 secures the frame 265 of the coalescer 260 to the support bracket 285 . When the pressure differential across the coalescer 260 exceeds a predetermined level, the bottom portion 335 deforms to allow the bottom portion 335 to be detached from the support bracket 285 thereby allowing the coalescer 260 to pivot and the airflow to bypass the coalescer 260 .
[0029] Illustrated in FIG. 5 is an embodiment of a release mechanism 280 which comprises a magnet assembly 400 . The magnet assembly 400 may include a first magnet 405 secured to the frame 265 and optionally a second magnet 410 secured to the support bracket 285 . Although the first magnet 405 and a second magnet 410 are illustrated in FIG. 5 , it would be apparent to one of ordinary skill in the art that a single magnet (e.g. first magnet 405 ) may be employed, and the single magnet may be attached to either the frame 265 or the support bracket 285 .
[0030] In operation, when the pressure differential across the coalescer 260 exceeds a predetermined level sufficient to overcome the attraction forces of the first magnet 405 , the first magnet 405 will release. The coalescer 260 will then pivot, thereby allowing the airflow to bypass the coalescer 260 .
[0031] Illustrated in FIG. 6 is an embodiment of an electromagnet release mechanism 500 including an electromagnet 501 . The electromagnet release mechanism 500 includes a ferromagnetic rod 505 with a coil 510 . The coil is coupled to a power source 515 such as a battery. A controller 520 may be provided to control a switch 525 enabling the operator to release the frame 265 . The controller 520 provides an operator with additional flexibility to control when the electromagnet release mechanism 500 releases. The controller 520 may cut the power and release the electromagnet 501 at any desired time. The controller 520 may also re-engage the electromagnet circuit thereby providing a positive force which causes the electromagnet 501 to re-engage the frame 265 and close the coalescing panel.
[0032] Although three embodiments of the release mechanism 280 have been presented in detail, other release mechanisms 280 are contemplated by the present invention. For example, a fabric hook-and-loop fastener, a detachable or frangible cable or other detachable fasteners may be used.
[0033] Where the definition of terms departs from the commonly used meaning of the term, applicant intends to utilize the definitions provided below, unless specifically indicated.
[0034] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Where the definition of terms departs from the commonly used meaning of the term, applicant intends to utilize the definitions provided herein, unless specifically indicated. The singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be understood that, although the terms first, second, etc. may be used to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. The term “and/or” includes any, and all, combinations of one or more of the associated listed items. The phrases “coupled to” and “coupled with” contemplates direct or indirect coupling.
[0035] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements.
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A system including an air intake subsystem having a housing is provided. A coalescer having a frame is disposed inside the housing. The system includes a mounting bracket, and a release mechanism coupled to the frame and the mounting bracket. The release mechanism is adapted to selectively release the frame.
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BACKGROUND OF THE INVENTION
[0001] It is widely known that a hand trowel is a flat-bladed tool with a handle and flat metal blade, used by masons and others for leveling, spreading, or shaping substances such as cement, plaster, or mortar. Also appreciated is the fact that the work output required by the user finishing a work surface with a hand trowel is decreased significantly if some other additional energy input is provided on the trowel, such as a vibration or a sonic energy generator. It is also agreed upon that vibration and/or sonic energy added to a hand trowel makes the trowel increasingly efficient over those trowels where the user alone provides the only work input. Thus, the trend in hand trowel construction is to increase the efficiency of the hand trowel and decrease the work input required by the user by increasing the work input to the hand trowel using an alternative energy source.
[0002] Therefore, what is needed is an orbital vibrating hand trowel that combines the use of vibration energy with the orbital movement of the trowel for quickly and efficiently finishing a work surface, while demanding less physical input by the user.
[0003] Another purpose of the present invention is to provide an apparatus that is inexpensive to manufacture, easy to use, free from electrical cords (cordless), rechargeable and capable of being fitted to various sized and operational float bodies, as well as significantly reducing the physical work input provided by the user and time requirement to finish a surface.
BRIEF SUMMARY OF THE INVENTION
[0004] Therefore it is a primary object, feature, or advantage of the present invention to improve over the state of the art.
[0005] It is a further object, feature, or advantage of the present invention to provide a hand trowel that is comfortable to operate.
[0006] It is a still further object, feature, or advantage of the present invention is to provide a hand trowel that does not fatigue the user.
[0007] Another object, feature, or advantage of the present invention to provide a hand trowel that is adaptable to accommodate a float body of various sizes and applications.
[0008] Yet another object, feature, or advantage of the present invention to provide a hand trowel that uses orbital translation in combination with vibration of the float for efficiently finishing a work surface.
[0009] A further object, feature, or advantage of the present invention to provide a hand trowel for finishing off cement.
[0010] It is a further object, feature, or advantage of the present invention to provide a hand trowel for finishing off a plaster surface.
[0011] Another object, feature, or advantage of the present invention is to provide a hand trowel for finishing off mortar.
[0012] Yet another object, feature, or advantage of the present invention is to provide hand trowel wherein the electrical components are encased in the handle for protection from the work environment.
[0013] A still further object, feature, or advantage of the present invention is to provide a hand trowel wherein the motor and electrical leads from the battery and/or switch to the motor are quickly accessible.
[0014] Another object, feature, or advantage of the present invention is to provide a hand trowel wherein a switch for selectively applying power to the motor is operatively located on the handle.
[0015] Yet another object, feature, or advantage of the present invention is to provide a hand trowel wherein the battery is a replaceable, chargeable NiCad battery.
[0016] A further object, feature, or advantage of the present invention is to provide a hand trowel wherein the battery encased in the handle is chargeable using a DC connector operatively positioned on the handle.
[0017] Another object, feature or advantage of the present invention is to provide a hand trowel wherein the motor is positioned in the handle and is replaceable without undue labor and time involvement.
[0018] Yet another object, feature, or advantage of the present invention is to provide a hand trowel wherein an eccentric mass is attached to the shaft of the motor.
[0019] A still further object, feature, or advantage of the present invention is to provide a hand trowel wherein a housing having an aperture for receiving the eccentric mass is attached to the float.
[0020] Another object, feature, or advantage of the present invention is to provide a hand trowel wherein the diameter of the aperture in the housing is approximately the diameter of the eccentric mass.
[0021] Still another object, feature, or advantage of the present invention is to provide a hand trowel wherein the motor is a high-speed motor with high-speed bearings.
[0022] Yet another object, feature, or advantage of the present invention is to provide a hand trowel wherein slack between the sidewall of the aperture and the eccentric mass allows for rotation of the eccentric mass with the aperture.
[0023] A still further object, feature, or advantage of the present invention is to provide a hand trowel wherein rotation of the eccentric mass within the aperture affects orbital translation of the float.
[0024] Another object, feature, or advantage of the present invention is to provide a hand trowel that is collapsible for cleaning, storing, repairing and maintaining.
[0025] Yet another object, feature, or advantage of the present invention is to provide a hand trowel wherein the eccentric mass has an aperture for receiving and attaching to the shaft of the motor.
[0026] Still another object, feature, or advantage of the present invention is to provide a hand trowel wherein the aperture for housing the eccentric mass is fitted with a high-speed bearing to facilitate transfer of orbital movement and vibration from the eccentric mass to the float body.
[0027] A still further object, feature, or advantage of the present invention is to provide a hand trowel wherein the aperture in the eccentric mass is off-center for producing vibration and an orbital movement during rotation of the eccentric mass.
[0028] Another object, feature, or advantage of the present invention is to provide a hand trowel wherein off-center rotational movement of the eccentric mass within the aperture in the housing causes the housing to vibrate and translate in an orbital pattern which in-turn is transferred to the float body thereby providing vibration and orbital translation of the float body in a plane parallel to the float body.
[0029] Yet another object, feature, or advantage of the present invention is to provide a hand trowel wherein the eccentric mass has a first stage having a first diameter and a second stage having and second diameter and the second diameter being larger than the first diameter for driving the adaptor body about an orbital pathway.
[0030] Still another object, feature, or advantage of the present invention is to provide a hand trowel wherein the shaft from the motor is supported by a high-speed bearing to facilitate rotation of the shaft and the attached eccentric mass.
[0031] According to one aspect of the present invention an orbital vibrating hand trowel, is disclosed. The trowel has a body having a first and second opposite end and a handle between the ends for grasping. The trowel also includes a motor and power source within the body. The power source is in electrical communication with the motor. An eccentric mass is connected to the motor and an adapter body is connected to a float body. The adapter body has an aperture for housing the eccentric mass. The eccentric mass rotates within the aperture of the adaptor body to move and vibrate the adaptor body and attached float body in an orbital path along a horizontal plane with respect to the float body for finishing a work surface.
[0032] According to another feature of the present invention, the handle having a switch positioned thereon for switching power on and off from the power source to the motor.
[0033] According to another feature of the present invention, the power source positioned within the handle is a rechargeable power source.
[0034] According to another feature of the present invention, the handle having a DC connection positioned thereon for communicating power to the power source for recharging the power source.
[0035] According to another feature of the present invention, rotation of the eccentric mass thereby affects translation of the float body along the orbital path.
[0036] According to another feature of the present invention, rotation of the eccentric mass thereby affects vibration of the float body along the horizontal plane with respect to the float body.
[0037] According to another feature of the present invention, the diameter of the aperture in the adaptor body is approximately the diameter of the eccentric mass.
[0038] According to another feature of the present invention, the aperture in the adaptor body having a collar for securing the eccentric mass within the aperture.
[0039] According to another feature of the present invention, the eccentric mass having a dimensional center and an aperture positioned off center of the dimensional center for connecting to a shaft on the motor.
[0040] According to another feature of the present invention, the eccentric mass is removably attached to the shaft of the motor.
[0041] According to another feature of the present invention, the diameter of the aperture in the adaptor body varies to accommodate variation in the diameter of the eccentric mass.
[0042] According to another feature of the present invention, the adaptor body having at least one pilot hole for securing the float body to the adaptor body using a screw.
[0043] According to another feature of the present invention, the float and adaptor body follows the lateral translation of the eccentric mass along the orbital pathway.
[0044] According to another feature of the present invention, the first end of the body housing the motor therein.
[0045] According to another feature of the present invention, the second end of the body having a spacer connected thereto, the spacer being connected to the float body.
[0046] According to another feature of the present invention, the spacer having at least one pilot hole for securing the spacer to the second end of the body.
[0047] According to another feature of the present invention, the spacer and the adaptor body having the same thickness.
[0048] According to another feature of the present invention, the spacer having at least one screw for connecting the spacer to the float body.
[0049] According to another feature of the present invention, the float body having a first and second opposite end and an elevated rib running the length of the float body, the first end being connected to the adaptor body and the second opposite end being connected to the spacer.
[0050] According to another feature of the present invention, the float body being pivotable about the spacer on the second end to thereby assist orbital translation and vibration of the float body about the first end.
[0051] According to another aspect of the present invention, an orbital vibrating hand trowel, is disclosed. The trowel has a motor within a handle. The trowel includes an eccentric mass connected to the motor and an aperture within an adaptor body attached to a float body. The aperture is for housing the eccentric mass. Rotation of the eccentric mass within the aperture affects orbital translation and vibration of the attached float body for finishing a work surface.
[0052] According to another aspect of the present invention, an orbital vibrating hand trowel for finishing a work surface, is disclosed. The trowel has a body for gripping and housing a motor. The trowel includes a housing having an aperture and adapted for attachment to a float body. An eccentric mass is connected to the motor and received within the aperture for affecting orbital translation and vibration of the float for finishing the work surface.
[0053] One or more of these and/or other objects, features, or advantages of the present invention will become apparent from the specification and claims that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0054] FIG. 1 is an isometric view of the present invention.
[0055] FIG. 2 is a cross-sectional view of the present invention taken along line 2 - 2 of the isometric view in FIG. 1 .
[0056] FIG. 3 is an exploded cross-sectional view of the housing and eccentric mass of the present invention taken along line 3 - 3 in FIG. 2 .
[0057] FIG. 4 is an exploded plan view of the housing and eccentric mass of the present invention taken along line 3 - 3 in FIG. 2 .
[0058] FIG. 5 is a top plan view of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0059] The present invention includes a number of aspects all of which have broad and far-reaching application. Although specific embodiments are described herein, the present invention is not to be limited to these specific embodiments.
[0060] FIG. 1 is an isometric view of the present invention. In FIG. 1 , one embodiment of the trowel 10 is shown as having generally a body 12 having a first end 14 and a second opposite end 16 and handle 18 extending between the two ends 14 , 16 for gripping. The first end 14 of the body 12 further comprises a motor cap 20 providing quick access and protection for a motor positioned within the body 12 . The second end of the body 12 has pilot holes 17 allowing passage of a screw for attaching the body 12 to the spacer 24 . The spacer 24 is in-turn connected to the float body 30 . The body 12 also comprises a switch 26 for selectively providing power to a motor. Also included on the body 12 is a DC connector 28 for charging or providing power to a power source housed within the body 12 . An adaptor body 22 is connected to the first end 14 of the body 12 . In addition, the adaptor body 22 is attached to the float body 30 . Both the spacer 24 and the adaptor body 22 may be separate pieces or part of the body 12 . The float body 30 has a first end 32 and an opposite second end 34 and an elevated rib 36 running between the ends 32 , 34 for connecting to the body 12 . The float body 30 is preferably a float for finishing a surface consisting of a workable material, such as concrete or plaster. The float body 30 may be of different shapes and sizes thereby accommodating different tasks. The float body 30 may be interchangeable. It is preferred that the spacer 24 on the second end 16 of the body 12 and the adaptor body 22 on the first end 14 of the body 12 are of equal thickness. However, the spacer 24 and adaptor body 22 may have a different thickness to accommodate manufacturing and application needs. Furthermore, the thickness of the spacer 24 and adaptor body 22 may be varied jointly or separately to accommodate a different size and shape float body 30 . The thickness of the spacer 24 and the adaptor body 22 may also be varied to change the pitch of the handle 18 on the body 12 with respect to the float body 30 . Both the adaptor body 22 end the spacer 24 are attached to the float body 30 along the elevated rib 36 . It is preferred that the body 12 be constructed of a high impact material capable of protecting the device from the abuse commonly associated with commercial grade tools. Additionally, it is preferred that the body 12 of the trowel 10 be constructed of a material that is easy to grip and non-fatiguing.
[0061] FIG. 2 is a cross-sectional view of the present invention taken along line 2 - 2 of the isometric view in FIG. 1 . In FIG. 2 , one embodiment of the trowel 10 is shown as having a body 12 . Within the body 12 is a power source 19 . It is preferred that the power source be a rechargeable NiCad battery or any other power source which permits stand-alone operation of the trowel 10 , where stand-alone operation means without a power cord being attached. Thus, any power source that is rechargeable, durable and provides stand-alone operation of the trowel is suitable as a power source. The power source 19 is in electrical communication with the motor 15 positioned in the first end 14 of the body 12 . The motor is preferably a commercial or industrial grade motor. The motor also should be a high-speed motor with high-speed bearings suitable for the wears of use in a commercial or industrial setting. The motor is preferably a sealed motor if exposed to work elements, but may have an impervious casing if protected within the body of the trowel. The power source 19 is also in electrical communication with the switch 26 for selectively providing power from the power source 19 to the motor 15 . The switch 26 may be a variable power switch for varying the speed of the motor 15 and subsequently the orbital rotation and vibration of the float body 30 . The switch 26 may be lockable to permit sustained operation of the trowel 10 without having to depress or continually hold the switch in the on position. The power source 19 and the motor 15 are encased within the body 12 and protected from being interrogated by elements external to the trowel 10 . The power source 19 and the motor 15 are both accessible within the body 12 . By removing the motor cap 20 electrical communication to motor 15 from the switch 26 and the power source 19 can be verified and remedied. The body 12 of the trowel 10 may be a single piece or a multi-piece body thereby permitting easy access to the internal workings of the trowel 10 . The second end 16 of the body 12 comprises pilot holes 17 for inserting a screw 25 for securing the spacer 24 to the body 12 . An additional pilot hole 17 is placed within the spacer 24 for securing the float body 30 to the spacer 24 using a screw 25 . The pilot hole 17 within the spacer is intentionally oversized with respect to the size of the screw 25 so as to allow transitional movement of the float body 30 with respect to the spacer 24 while yet keeping the float body 30 attached to the spacer 24 . Thus, as the first end 32 of the float body 30 is translated along an orbital pathway, the second end 34 translates in reciprocating fashion along the same axis of the body 12 and about the oversized pilot hole 17 in the spacer 24 . The spacer may be constructed of numerous materials and in numerous ways. It is preferred that the attachment used to affix the body 12 of the trowel 10 to the float body 30 be rigid and strong yet permit translation of the float body 30 forward and backwards with respect to a line of axis collinear with the length of the body 12 .
[0062] Also illustrated by FIG. 2 is the first end 14 of the body 12 that houses the motor 15 . The motor has a shaft 21 extending downward toward the float body 30 and an eccentric mass 23 attached thereto. The eccentric mass 23 is housed within the aperture 38 in the adaptor body 22 . high-speed bearing may be used to the form the inner liner of the aperture 38 to ease the stress on the motor 15 and friction on the eccentric mass 23 , as well as increase the efficiency of the trowel 10 . Using a high-speed bearing to form the aperture 38 would also diminish the amount of wear and tear on the eccentric mass 23 gyrating within the aperture 38 . The diameter of the aperture 38 in the adaptor body 22 is approximately the diameter of the eccentric mass 23 , where the eccentric mass has two different stages; the first stage 52 having a first diameter 54 and the second stage 56 having a second diameter 58 . The difference between the diameters of the eccentric mass 23 and the aperture 38 within the adaptor body 22 is sufficient to allow rotational movement of the eccentric mass 23 within the aperture 38 . The adaptor body 22 has also a collar 40 for retaining the eccentric mass 23 within the aperture 38 , as best shown by FIG. 3 . Also within the adaptor body 22 are pilot holes 17 . Screws 25 are placed within pilot holes 17 for securing the adaptor body 22 to the float body 30 . The eccentric mass 23 is preferably attached to the shaft 21 of the motor using set screw 48 , but may be attached using a keyway and key, or simply by a press-fit.
[0063] FIG. 3 is an exploded cross-sectional view of the housing and eccentric mass of the present invention taken along line 3 - 3 in FIG. 2 . Similarly, FIG. 4 is an exploded plan view of one embodiment of the housing and eccentric mass of the present invention taken along line 3 - 3 in FIG. 2 . Both FIG. 3 and FIG. 4 illustrate how rotation of the eccentric mass 23 within the aperture 38 in the adaptor body 22 effects orbital translation and vibration of the float body 30 . In particular, the motor 15 rotates shaft 21 having the eccentric mass 23 attached thereto, using set screw 48 . The eccentric mass 23 is attached to the shaft 21 by inserting the shaft 21 of the motor 15 into the aperture 42 within the eccentric mass 23 . The aperture 42 in the eccentric mass 23 has an offset center 46 from the actual or true dimensional center 44 of the eccentric mass 23 , as best illustrated by FIG. 4 . The center offset 46 of the aperture 42 within the eccentric mass 23 affects orbital movement of the eccentric mass 23 about the true or actual dimensional center 44 of the eccentric mass 23 . Movement of the adaptor body 22 and the attached float body 30 occurs as the eccentric mass 23 rotates orbitally keeping the outer periphery 50 of the second stage 56 of the eccentric mass 23 in continuous contact with the aperture wall 60 thereby pushing the adaptor body 22 radially outward along the rotating orbital point of contact between the aperture wall 60 and the outer periphery 50 of the second stage 56 of the eccentric mass 23 . Thus, the rotation of the eccentric mass 23 within the aperture 38 effects translation of the adaptor body 22 along an orbital path. Additionally, the rotation of the eccentric mass 23 induces a vibration into the adaptor body 22 attached to the float body 30 . Thus, when a user activates the motor 15 using the switch 26 the eccentric mass 23 begins to rotate within the aperture 38 thereby effecting orbital translation and vibration of the adaptor body 22 . The orbital translation and vibration of the adaptor body 22 attached to the float body 30 effects orbital translation and vibration of the float body 30 , as the adaptor body 22 is attached to the float body 30 .
[0064] FIG. 5 is a top plan view of the present invention. In FIG. 5 , the orbital vibration and translation of the float body is illustrated. The movement of the rotation of the eccentric mass 23 within the aperture 38 in the adaptor body 22 causes the float body 30 to translate in an orbital manner about the actual or true dimensional center 44 of the eccentric mass 23 . The float body 30 is permitted to translate back and forth with respect to the body 12 and along a line of axis that is collinear with the length of the body 12 . Additionally, by offsetting the aperture 42 from the actual or true dimensional center 44 causes a vibration to resonate from the eccentric mass 23 into the float body 30 . Thus, the combination of the orbital translation of the float body 30 as well as the vibration introduced in the float body 30 allows the user to efficiently and quickly close off or finish a surface of workable material such as cement, plaster, mortar, or any other shapeable, spreadable, or levelable substance.
[0065] The present invention contemplates numerous other options in the design and use of the trowel.
[0066] These and/or other options, variations, are all within the spirit and scope of the invention.
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The orbital vibrating hand trowel has a body with first and second opposite ends and a handle between the ends for grasping. The body houses a motor and power source. An eccentric mass is connected to the motor. An adapter body is connected to a float body. The adapter body has an aperture for housing the eccentric mass such that rotation of the eccentric mass within the aperture of the adaptor body moves and vibrates the adaptor body and attached float body in an orbital path along a horizontal plane with respect to the float body for finishing a surface.
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This is a division of application Ser. No. 655,925, filed Sept. 28, 1984, now U.S. Pat. No. 4,638,039.
BACKGROUND OF THE INVENTION
An effective method for the preparation of a block copolymer offers one the opportunity to modity the copolymer with monomers which are normally incompatible. Thus the process permits the chemical union of two incompatible macromolecules which would otherwise be difficult to link. A successful process for synthesis of a block copolymer requires a reliable polymerization process which is not hindered by the usual problems of linking already formed polymer chains.
It was the hope that a phase transfer catalyzed (PTC) reaction would lend itself to the synthesis of desirable polymers and free the process from the use of anhydrous aprotic solvents, which led me to exploit the particular characteristics of a PTC reaction for the purpose at hand. In nucleophilic displacement step-growth polymerizations, for example in the synthesis of polyethers and polycarbonates, these characteristics are as follows: (a) the reaction is very fast, reaching 100% yield and high molecular weight (mol wt) in a few minutes; (b) the polymer's mol wt does not depend strongly on the ratio between the nucleophilic and electrophilic reactants as in conventional step polymerizations; and, (c) the obtained polymer almost always contains electrophilic species as chain ends, independent of the reaction yield and reactant ratio.
It is hypothesized that the etherification reaction occurs in the organic phase according to a mechanism similar to that of interfacial polycondensation. The concentration of reactive bisphenolate in the organic phase is controlled by the concentration of the PTC and is very low in comparison with that of the electrophilic monomer. I eventually came to realize that PTC reactions can be exploited as a simple method for the synthesis of telechelic polymers containing electrophilic chain ends. These polymers with functional electrophilic end groups are useful polymeric materials because they can be further used as macroinitiators for cationic polymerization and for synthesis of ordered and block copolymers by condensation polymerization in the presence of a PTC.
The particular interest of this invention is to tailor an (A)(B) type block copolymer of polyarylene polyether ("PAPE") segments so that the block copolymer exhibits desired properties, for example, the ability to withstand thermal degradation at a temperature in the range from above 100° C. to about 200° C.
This invention is more particularly related to block copolymers formed by combining a PAPE segment A having phenolic (Ph) or thiophenolic (TPh) chain ends with a PAPE segment B having haloallylic chain ends. Segment A consists essentially of polymers of dihydroxybenzene, dihydroxynaphthalene, and diphenols, all referred to herein as dihydric phenols ("DHP"), and the corresponding sulfur (thio) compounds referred to as dihydric thiophenols ("DHTP"), which polymers have a Mn (number average mol wt) less than about 10,000, hence termed oligomers. One or the other DHP and DHTP, or both, are referred to herein as "DH(T)P" for brevity. Such oligomers are defined herein as polymers containing from 2 to about 100 repeating units each having the formula --DH(T)P 1 --DH(T)P 2 --, where DH(T)P 1 and DH(T)P 2 each represents the residue of a DH(T)P. These oligomers contain at least three phenyl or thiophenyl rings which may have inert substituents, each ring linked to another through an O, Si, C or S atom. Such DHP and DHTP oligomers, also, poly[DH(T)P], or [DH(T)P] n , are terminated at each end (hence "di-terminated") with a phenol ("Ph") or thiophenol ("TPh") group respectively, which group may also have inert substituents. For brevity, "di-(T)Ph-terminated" refers herein to either or both oligomers which are Ph- and TPh-terminated respectively, the preparation of which oligomers is described in detail in my copending U.S. patent application Ser. No. 586,678, now U.S. Pat. No. 4,562,243, the disclosure of which is incorporated by reference thereto as if fully set forth herein.
Specific alternating block copolymers and regular (chain extended) polymers and details of their preparation, analyses of the copolymers obtained, and a discussion of various aspects of their preparation and results of the analyses, are provided in an article titled "Functional Polymers and Sequential Copolymers by Phase Transfer Catalysis. 6. On the Transfer Catalyzed Williamson Polyetherification as a New Method for the Preparation of Alternating Block Copolymers" by Virgil Percec, Brian C. Auman and Peter L. Rinaldi, Polymer Bulletin 10, 391-396 (1983), and in another article titled "Functional Polymers and Sequential Copolymers by Phase Transfer Catalysis, 1.--Alternating Block Copolymers of Unsaturated Polyethers and Aromatic Poly(ether sulfone)s" by Virgil Percec and Brian C. Auman, Makromol. Chem. 185 617-627 (1984), the disclosures of which articles and relevant portions of the references cited therein are incorporated by reference thereto as if fully set forth herein.
SUMMARY OF THE INVENTION
It has been discovered that a Williamson etherification in the presence of a phase transfer catalyst (referred to as a modified Williamson etherification) yields alternating block copolymers and regular copolymers.
More particularly, it has been discovered that a bisphenolate or bisthiophenolate ("bis(thio)phenolate") salt of a DH(T)P may be polymerized with a monomer having a haloallylic group, preferably in situ, in the presence of an effective amount of phase transfer catalyst "PTC" sufficient to solubilize the salt in the organic phase and essentially to negate hydrolysis of the oligomer.
It is therefore a general object of this invention to provide unsaturated alternating block copolymers consisting essentially of PAPE-containing segments by first forming the bis(thio)phenolate of a PAPE oligomer, preferably in situ, by combining di-(T)Ph-terminated PAPE segments with PAPE segments having haloallylic end groups in the presence of an effective amount of PTC sufficient to solubilize the salt in the organic phase and essentially to negate hydrolysis of the oligomer.
It is also a general object of this invention to provide unsaturated chain extended copolymers consisting essentially of a PAPE oligomer extended by the residue of a reactive moiety containing a haloallylic group, by first forming the bisphenolate or bisthiophenolate of a PAPE oligomer, preferably in situ, by combining di-(T)Ph-terminated PAPE segments with PAPE segments having haloallylic end groups in the presence of an effective amount of PTC sufficient to solubilize the salt in the organic phase and essentially to negate hydrolysis of the oligomer.
It is a specific object of this invention to provide novel alternating block and unsaturated regular copolymers by combining aromatic polyether sulfone "APS" segments having terminal phenol groups (prepared from 4,4'-dichlorodiphenyl sulfone "DCPS" and bisphenol A "BPA"), with unsaturated polyethers containing chloroallylic end groups (prepared from cis- or trans-1,4-dichloro-2-butene "DCB" and BPA) as the nucleophilic chain ends; or, by chain extending the APS segments with DCB.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In preferred embodiments of my invention which yield novel unsaturated alternating block copolymers, or unsaturated regular copolymers, the method consists of a PTC polyetherification of telechelic polymers containing α-ω-di(nucleophilic) and α-ω-di(electrophilic) chain ends. The result is the formation of a difunctionalized substantially linear thermoplastic polyarylene polyether oligomer, or polyarylene polythioether oligomer (PAPE) represented by the formula:
R.sup.e --R--"PAPE"--R--R.sup.3 I
wherein,
R represents O or S in an ether linkage with R e ;
R e represents a residuum selected from R 1 e X' and R 2 e RH;
R 1 e X' represents a residuum of a reactive bis(haloallyl)moiety "HAM";
R 2 e represents the group ##STR1## X' represents halogen selected from the group consisting of fluorine, chlorine and bromine;
X" represents an inert substituent defined hereinbelow; and,
"PAPE" represents the residuum of an oligomer selected from an unsaturated alternating block copolymer represented by
["DH(T)P.sub.1 "--"DH(T)P.sub.2 "].sub.n' --HAM--"DH(T)P.sub.3 "].sub.n"III
and a regular unsaturated oligomer formed by chain extension represented by
[HAM--"DH(T)P.sub.1 "--"DH(T)P.sub.2 ⃡--HAM].sub.n'"IV
wherein, "DH(T)P 1 " and "DH(T)P 2 " are the residues of DH(T)P 1 and DH(T)P 2 which are the same or different, and "DH(T)P 3 " is the residue of DH(T)P 3 which may be the same as either DH(T)P 1 or DH(T)P 2 , or different;
HAM represents the residue of a reactive bis(haloallyl)moiety selected from a bis(haloallyl)olefin having from 4 to about 20 carbon atoms such as cis- or trans-dichlorobutene, a bis(haloallyl)cycloolefin having from 4 to about 8 ring carbon atoms such as 1,4-bis(chloromethyl)-1,3-cyclohexadiene, a bis(haloallyl)arylene having from 8 to about 26 carbon atoms and 1,4-bis(chloromethyl)benzene; and, n', n" and n'" independently represent an integer in the range from 2 to about 100.
Preferred [DH(T)P] n are oligomers formed from one or more polynuclear dihydric phenols or thiophenols having a structure
(X")(RH)Ar--X--Ar(RH)(X") ##STR2## wherein, R represents O or S;
X represents a bond between aromatic carbon atoms or a divalent connecting radical selected from the group consisting of C═O, --O--, --S--, --S--S--, --SO 2 --, --Si-- and divalent organic hydrocarbon radicals such as alkylene, alkylidene, cycloaliphatic, or the halogen, alkyl, aryl, or like substituted alkylene, alkylidene and cycloaliphatic radicals as well as alkarylene, cycloalkyl and aromatic radicals, and a ring fused to both Ar groups; and,
X" represents one or more inert substituents which if present, may each be the same or different and represent halogen, particularly chlorine or bromine; NO 2 ; alkyl having from 1 to about 18 carbon atoms, without regard for the spatial configuration such as normal, iso or tertiary; alkoxy having from 1 to about 18 carbon atoms; and, hydrogen.
As written in the structural formulae, it will be evident that the polynuclear phenol will have an RH on each phenyl ring, most preferably para- to each other, such substituents as may be present occupying one or more other positions on the ring.
Reaction between the DH(T)P 1 and DH(T)P 2 is effected with an electron withdrawing group as an activator to facilitate reaction between the two DH(T)Ps. For example, when one is BPA and the other is 4,4'-dichlorodiphenyl sulfone "DCPS", the SO 2 group is the activator, and the terminal C1 atoms react with the H of the BPA to provide an oligomer (segment A) with an alternating configuration. The identity of the activator group is not critical as long as it is inert in the reaction coupling the DHPs in the alternating configuration. Thus it will now be evident that when either of the DH(T)Ps is a diphenol linked with a weak activator group such as --O--, --S--, --S--S-- or --Si--, then the other DH(T)P should be a diphenol linked with a strong activator group such as --CO-- or --SO 2 -- to provide the alternating configuration. Most preferred are the strong activating groups such as the sulfone which bonds two halogen substituted benzenoid nuclei as in the 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, although such other strong withdrawing groups as hereinbefore mentioned may also be used with ease.
The alkyl substituents may be cyclic or acyclic, including alkyl-substituted cyclic, as long as the total carbon content conforms to the defined amount, and the same is true for alkoxy groups, provided all substituents are inert under reaction conditions. The inert substituents may be the same or different, though it will be apparent that some substituents will be easier than others for steric and other reasons.
Thus, it is seen that the particular structure of the dihydric phenol moiety is not narrowly critical. However, as would be expected, this moiety or residuum in the polymer chain can alter or vary the properties of the resultant polymer produced. Similarly, the reaction rate, optimum reaction temperature and like variables in the process can be varied by the selection of the particular dihydric phenol so as to give any desired change in rate, temperature, physical properties of the polymer and like changes.
As herein used the DH(T)P term defined as being the "residuum of the dihydric (thio)phenol" of course refers to the residue of the dihydric phenol or dihydric thiopehnol after the removal of the two H atoms from the two aromatic hydroxyl groups. Thus as is readily seen these polyarylene polyethers contain recurring groups of the residua of DH(T)Ps, or of a DH(T)P and a compound containing a reactive HAM, bonded through aromatic ether oxygen or thioether atoms.
It is preferred that, of the two or more DH(T)P compounds used for alternating block copolymers, the first in segment A be a bisphenol type of compound, and the other in segment A be a dihalobenzenoid compound which has the two halogns bonded to benzene rings having an electron withdrawing group in at least one of the positions ortho and para to the halogen group. The dihalobenzenoid compound can be either mononuclear where the halogens are attached to the same benzenoid ring, or polynuclear where they are attached in different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of that benzenoid nucleus.
Any of the halogens may be the reactive halogen substituents on the benzenoid compounds. Fluorine and chlorine substituted benzenoid reactants are preferred; the fluorine compounds for fast reactivity and the chlorine compounds for their inexpensiveness.
More preferred are dihydric polynuclear phenols of the following four types including the derivatives thereof which are substituted with inert substituents: ##STR3## in which R 5 represents hydrogen, lower alkyl having from 1 to about 5 carbon atoms, phenyl and the halogen substituents thereof, and R 5 may each be the same or different. ##STR4##
Most preferred are PAPE oligomers exemplified by alternating configurations of VI and VIII; VI and IX; VI and X; VIII and X; VII and IX; and IX and X, which oligomers are then difunctionalized by the process of this invention to yield difunctionalized poly[dihydric phenols]("di-[DHP]" for brevity).
Examples of the particular foregoing polynuclear phenols, and others referred to by the structure (IV) are given in U.S. Pat. No. 4,108,837 the disclosure of which is incorporated by reference thereto as if fully set forth herein.
A preferred segment A is represented by the formula
HO--BPA--O--DPS--BPA--.sub.n' --BPA--OH
wherein BPA and DPS represent the residua of BPA and DHPS. The DHPS may be represented by the structure ##STR5## wherein the ring may have inert substituents and X' has the same connotation as that set forth hereinabove.
In the particular example of a specific APS (segment A), namely the oligomer of BPA and DCPS, it is formed by the reaction of an alkali metal salt of the BPA, or BTPA preferably the potassium or sodium salt, and DCPS in a PTC reaction, as described hereinbelow. The chain length of the APS oligomer formed is controlled by the relative ratio of BPA or BTPA and DCPS, a relatively lower Mn being obtained with a molar excess of BPA or BTPA; the larger the excess, the lower the Mn. The oligomer has a backbone which includes a repeating unit [DPS--BPA], it being evident that when either moiety in the repeating unit is substitued with inert substituents, the repeating unit will be represented by [DPS(X")--BPA(X")]. Analogously, when the DHTP is BTPA, the repeating unit wil be represented by [DPS(X")--BTPA(X")]
Though it is evident that the DH(T)P must always be a dihydric (thio)phenol, that is, have a single OH or SH group on each phenyl ring, it is not essential that the OH or SH group be at the 4-position, though this is the most convenient.
The physical and chemical properties of the di-[DH(T)P] oligomer formed may be tailored by the choice of the substituted (or not) DHP or DHTP used. Alkylation, alkoxylation or halogenation of BPA or BTPA yields a mixture of substituted products, alkylated products being most preferred among which the ortho-substituted BPA or BTPA predominates.
In the particular example of a specific segment B, namely an oligomer of BPA and cis- or trans-dichlorobutene "DCB", it is formed by the reaction of an alkali metal salt of the BPA, preferably the sodium salt, in a PTC reaction, as described hereinbelow. Again, the chain length is controlled by conventional means, and the resulting segment B is represented by the following formula XII
ClCH.sub.2 CH═CHCH.sub.2 --O--BPA--O--CH.sub.2 CH═CHCH.sub.2 --.sub.n'" O--BPA--O--CH.sub.2 CH═CHCH.sub.2 Cl
in which the backbone includes a repeating unit [BPA--DCB], it being evident that when the BPA is substituted with inert substituents the repeating unit will be represented by [BPA(X")--DCB].
In another specific example, segment B may be formed from an oligomer of DPK and DPS represented by the formula
OH--DPK--O--DPS--DPK--.sub.n' --DPK--OH
the sodium salt of which is reacted with DCB in a PTC reaction to yield a segment B having the formula
ClCH.sub.2 CH═CHCH.sub.2 --O--DPK--O--DPS--DPK--.sub.n' --O--CH.sub.2 CH═CHCH.sub.2 Cl
which is an α-ω-di(chloroallyl)polyether ("PE").
A simple chain extended copolymer is represented by the formula
R.sup.e --R--"DH(T)P.sub.1 --.sub.n' --HAM--"DH(T)P.sub.1 "--.sub.n'" --R--R.sup.e
in which the repeating unit corresponds to formula (III) hereinbefore where DH(T)P 1 , DH(T)P 2 and DH(T)P 3 are the same. Of course chain extension may be obtained when DH(T)P 1 and DH(T)P 2 (segment A) are different, and segment B would be formed by providing segment A with haloallylic chain ends, before they were polycondensed.
In the simple example, chain extension is obtained with BPA and chloroallyl-terminated BPA formed by reacting BPA and cis- or trans-DCB. In another chain extension, an oligomer of BPA--DPS having a Ms of about 2550 is reacted with another oligomer of BPA--DPS having a Mn of about 4175 which has chloroallyl chain ends.
The PTC reaction:
A PAPE segment A oligomer is prepared by reaction of an excess of the sodium salt of BPA (to provide R 2 e RH phenolic or thiophenolic end groups) with DCPS in the presence of a solubilizing amount of a PTC under aqueous alkaline conditions. By a "solubilizing amount" of PTC I refer to an amount sufficient to solubilize the alkali metal salt (bisphenolate) of the [DH(T)P] n' formed in the aqueous phase. By "aqueous alkaline conditions" I refer to a large excess of an aqueous solution of an alkali metal hydroxide containing from about 15% to about 75% by weight (% by wt), and preferably from about 30% to about 50% by wt of alkali metal hydroxide. Preferred alkali metal hydroxides are those of sodium and potassium. By "large excess" I refer to an excess based on the number of moles of OH or SH groups originally present in the [DH(T)P] n , preferably from about a two-fold (2 times) to a twenty-fold (20 times) excess.
A PAPE segment B oligomer is prepared in an analogous manner by condensation polymerization of an excess of a reactive HAM (say DCB) to provide haloallylic end groups, with BPA in an aromatic solvent and 3N aqueous NaOH reaction mixture in the presence of a large excess of PTC, at room temperature or slightly higher, and the segment B obtained by successive precipitaitons.
The alternating block or regular copolymers of PAPE segment A and PAPE segment B, are also prepared in an analogous manner by precipitating the salt of segment A in an aromatic solvent and aqueous alkali reaction mixture, redissolving the salt by addition of a large excess of PTC and adding a solution of the PAPE segment B in a halogenated aromatic solvent.
Because the rate of the PTC reaction is slow at low concentrations of PTC, the concentration of PTC used is a major molar amount, that is more than 50 mol %, so that the reaction proceeds at an economical rate.
The PTC reaction may be carried out in either (i) the precipitation mode, or (ii) the in situ mode, as described in greater detail in my copending application Ser. No. 586,679 filed Mar. 6, 1984, the disclosure of which is incorporated by reference thereto as if fully set forth herein.
The PTC reaction to prepare the alternating block copolymer, for example, may be carried out in the precipitation mode by (a) precipitating the salt of segment A from an organic solvent for the oligomer by reaction with an excess, based on the moles of --OH or --SH groups originally present in the oligomer, of an aqueous solution of an alkali metal hydroxide; (b) solubilizing the salt by adding a major molar amount of the PTC, based on the mole equivalents (mol equivs) of --OH or --SH groups originally present in the oligomer; and, (c) condensation polymerizing the solubilized salt with segment B present in at least an equimolar amount, based on the moles of --OH or --SH groups originally present in the segment A so that the alternating block PAPE copolymer formed has haloallylic chain ends which are reactive.
The foregoing PTC reaction may be carried out in the in situ mode by forming the salt of segment A in situ by (a) contacting the segment A with the PTC dissolved in an organic solvent for the oligomer and PTC; thereafter (b) adding at least one molar equivalent of segment B for each mole of --OH or --SH groups originally present in the oligomer; then (c) adding an excess, based on the moles of --OH or --SH groups present, of an aqueous solution of an alkali metal hydroxide to obtain allylic chain ends.
By PTC, I refer to onium salts, macrocyclic polyethers (crown ethers), macrobicyclic polyethers (cryptands), and the like, most preferred being the onium salts of a Group VA element of the Periodic Table having certain structural limitations. The preferred salts have the formula R n Y + X - where Y is chosen from N, P and S; R represents either different or identical monovalent organic radicals bonded to Y by covalent linkages; X - is a counterion; and n is an integer which may be 3 or 4. When Y is pentavalent, for example P or N, then N=4, and when Y is tetravalent, for example S, then n=3. In an analogous manner, onium salts having certain multivalent organic substituents may be useful in this invention. Examples include multivalent organic radicals that include Y in a ring, and those that are bonded to more than one Y.
More preferred onium salts for use in this invention have the formula (R a R b R c R d Y + )X - wherein Y is N or P, and R a -R d are monovalent hydrocarbon radicals preferably selected from the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl moieties or radicals, optionally substituted with suitable heteroatom-containing functional groups. The total number of carbon atoms in R a , R b , R c , and R d if the salt is quaternary, should be at least 10 and is preferably in the range from about 15 to 40. No theoretical maximum number of carbon atoms for inclusion in the onium salts exists, although in general, about 70 carbon atoms represents the upper limit imposed by practical limitations. Since the liquid phase involved are aqueous and organic, the number of carbon atoms and structure of the onium salts are usually selected to impart to the salt the requisite solubility in the organic phase. The onium salt itself is nonreactive to all materials in the reaction mixture except the reactants themselves, and the addition of the HAR to the PS takes place in the organic phase.
Most preferred onium salts have Y=N, and the hydrocarbon radicals where R a is C 2 H 5 , and R b , R c , and R d are each selected from the group consisting of n-C 4 H 9 ; n-C 5 H 11 ; mixed C 5 H 11 ; n-C 6 H 13 ; mixed C 6 H 13 ; C 6 H 5 ; C 6 H 5 CH 2 ; n-C 8 H 17 ; n-C 12 H 25 ; n-C 18 H 37 ; mixed C 8 -C 10 alkyl; and the like. However, R a may also be selected from n-C 3 H 7 and n-C 4 H 9 .
Various counterions may be used, including Cl - , Br - , I - , F - , HSO 4 - and the like. Most preferred is HSO 4 - . A commercially available and highly effective onium salt PTC is tetrabutylammonium hydrogen sulfate ("TBAH").
The reaction temperature and pressure conditions for forming segment A, segment B and the alternating block or regular copolymers of this invention are not critical, most reactions occuring at ambient (atmospheric) pressure and above ice-bath temperature (0° C.) but below a temperature at which the PAPE formed will prematurely polymerize, or above that which will deleteriously affect the structure of the oligomer. The pressure may range from about 1 to about 20 atms, and the precise temperature at which a particular reaction will proceed most favorably will depend upon the particular DH(T)P or reactive HAM chosen, the mol wt of the PAPE segments formed, and the solvent medium, inter alia, as one might expect, and may be determined with a little trial and error, as one skilled in the art would expect to do. Most preferred for forming the alternating block copolymers and regular copolymers is a temperature in the range from about 10° C. to about 150° C.
The main criterion for choice of the solvent is its insolubility in the aqueous alkaline phase, because the solubilization of the DH(T)P-salt or PAPE-salt with the PTC (say, TBAH) occurs quite readily in most organic phases, whether the salt is precipitated, or whether it is formed in situ and is solubilized without actually being precipitated. Solvents such as DMSO and THF which are soluble in water, but are essentially insoluble in this aqueous alkaline phase, may be used. To tailor an alternating block PAPE copolymer to conform with theoretical expectations, it is most preferred to use an inert, that is non-reactive, solvent such as dichlorobenzene or other inert halogenated aromatic, aliphatic or cycloaliphatic liquids.
Precipitation of the DH(T)P-salt or PAPE-salt will occur when the excess aqueous alkali is added to a solution of the salt in the organic solvent. The salt so formed is then solubilized by the PTC and is taken up by the organic phase. When the reactive HAM is added to form segment B, or to form a chain extended regular copolymer, reaction occurs and the PAPE oligomer is difunctionalized. This first mode of carrying out the difunctionalization is referred to as the "precipitation mode".
Precipitation of the salt is avoided when the PTC is dissolved in the organic phase and added to the DH(T)P and the reactive HAM then added. Added last, is the aqueous alkali so that the PAPE-salt is formed in situ and the desired difunctionalization results without actual precipitation of the PAPE-salt. This second mode of carrying out the difunctionalization is referred to as the "in situ mode". The reaction mixture is always homogeneous. The phenolate of the PAPE oligomer is not in contact with a solvent which might react with the terminal --OH or --SH group in the absence of the reactive HAM. As will be evident, such a reaction will preclude the effective difunctionalization sought. Formation of the alternating block PAPE copolymer or the regular copolymers formed by chain extension is in a manner analogous to that described hereinabove.
In a specific embodiment the invention is illustrated for a [DHP] n oligomer, APS segment A formed from BPA and DCPS, and, a sement B oligomer formed from BPA and DCB. The relatively now Mn APS oligomer was formed by the condensation of excess postassium salt of BPA with DCPS in anhydrous DMSO according to known methods, for example as described by R. N. Johnson et al in J. Polym. Sci., A-1, 5, 2375 (1967), inter alia. The yield is nearly 100% and the di-hydroxy oligomer obtained may be purified by precpitation from chloroform solution into methanol.
The Mn of the APS oligomer was determined by quantitatively esterifying the phenolic end groups and the degree of polymerization was determined by 1 H-NMR spectra from the following relationships: ##EQU1## wherein DNBC=3,5-dinitrobenzoyl chloride, and
CBC=4-cyanobenzoyl chloride.
Measured Mn were in the range from about 1000 to about 7000.
The degree of polymerization of the BPA--DCB segment B was determined by 200 MHz 1 H-NMR spectrsocopy, based on the structure XII, and using the following relationships: ##EQU2## Measured Mn were in the range from about 1000 to about 15000. Various segment A and segment B oligomers listed in Table I were prepared and polycondensed to yield the chain extended (regular), and alternating block copolymers listed in Table II hereinbelow.
Relatively high mol wt alternating block copolymers and regular copolymers in the range from about Mn 10,000 to about 200,000 may be used with a conventional free radical initiator or simply thermally crosslinked while it is being injection molded into pump housings and the like. The crosslinked polymer is an engineering plastic which has excellent solvent resistance quite unlike commercially available PAPE, for example Udel® APS which is available in the mol wt range of from about 20,000 to about 50,000, but with comparable physical strength. Lower Mn alternating block and regular copolymers in the mol wt range from about 10,000 to about 100,000 may be crosslinked in solution with any monomer or macromer with a reactive vinyl group to form polymers which may also be used for various forming and molding applications. When crosslinking is not desired, the copolymers may have an even higher mol wt than 200,000 though the time required to form such copolymers militates against their economical preparation. Still another use for the alternating block and regular copolymers is for blending with polymers to improve their processability, and to increase the T g of the finished product because of the generally high T g contributed by the copolymers after crosslinking.
A particular segment B formed by the polycondensation of BPA with cis- and/or trans-DCB is given in the following example 1.
EXAMPLE 1
A mixture of 5.02 g (0.022 mol) of BPA dissolved in 72 ml (0.24 mol) of 3N NaOH, 72 ml of toluene, 3.025 g (0.0242 mol) of cis- or trans-DCB, and 1.64 g (4.84 mmol) of TBAH was stirred at 70° C. for 5 hr. After cooling, the organic layer was diluted with toluene, washed with dil HCl solution and then with water, and dried over anhydrous MgSO 4 . The polymer was precipitated twice into methanol; the second time from CHCl 3 solution. The yield was about 100% in both cases. The mol wt of segment B oligomers made in an analogous manner is controlled by conventional methods to yield oligomers preferably in the range from about 1200 to about 9,000.
Chain extension by copolymerization of an APS with a reactive HAM is illustrated in the following example 2.
EXAMPLE 2
2.42 g (0.95 mmol) of APS-1 (see Table I) were dissolved in 10 ml of chlorobenzene. 5 ml (0.015 mol) of 3N NaOH were added to the stirred solution and the sodium salt of the polysulfone precipitated immediately. After the addition of 0.645 g (1.9 mmol) of TBAH, the reaction mixture turned to a clear solution. 0.12 g (0.95 mmol) of cis-DCB were added and the reaction stirred at 70° C. for the reaction times given in Table II. After cooling, the polymer solution was washed with dilute HCl, water, and precipitated into methanol. The mol wt of the chloroallyl-chain ended APS is determined by that of the starting APS oligomer.
EXAMPLE 3
Formation of an alternating block copolymer of an APS or other DH(T)Ps with a segment B, particularly the BPA--DCB oligomer formed above having chloroallyl chain ends takes place in a manner analogous to that described hereinabove in example 2, except that segment B is first prepared and is used in a required amount sufficient to yield an alternating block copolymer of desired mol wt, instead of the reactive HAM used for chain extension.
Other alternating block copolymers may be prepared in an analogous manner using any preselected combination of one or more DH(T)Ps and reactive HAMs.
TABLE I__________________________________________________________________________SampleBPA:DCPS --Mn --Mn Mi V.sub.E, ml T.sub.gidentif.mole ratio (theor.)** (NMR) (GPC)* (GPC)* °C.__________________________________________________________________________APS-11.50:1.0 24431 2550 2350 28.1 135APS-21.33:1.0 3353 3050 3900 27.5 138APS-31.25:1.0 4211 3410 5400 27.0 148APS-41.20:1.0 5096 3875 5700 26.9 146APS-5 2.0:1.0 1556 1210 1000 29.1 87__________________________________________________________________________ *each corresponds to the maximum of the GPC curve. **calculated from theoretical DP and adding a BPA unit for the second chain end.
Chain extension of an APS with cis- or trans-DCB, and multiblock copolymerization of an APS with a PE having chloroallyl chain ends yield chain extended copolymers and alternating block copolymers listed in Table II hereinbelow. The first four APS-1 alternating block copolymers are with segment B PEs containing only trans-DCB; the last two are with APS-4 and APS-5 which contain only cis-DCB in the PE.
TABLE II__________________________________________________________________________SampleSegments Reaction V.sub.e, ml Mi T.sub.gidentif(A)/(B) mole ratio time, hr. (GPC)* (GPC)* °C.__________________________________________________________________________chain ext.APS/t-DCB 1.0:1.0 24.0 22.7 42000 153chain ext.APS/c-DCB 1.0:1.0 24.0 21.8 63000 160chain ext.APS/c-DCB 1.0:1.0 17.0 23.9 25000 --alt. blockAPS-1/PE 1.0:1.0 24.0 23.4 31000 88**alt. blockAPS-1/PE 1.0:1.2 24.0 21.8 63000 --alt. blockAPS-1/PE 1.0:1.0 40.5 21.9 61000 79***alt. blockAPS-1/PE 1.2:1.0 23.0 22.5 46000 --alt. blockAPS-4/PE 1.0:1.0 37.5 23.2 34000 --alt. blockAPS-5/PE 1.0:1.0 38.0 21.9 61000 --__________________________________________________________________________ *each corresponds to the maximum of the GPC curve. ***T.sub.g of APS/PE blend (mole ratio 1.0:1.0) = 70° C. ***T.sub.g of APS/PE blend (mole ratio 1.0:1.0) = 56° C.
The structure of the segments A and B, and those of the alternating block and regular copolymers formed by chain extension, were confirmed by gel permeation chromatography, by differential scanning calorimetry (DSC), by infra-red (IR) and nuclear magnetic resonance (NMR) analyses, details of which are set forth in the aforementioned articles co-authored by me.
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A modified Williamson etherification in the presence of phase transfer catalyst is used to synthesize alternating block copolymers and regular copolymers. Unsaturated polyethers of a polynuclear dihydric phenol containing chloroallylic (electrophilic) end groups (prepared from cis- or trans-1,4-dichloro-2-butene and Bisphenol A) and aromatic poly(ether sulfone)s containing terminal phenol (nucleophilic) groups are polycondensed in the presence of tetrabutylammonium hydrogen sulfate as phase transfer catalyst to give alternating block copolymers. The same telechelic polymers were chain-extended with dinucleophilic or dielectrophilic monomers under similar reaction conditions. Both the regular copolymers and the alternating block copolymers were characterized by gel permeation chromatography and DSC.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/584,965, entitled “A Process to Recommend and Discover Interesting On-Line Documents”, filed Jan. 10, 2012, which is herein incorporated by reference in its entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
This invention was made with government support under Contract No. DE-AC05-00OR22725 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present disclosure relates to document searching and more specifically to a system and method of identifying relevant documents.
2. Description of the Related Art
One method of searching for electronic documents online is by entering one or more keywords into a search engine, such as a search engine webpage on the Internet. In general, the quality of such a search depends on the skill of the user and their ability to craft and submit an appropriate query. There are some systems that can return results from a keyword search and offer to find more documents based on a given result. If someone was interested in several different topics, they may need to spend a significant amount of time searching for and reviewing documents that may meet the search criteria, but may not be of any real interest.
Earlier works by Potok et al., address the need for automated document searching and the following three references are incorporated by reference as if included here at length. Potok et al., Agent-based method for distributed clustering of textual information, U.S. Pat. No. 7,805,446; Potok et al., Method for gathering and summarizing internet information, U.S. Pat. No. 7,693,903; and Jiao and Potok, Dynamic reduction of dimensions of a document vector in a document search and retrieval system, U.S. Pat. No. 7,937,389.
Further improvements can advance the state of the art.
BRIEF SUMMARY OF THE INVENTION
The system and method includes searching with a set of multiple seed documents, rather than one or more keywords or a single seed document. The disclosed system and method can find target documents that are similar to the seed documents, and return the results. The results can be sorted and recommendations can be made.
This system and method is capable of comparing a large number of target documents to multiple seed documents chosen by a user to determine which target documents are relevant to user. Recommendations of target documents can be made based on the similarity of the individual seed documents to the target documents. That is, the individual seed document vectors and their similarity to the target documents are preserved.
Disclosed is a method for discovering documents, i.e. on-line documents, using a computer and bringing them to the attention of a human observer. A computer may be programmed with a series of instructions that, when executed, cause the computer to perform a series of method steps. The method steps may include: defining a set of multiple seed documents of interest; processing each seed document, i.e. by removing stop words and stemming the terms; generating seed document vectors; obtaining target document vectors, i.e. retrieving one or more target documents and generating a target document vector or receiving a predetermined target document vector; comparing each target document vector to each seed document vector, i.e. by using a dot product of the two vectors to represent the similarity of the terms within the seed document and the target document to obtain a similarity value; sorting by the similarity values, i.e. creating similarity tuples including a seed document identifier, a target document identifier, and a similarity value between the two and sorting the similarity tuples from highest similarity value to lowest similarity value; and recommending one or more target documents based on the sorted values, i.e. displaying information about the sorted data for the human observer.
A system for discovering documents, i.e. on-line documents, for a human observer is also disclosed. The system may include a computer with a storage device, a processor, an input device, and a display device. The computer obtains a set of multiple seed documents from the input device, processes each seed document by removing the stop words and stemming the terms, generates a seed document vector for each seed document, obtains a target document vector, i.e. retrieves one or more target documents and generates a target document vector for each target document, compares the target document vector to the seed document vector to obtain a similarity value, i.e. using a dot product of the two vectors to represent the similarity of the terms within the seed document and target document, sorts by the similarity values from highest to lowest with the processor, and displays the similarity values for the human observer on the monitor.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
A more complete understanding of the preferred embodiments will be more readily understood by reference to the following detailed description when considered in conjunction with the accompanying drawings where like numerals indicate common elements among the various figures.
FIG. 1 is a flow diagram in accordance with an example system and method of the present invention; and
FIG. 2 is a flow diagram in accordance with an example system and method of the present invention.
FIG. 3 is a flowchart in accordance with an example system and method of the present invention.
FIG. 4 is a system diagram in accordance with an example system and method of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of a method of the present invention is described in connection with the flowchart 300 illustrated in FIG. 3 . The method for discovering and recommending interesting documents includes obtaining a seed document vector for each of a plurality of seed documents 302 , obtaining a target document vector for each of a plurality of target documents 304 , comparing each target document vector to each seed document vector to obtain a similarity value for each comparison 306 , sorting by the similarity values 308 , and recommending one or more target documents based on the sorted results 310 .
A document vector is a mathematical representation of the term frequencies of a document. For example, a document vector can be represented by a list of words and the number of times each word appears in the document. Seed documents are the documents of interest upon which a search is performed. Target documents are the documents that make up the pool of documents that are being searched. Seed document vectors and target document vectors refer to the document vectors of the seed documents and the document vectors of the target documents, respectively.
In some embodiments, seed document vectors and target document vectors can be generated. In such embodiments where document vectors are generated, the steps of obtaining seed document vectors 302 or obtaining target document vectors 304 may include obtaining documents, processing the documents, and generating the document vectors.
Documents can be obtained from essentially any source and the way in which a user obtains documents can vary from application to application. For example, seed documents or target documents can be obtained from the Internet, or another database. In one example, ten publicly available research papers can be used as a set of seed documents, i.e. documents of interest chosen by the user of the system. These seed documents can be downloaded to a local computing machine, converted to text files, and stored on a local computing machine. The documents may be stored in a local or remote database. Although ten seed documents were chosen in this example, additional or fewer documents can be used as the plurality of seed documents. In one embodiment, documents may be scanned using a scanner and processed with optical character recognition software.
As another example, the system and method may include gathering a collection of target documents to be searched. For example, the target documents can be obtained from the Internet or other sources, such as a database. The source of the documents may be static, meaning that no additional documents are added over time, or may be dynamic, meaning that documents may be added or deleted from the source over time. For example, target documents can be obtained from one or more Really Simple Syndication (“RSS”) feeds. In one embodiment, the target documents include several thousand RSS feeds as the source. In one example, these entries were downloaded to a local computing machine and stored in a local database.
The content of the documents can vary from application to application. For example, seed documents can be related or unrelated to one another. That is, the seed documents may include a plurality of documents with disparate subject matter relative to one another, a plurality of documents with similar subject matter relative to one another, or a combination of some seed documents with disparate subject matter relative to other seed documents and some seed documents with similar subject matter relative to other seed documents. As another example, the target documents can be related to a certain topic, be derived from a particular source or set of sources, or be a random sampling of publicly available documents, for example, target documents available on the Internet.
Before generating a document vector, the documents may undergo some processing. For example, in one embodiment, the system iterates through each of the seed documents, performing a number of steps, including the removal of stop words and the stemming of terms. Then, after processing, the document vector can be generated for each seed document.
Essentially any method for generating a document vector can be utilized. In the current embodiment, a document vector can be generated for a document using the Term Frequency/Inverse Corpus Frequency (TFICF) method, as disclosed in U.S. Pat. Nos. 7,693,903 and 7,805,446, which were incorporated by reference above. In alternative embodiments a document vector can be generated using a different method.
In another embodiment, predetermined seed document vectors and target document vectors can be received. Generating document vectors may be unnecessary, for example, if they have already been generated previously. Document vectors, either seed document vectors or target document vectors, can be received by retrieving them from memory. For example, a database of document vectors may be available. The database may be available internally in memory of the computer handling the search or alternatively may be available externally in memory of a different system.
Some embodiments can include a combination of receiving predetermined document vectors and generating document vectors. For example, in some embodiments, predetermined target document vectors are received and seed document vectors are generated. In other embodiments, some target document vectors and/or seed document vectors are generated and some predetermined target document vectors and/or predetermined seed document vectors are received.
The similarity between a seed document and a target document can be ascertained by comparing the seed document vector and the target document vector. This can also be referred to as a search. Perhaps the comparison can be best understood in connection with FIG. 1 , which illustrates a representative flow diagram 100 .
Referring to FIG. 1 , an embodiment that includes generating seed document vectors and target document vectors, the system retrieves a single target document 102 and creates a target document vector 104 for that document. The system also retrieves a single seed document 106 and creates a seed document vector 108 for that document. The first target document vector 104 is then compared to the first seed document vector 108 using a dot product of the two vectors to represent the similarity 110 of the terms within the two documents. The result can be recorded as a similarity tuple 112 including <profile document name or ID>, <target document name or ID>, and <similarity>.
This process can be iterated to generate a similarity tuple for every combination of target document and seed document. For example, with three seed documents and 1000 target documents, the process can generate 3000 similarity tuples—one tuple for every combination of seed document and target document.
The order of the comparisons can vary. For example, the target document vector can be compared to each of the remaining seed document vectors, for example where there are ten seed documents there would be nine remaining seed documents, and the similarities tuples can be recorded for those comparisons. At that stage, one target document has been compared to all of the seed documents. Each of the remaining target documents may then be compared to each of the ten seed document vectors, and the similarities tuples can be recorded for each comparison. Now, all of the target documents have been compared to all of the seed documents, and the results recorded. In another embodiment, each seed document vector could be taken in turn and compared to every target document before moving to the next.
The results of the comparison can be sorted based on the similarity values. For example, in embodiments where similarity tuples are recorded, the similarity tuples can be sorted based on the similarity values from highest to lowest, so that the similarity tuple with the most similar seed and target documents are at the top of the list. This can simplify the review by the user or a piece of software of the most relevant document for each of the seed documents. In alternative embodiments, the results can be sorted differently. For example, the results can be sorted in reverse, from lowest similarity value to highest similarity value.
Recommendations of target documents are made based on the similarity of the individual seed documents to the target documents as opposed to recommendations based on the similarity of a collection of seed documents to the target documents. That is, the individual seed document vectors and their similarity to the target documents can be preserved.
Recommendations based on the search can be provided to a user. For example, the system can recommend a certain target document that is similar to a certain seed document. In one embodiment, the recommendation can include displaying on a computer monitor a filtered list of sorted similarity tuples. Such an approach is illustrated in FIG. 2 . A list of unsorted similarity tuples 202 are shown being sorted into a list of sorted similarity tuples from highest similarity value to lowest similarity value 204 . The list of sorted similarity tuples 204 is shown being formatted into a recommendation 206 including a list of the three similarity tuples with the highest similarity values. The recommendation 206 is in the form <seed document name> recommends <target document name> at similarity <similarity>. Thus one of the seed documents is “recommending” a target document with an indication of the similarity ranking.
Although the embodiment illustrated in FIG. 2 recommends the three similarity tuples with the three highest similarity values, in alternative embodiments, the system can provide a recommendation by filtering or otherwise organizing the results differently in order to identify interesting target documents that are similar to a seed document. For example, the results can be filtered to provide a certain number of the highest similarity tuples for each seed document, instead of a certain number of the highest similarity tuples regardless of the originating seed document.
The recommendation or output can be produced in a variety of different formats. For example, the output can be produced in XML format so that an RSS Reader can format the XML. This can allow for easy Internet access to the recommendations. As another example, the recommendation can be provided in a text file.
Referring to FIG. 4 , a computer apparatus 402 is part of a system 400 used to execute a series of commands representing the method steps described above. The computer 402 may be a mainframe, a super computer, a PC or Apple Mac personal computer, a hand-held device, a smart phone, or another central processing unit known in the art. The computer 402 is programmed with a series of instructions that, when executed, cause the computer 402 to perform the method steps as described and claimed in this application. The instructions that are performed are stored on a machine-readable data storage device 404 . In the illustrated embodiment, the computer 402 includes a processor 406 , input device 408 , and a display device 410 .
The machine-readable, non-transitory data storage device can be a portable memory device that is readable by the computer apparatus. Such portable memory device can be a compact disk (CD), digital video disk (DVD), a Flash Drive, any other disk readable by a disk driver embedded or externally connected to a computer, a memory stick, or any other portable storage medium currently available or yet to be invented. Alternately, the machine-readable data storage device can be an embedded component of a computer such as a hard disk or a flash drive of a computer.
The computer and machine-readable data storage device can be a standalone device or a device that is imbedded into a machine or system that uses the instructions for a useful result. The computer may be part of a larger system or network of connected computers.
While this disclosure describes and enables several examples of a system and method for recommending and discovering interesting documents, other examples and applications are contemplated. Accordingly, the invention is intended to embrace those alternatives, modifications, equivalents, and variations as fall within the broad scope of the appended claims. The technology disclosed and claimed herein is available for licensing in specific fields of use by the assignee of record.
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Disclosed are several examples of systems that can read millions of news feeds per day about topics (e.g., your customers, competitors, markets, and partners), and provide a small set of the most relevant items to read to keep current with the overwhelming amount of information currently available. Topics of interest can be chosen by the user of the system for use as seeds. The seeds can be vectorized and compared with the target documents to determine their similarity. The similarities can be sorted from highest to lowest so that the most similar seed and target documents are at the top of the list. This output can be produced in XML format so that an RSS Reader can format the XML. This allows for easy Internet access to these recommendations.
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BACKGROUND OF THE INVENTION
This invention relates to production of false-twist textured yarn of polyester filaments, and is more particularly concerned with a process for producing a feed yarn for draw-texturing into yarn having distributed therethrough portions which dye to deeper shades than other portions of the yarn.
Conventional processes for producing textile yarns of polyester filaments have involved melt-spinning polyethylene terephthalate into yarn at take-off speeds of 500 to 1,500 meters per minute (500 to 1,640 yards/minute). The take-off speed refers to the speed of the solidified yarn at windup or at roll for forwarding the yarn to subsequent processing.
Conventional as-spun yarn is usually drawn at a draw ratio of about 3.5 to 4.5X (3.5 to 4.5 times greater length) to produce the fully-drawn, uniform yarn of commerce. Alternatively, the yarn can be incompletely drawn to provide a random distribution of thick and thin sections along the filaments, of which the incompletely drawn thick sections have a higher dye uptake (dye to deeper shades) to provide attractive dyed fabrics. Lewis U.S. Pat. No. 2,278,888 discloses in Example V that the thin sections can be formed at desired locations along the yarn by contacting these portions of the yarn with a heated surface during drawing. Bates U.S. Pat. No. 3,662,055 discloses a programmed heating of portions along the yarn with a flame as the yarn is drawn. A running yarn can be intermittently vibrated in and out of contact with the flame by means of an electromagnetic vibrator acting on guides through which the yarn is passing. The vibrator can be programmed electrically according to any desired periodical or random or psuedo-random program and the program will be reproduced along the yarn in a corresponding arrangement of thick and thin sections. Instead of vibrating the yarn, the flame can be deflected in and out of contact with the yarn by modulating the flame or by deflecting the flame with an impinging stream of gas which is modulated in a programmed manner.
Petrille U.S. Pat. No. 3,771,307 discloses a false-twist texturing process for texturing spin-oriented polyester yarn prepared by melt-spinning at take-off speeds of 3,000 to 4,000 yards per minute (2,744 to 3,660 meters/minute). The as-spun yarn is drawn at a draw ratio of 1.3 to 2.0 as it is false-twist textured. The above methods, of intermittently heating conventional yarn while incompletely drawing the yarn to form thick and thin sections along the yarn, will not accomplish the desired result when used to produce a feed yarn for false-twist texturing processes. The incompletely drawn thick sections will melt or stick together at the high heater temperature used to set crimp in the yarn, or will be fully drawn at the tensions used. Spin-oriented yarn can be incompletely drawn while intermittently heating it to form thick and thin sections along the yarn, but the incompletely drawn thick sections of this feed yarn will be fully drawn at the temperatures and tensions used in draw-texturing processes and the desired deeper-dyeing sections will not be obtained.
SUMMARY OF THE INVENTION
The present invention provides a process for producing a feed yarn which can be draw-textured, without difficulty with filaments melting or sticking together, to have a programmed distribution of deeper-dyeing sections along the resulting false-twist textured yarn.
In the process of this invention, a spin-oriented polyester yarn is passed in a substantially undrawn condition past a source of heat where it is intermittently heated to provide a programmed distribution of heat-treated sections corresponding to the desired distribution of deeper-dyeing sections in the false-twist textured yarn to be produced from the treated yarn. The heating should be sufficient to provide heat-treated sections having a force to draw value which is at least 1.12 times the force to draw of adjacent sections along the yarn, and a density at least 0.005 gram per cubic centimeter greater than the density of adjacent sections.
Preferably, the heat-treated sections are about 0.5 to 2 inches in length. Lengths which are too short provide a less pleasing appearance when the yarn is draw-twist textured and used to prepare dyed fabric. On the other hand, the drawing performance is poor when yarn containing 3-inch or longer heated sections is draw-textured, resulting in an undesirable appearance in dyed fabric. Preferably the total length of the heat-treated sections is about 10 percent of the length of the yarn.
Any of the heating procedures of the prior art can be used to form heat-treated sections in accordance with the present invention. However, it should be noted that the deeper-dyeing sections of the prior art yarns are the unheated sections, whereas the opposite result is obtained in the process of the present invention. Preferably, the heat-treated sections of the present invention are formed by contacting the yarn with a surface heated to a temperature of about 190° C. Better heat transfer is provided by a heated metal surface, which is particularly desirable at the higher yarn speeds. The example illustrates the use of yarn speeds of about 300 to 600 feet per minute with the yarn being brought into contact with a heated pin about 240 to 1,200 times per minute; the advantage of a metal pin an Alsimag® pin is shown.
The treated feed yarn produced by the process of this invention is typically false-twist textured on a conventional draw-texturing machine, using a draw ratio of about 1.55X for yarn which would fully draw at a draw ratio of about 1.7X if the spin-oriented yarn had not been treated in accordance with this invention.
Definitions
Spin-oriented yarn is yarn which is withdrawn from the spinneret at a take-off roll speed greater than about 3,000 yards per minute (about 2,745 meters/minute) such as shown by Petrille in U.S. Pat. No. 3,771,307. The yarn has a birefringence greater than 0.025 and is substantially amorphous.
Relative viscosity (RV) is the ratio of the viscosity of a solution of 0.8 gram of polymer dissolved at room temperature in 10 ml of hexafluoroisopropanol to the viscosity of the hexafluoroisopropanol itself, both measured at 25° C in a capillary viscometer and expressed in the same units.
Break elongation, tenacity, and boil-off shrinkage are measured as in U.S. Pat. No. 3,772,872, Col. 2, 11. 17-33 and 49-55.
Cross-sectional area of a filament is measured by microscopic techniques or by calculation based on denier which may be measured on a standard Uster Evenness Tester.
Force-to-draw is the force required to draw a portion of the yarn 1.536X over a hot plate heated to 210° C. It is measured as follows:
The yarn to be tested is withdrawn from the bobbin and passed around two parallel rolls which rotate at a surface speed of 50 fpm (15.2 mpm). A sufficient number of wraps are taken to insure that there is no slippage. The yarn is passed through a strain gauge, thence over and just in contact with a heated, low friction 4.7-inch (about 12 cm) long hot plate at 210° C, over a second pair of draw rolls rotating at a speed to draw the yarn 1.536X and finally to a yarn take-up system. The length of yarn between the feed rolls and draw rolls is about 4 feet (about 122 cm). Again, enough wraps are taken on the draw rolls to insure that there is no slippage. The "force-to-draw" is measured by the strain gauge and appropriately recorded.
Birefringence is measured as shown in Piazza & Reese U.S. Pat. No. 3,772,872, at Col. 3, 11. 19-32.
Density, used as an indication of crystallinity, may be determined by the method described in "Physical Methods of Investigating Textiles", R. Meridith and J. W. S. Hearle, Textile Book Publishers, Inc. (1959) pages 174-176. Carbon tetrachloride and n-heptane are suitable liquids for use with polyethylene terephthalate. Density difference is the density of the treated portion of the yarn minus the density of the untreated portions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view of a procedure for treating yarn in accordance with this invention.
FIG. 2 is a partial cross-sectional view taken along line 2--2 of FIG. 1.
FIG. 3 is a schematic side view of an apparatus suitable for draw-texturing yarn produced by the process of this inventon.
DETAILED DESCRIPTION
In the process illustrated in FIG. 1, as-spun spin-oriented yarn 1 from package 2 passes over feed roller 3, passes through two eyelets of yoke 4, over delivery roller 5, and is then packaged by a windup system (not shown). Feed roller 3 and delivery roller 5 have the same peripheral speed so that the yarn is not drawn during treatment. Yoke 4 is connected to reciprocating means 6 for moving the yoke rapidly up and down in a programmed manner. A heated cylindrical pin 7 is located between the tines of the yoke in position to contact the yarn during part of the movement of the yoke. As the yarn passes through the eyelets of the yoke it is caused to move into and out of contact with the hot pin. The heat of the pin causes the polyester to become more highly crystallized in the heated sections of the yarn than in the other portions of the yarn. FIG. 2 shows an eyelet 8 in the yoke, through which the yarn is passed to control its movement.
FIG. 3 illustrates the process of false-twist texturing the treated yarn. This process will usually be performed by a customer, starting with a package 10 of yarn which has been produced as described above. Yarn 11 passes from the package between feed rolls 12 and 13, passes by texturing heater 14, is twisted by false-twist spindle 15, passes between upper rolls 16 and 17 and is wound up on package 18. The yarn is preferably draw-textured by driving the upper rollers at a higher speed than the feed rollers. The procedure is then as described in Petrille U.S. Pat. No. 3,771,307, except that a lower draw ratio is used because the heat-treated sections of the yarn draw to a lesser extent than the as-spun portions of the yarn.
Alternatively, the treated yarn can be drawn before it is false-twist textured. For example, the treated yarn can be drawn immediately after delivery roller 5 of FIG. 1, before the yarn is packaged. The drawn, packaged yarn would then be false-twist textured by processes conventionally used for fully drawn yarn. In either case, the heat-treated sections of the drawn yarn will dye to deeper shades than other sections.
EXAMPLE
A 235-denier spin-oriented polyester yarn is prepared by melt spinning 20 relative viscosity polyethylene terepthalate at 284° C, using a spinneret having 34 round orifices (each orifice 0.28 mm wide, 0.51 mm deep) and winding the filaments and 3,107 meters per minute (3,398 ypm). The yarn is interlaced during its travel to the windup as shown in U.S. Pat. No. 2,985,995 to a pin count of 40 centimeters (the length of yarn that passes by probe 18 of Hitt U.S. Pat. No. 3,290,932 before the probe is deflected about 1 mm. A force of about 8 gms is required to deflect the probe). The yarn has a birefringence of 0.038, a tenacity of 2.2 grams per denier, an elongation of 120%, and a boil-off shrinkage of 55%.
The spin-oriented yarn is treated as shown in FIG. 1. The yarns are wound up at about 0.5% less speed than the delivery roller speed. An Alsimag pin, 1.6 inches (4.06 cm) in diameter and 1.25 inches (3.2 cm) long, is used for runs 1-5 and a brass pin of the same dimensions is used for runs 6-9. Better results are obtained using the brass pin. The stroke of the yoke is such that the yarn actually contacts the pin about 10% of the running time.
Nine runs are made using conditions given in Table I. Feed and delivery rollers having the same peripheral speed ar used to provide the yarn speeds shown.
TABLE I______________________________________ Number of Contacts WithRun Min. (Meters/Min) (Material) Pin Per Minute______________________________________1 300 (91.5) 150 (Alsimag) 2402 300 (91.5) 190 (Alsimag) 2403 300 (91.5) 190 (Alsimag) 12004 602 (184) 190 (Alsimag) 12005 602 (184) 190 (Alsimag) 2406 602 (184) 190 (Brass) 2407 602 (184) 190 (Brass) 12008 300 (91.5) 190 (Brass) 12009 300 (91.5) 190 (Brass) 240______________________________________
In Runs 2, 7, 8 and 9, the yarn sections which contacted the hot pin have a force to draw of at least 1.12 times the force to draw of adjacent sections along the length of the yarn, and a density at last 0.005 gm/cc greater than the density of adjacent sections.
Each yarn is then draw-textured on an experimental single-position single-heater Leesona draw-texturing machine. Feed speed is 205 feet per minute (62.5 meters/min) and the yarn is drawn 1.55X; heater temperature in the twist zone is 196° C. The yarn is twisted 63 turns per inch (24.8 turns/cm) in the texturing zone. No melting occurs in the texturing zone. The deep-dyeing sections formed in the yarn have transverse cross-sectional areas which are from 1.05 to 2 times greater than those of adjacent sections.
Each of the textured yarns is knit (Jersey stitch) into a circular knit fabric, using a Lawson FKA knitter, and into a double knit (Pique stitch) fabric using a Stoll Knitter.
The fabrics are dyed with 2% (on weight of fabric) of Latyl Blue FLW. Fabric evaluation is shown in Table II.
TABLE II______________________________________Fabric FromYarn Evaluation______________________________________1 No deep-dyeing sections.2 Deep-dyeing sections; very attractive circular knit fabric. Not much contrast in double knit fabric.3 Numerous too-short deep-dyed sections.4 No deep-dyeing sections.5 No deep-dyeing sections.6 Non-uniform appearance.7 Deep-dyeing sections, very attractive fabric.8 Deep-dyeing sections, most attractive fabric.9 Deep-dyeing sections, very attractive fabric.______________________________________
Fabrics from yarns 2, 7, 8, 9 are fabrics of this invention. It is readily seen that the yarn speed, number of pin contacts and temperature and heat transfer properties of the pin are important considerations. A 150° C pin temperature was not sufficient for Yarn 1; the heat transfer properties of the Alsimag pin were not adequate for the high yarn speed of Yarns 4 and 5 nor for the high contact frequency for Yarn 3. The high speed and low contact frequency for Yarn 6 produced yarns having 3-inch long (7.6 cm) deep-dyeing sections which caused non-uniform drawing performance in texturing. Based on an understanding of the above table, one skilled in the art can readily adjust the process to suit his needs.
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A process for producing a feed yarn which can be draw-textured, without difficulty with filaments melting or sticking together, to have a programmed distribution of deeper-dyeing sections along the resulting false-twist textured yarn. The feed yarn is prepared by passing a spin-oriented polyester yarn in substantially undrawn condition past a source of heat where it is heated intermittently along its length to provide a programmed distribution of heat-treated sections. When drawn, the heat-treated sections will draw to a lesser extent and will then dye to deeper shades than the rest of the yarn.
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TECHNICAL FIELD
This invention generally pertains to the temperature conditioning of a plurality of comfort zones using a plurality of variable air volume valves and more specifically pertains to reheating a cool supply airflow to meet a heating demand.
BACKGROUND OF THE INVENTION
Many refrigeration systems can provide a variable supply of cooled air to cool multi-zone buildings. The amount of cooled air conveyed to each zone is often regulated by valves to meet each zone's cooling demand. Valves used for such a purpose are commonly referred to in the industry as VAV (variable air volume) valves.
A problem exists when one or just a few zones require heating while the rest of the zones still require cooling. Simply shutting off the cool supply air to these few zones is an unsatisfactory solution to the problem, because each zone requires at least some ventilation. Providing each zone with an additional supply air duct for heating is another possible solution, but one which is very expensive, especially when retrofitting an existing structure.
SUMMARY OF THE INVENTION
To avoid the problems associated with present VAV systems, it is an object of the invention to independently temperature condition a plurality of comfort zones by heating some zones while cooling others by selectively reheating portions of a common supply of cool air prior to conveying the supply air to the zones.
Another object of the invention is to coordinate the positioning of a VAV valve and the cycling of a solenoid valve.
Another object of the invention is to coordinate the positioning of a VAV valve and the cycling of a solenoid valve in response to a temperature sensor and an airflow sensor.
Yet another object of the invention is to regulate the average flow rate of a hot fluid using a simple open-closed control scheme.
A further object of the invention is to vary the duty cycle of a PWM solenoid valve as a function of a temperature error plus the length of time the error exists.
A still further object of the invention is to vary the cycling rate of a PWM solenoid valve to minimize temperature fluctuations during periods of low heating demands by increasing the cycling rate, and to minimize valve wear during periods of
Another object of the invention is to provide a constant, non-varying airflow rate of variable temperature when heating and to provide a variable airflow rate of a constant, non-varying temperature when cooling.
Yet another object of the invention is to provide a VAV valve assembly with an attached fan and check valve to assist in warming a relatively cool supply airflow.
These and other objects of the invention are accomplished by a novel VAV assembly. The assembly includes an airflow valve for regulating the flow rate of a relatively cool supply airflow to be delivered to a comfort zone. The assembly also includes a hot fluid coil that, when needed, reheats the cool supply air. The average flow rate of fluid through the coil is regulated by cycling the valve open and closed in a PWM manner. When the temperature of the zone is above its set point temperature, the solenoid valve remains closed and the opening of the airflow valve is regulated to meet the zone's cooling demand. When the temperature of the zone is below its set point temperature, the solenoid valve is cycled with a variable duty cycle to meet the zone's heating demand and the airflow valve is controlled to provide a substantially constant airflow rate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the subject invention used for temperature conditioning a plurality of comfort zones.
FIG. 2 is a PWM signal controlling a solenoid valve with the signal having a constant frequency.
FIG. 3 is a PWM signal controlling a solenoid valve with the signal having a lower frequency at lower duty cycles.
FIG. 4 is a PWM signal controlling a solenoid valve with the signal having a higher frequency at lower duty cycles.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, several comfort zones 10a, 10b, and 10c within a building 12 are temperature conditioned by a refrigeration system 14. A refrigerant compressor 16, a condenser 18, an expansion device 20, and an evaporator 22 are connected in series to comprise a closed-loop refrigeration circuit 24. Evaporator 22 and an evaporator fan 26 serve as a source of supply airflow 28 to zones 10a, 10b, and 10c. Evaporator 22 cools supply airflow 28 to a temperature that is generally below the temperature of comfort zones 10a, 10b, and 10c.
Supply airflow 28 is distributed to zones 10a, 10b, and 10c by way of a supply air duct network means 30 comprising a plurality of supply air ducts 32 connected to each zone. A return air duct network 34 conveys air from these zones and returns it back to evaporator fan 26 for recirculation through the system.
Each zone 10a, 10b, and 10c is associated with a VAV valve 36, 38, and 40 that regulates the rate at which supply air 28 is delivered each zone. Each VAV valve assembly 36, 38, and 40 includes a valve body 42, 44, and 46 connected to a supply air duct 32.
Valves 36, 38, and 40 have several similar features so a description of their operation will be made with reference only to zone 10a and its associated VAV valve 36, keeping in mind that the description applies to valves 38 and 40 as well.
VAV valve 36 includes a moveable closing member 48 disposed within valve body 42. Closing member 48 is repositioned by a drive means 50. The variable positions of closing member 48 determines the flow rate of supply airflow 28 passing through valve 36. Closing member 48 is schematically illustrated as a rotatable damper blade; however, member 48 represents any device that can vary the flow rate of air such as a plug valve of linear movement (e.g., the valves of U.S. Pat. Nos. 4,749,000 and 4,749,001 specifically incorporated by reference herein), a gate-type valve, or even an inflatable bladder. Drive means 50 represents any device for varying the position of member 48. Few examples of drive means 50 include motors, cylinders, and diaphragms.
Drive 50 modulates the position of VAV valve 36 under the control of a command signal 52 provided by a microcomputer based control means 54. Control means 54 relies on an internally stored algorithm to generate command signal 52 in response to a temperature feedback signal 56 and a flow rate feedback signal 58. The specific design of control means 54 can vary widely, depending on the specific input and output devices employed (items 50, 60, 62, and 66 which are further explained below) It should also be appreciated that microcomputer based control means 54 can be replaced entirely by discrete electronic components.
The temperature feedback signal 56 is provided by a temperature sensor 60 associated with the same zone 10a that is associated with VAV valve 36. The temperature feedback signal 56 indicates the error between a selectable desired set point temperature of zone 10a and the actual temperature of zone 10 a as measured by temperature sensor 60. Flow rate feedback signal 58 is provided by a flow sensor 62 which senses the flow rate of supply air 28 leaving VAV valve 36. Flow rate sensor means 62 represents any device for sensing airflow, such as a Pitot tube. It should be noted that in addition to or as an alternative, sensor 62 can be connected upstream of VAV valve 36 (as is the case with valve 40) to measure the rate of airflow entering valve 36.
When the temperature of zone 10a exceeds the set point temperature, control 54 commands drive 50 to open valve 36 to an extent that will provide an airflow rate which meets the cooling demand. The desired rate of airflow, and thus the valve position, is a function of the temperature error and the length of time the error exists (e.g., porportional plus integral control). Control 54 uses flow rate feedback signal 58 to ensure that the commanded valve position actually results in the desired rate of airflow. If desired, control 54 may further adjust the position of closing member 48 to minimize the difference between the actual rate of airflow and the desired rate of airflow. The position of closing member 48 is adjusted to reduce the error between the zone temperature and its set point.
If the temperature of zone 10a drops below a set point temperature, valve 36 is still held partially open to provide at least some airflow 28 for adequate ventilation. However, to prevent zone 10a from getting uncomfortably cold, a heating coil 64 is employed within valve body 42. Coil 64 conveys a heated fluid, such as water and/or glycol, that is sufficiently warm to heat airflow 28 to a temperature greater than that of comfort zone 10a.
The extent to which airflow 28 is heated by coil 64 is controlled by a solenoid valve 66 connected in series with heating coil 64. Solenoid valve 66 is cycled open and closed in a pulse-width modulated manner to meet the heating demand of the comfort zone. The cycling of solenoid valve 66 is controlled by a command signal 68 generated by control 54 in response to the zone temperature error and, if desired, in further response to the length of time that the error exists.
Referring to FIG. 2, in one embodiment of the invention, solenoid valve 66 is cycled at a relatively constant frequency with a variable open-period 70 within each cycle 72. FIG. 2 illustrates a cycle period 72 of three minutes, or in other words, the frequency is once every three minutes. The percentage of open-period 70 within each cycle period 72 is referred to as duty cycle. The duty cycle increases with the heating demand. Region 74 represents a 90 % duty cycle to meet a relatively high heating demand. With a 90 % duty cycle, valve 36 has an open-period 70 of 162 seconds and a closed-period 76 of 18 seconds during a total cycle period 72 of three minutes. Region 80 represents a 20 % duty cycle to meet a relatively low heating demand, and Region 78 represents a 50 % duty cycle.
While coil 64 is being used to reheat airflow 28, closing member 48 of VAV valve 36 is positioned to provide a relatively constant flow rate to satisfy minimum ventilation requirements. This can be accomplished by generally holding closing member 48 at (or just below) a fixed predetermined position. For greater control, the position of closing member 48 can be modulated in response to the flow rate feedback signal 58 to ensure a constant flow rate.
In another embodiment of the invention, referring to FIG. 3, the duty cycle is varied to meet the demand by maintaining a constant open-period 70 while varying cycle period 72. Open-period 70 is set to allow sufficient time for a complete exchange of fluid within coil 64. Region 82 represents a 90 % duty cycle, region 84 represents a 50 % duty cycle, and region 86 represents an 80 % duty cycle.
In yet another embodiment of the invention, referring to FIG. 4, the frequencies vary to limit closed-period 76 to less than a predetermined maximum. Excessively long closed-period 76 between open-period 70 can cause uncomfortable temperature fluctuations of airflow 28. These fluctuations are minimized by increasing the cycle frequency at lower duty cycles, such as in region 88 where the duty cycle is 10 %. Region 90 represents a duty cycle of 50 %, and region 92 represents a duty cycle of 80 %.
Referring back to FIG. 1, to conserve energy in meeting a heating demand fan means 94 or 96 and check valve means 98 can be added to VAV valve assemblies 36, 38, and/or 40, check valve means 98 represents any device that provides greater flow resistance in one direction than n an opposite direction. Ideally, the flow will be substantially blocked in one direction and relatively unrestricted in the other direction. Fan means 94 and 96 represent any device for delivering kinetic energy to air such as an axial or centrifugal fan. Fan 94 is mounted outside of valve body 44 and discharges ambient air 100 into it. As an alternative, fan means 96 is disposed entirely within valve body 46 and draws ambient air 100 into valve body 46. Ambient air 100, as referred to herein, is the air surrounding any valve body 42, 44, or 46. Valve bodies 42, 44, and 46 and the surrounding ambient air 100 are generally above a ceiling 102 of a comfort zone where the air temperature is generally higher than that of the comfort zone. Thus the relatively warm ambient air 100 can assist in warming an uncomfortably cool comfort zone. Check valve means 98 is located downstream of closing member 48 and prevents cooled supply air 28 from discharging into ambient air 100. With internally mounted fan means 96, check valve means 98 can be eliminated by operating fan 96 at a sufficiently high speed that would ensure that the air pressure between closing member 48 and fan 96 is less than the ambient air pressure.
Although the invention is described with respect to a preferred embodiment, modifications thereto will be apparent to those skilled in the art. Therefore, the scope of the invention is to be determined by reference to the claims which follow.
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A refrigeration system for temperature conditioning several comfort zones includes several VAV (variable air volume) valves each having a hot water coil conveying water whose flow rate is regulated by a PWM (pulse-width modulated) solenoid valve. Each VAV valve is connected to a supply air duct conveying cool supply air. When a zone's temperature is above a set point temperature, the opening of the VAV valve is modulated to meet the cooling demand, and the water coil is shut off. When a zone's temperature is below the set point, the VAV valve is opened to provide a predetermined constant airflow rate and the hot water coil's solenoid valve is cycled open and closed in a pulse-width modulated manner to meet the heating demand.
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of provisional patent application Ser. No. 61/124,446, filed Apr. 17, 2008, entitled Training Drumsticks.
FIELD
The present invention relates to drumsticks and, more particularly, to a drumstick for training percussionists to use proper form, which will increase learning speed and enable faster and more efficient drum strokes.
BACKGROUND
Drumsticks for percussionists are generally known in the art. A drumstick is typically made from wood. The drumstick includes a tip or bead which strikes the drum head. Tips may come in many shapes such as acorn, barrel, oval and round. Immediately below the tip is the shoulder of the drumstick which tapers out to the shaft and ends with the butt of the opposite end to the tip. The shaft is typically an elongated, smooth cylinder with no features. Drumsticks vary in length from approximately 15 inches to 17 inches with a shaft diameter of approximately 0.5 inches to 0.6 inches.
The musician may hold the drumsticks in a variety of different manners. One being the overhand matched grip. There are three variations of the overhand matched grip—the French grip, the German grip and the American grip. With the French grip, the musician's palms face each other and control of the drumsticks is mainly accomplished using the fingers. With the German grip the musician holds the drumsticks with the palms parallel to the drum head, providing a more forceful strike. The musician's palms are at a 45 degree angle with an American grip which provides a compromise between the finesse of the French grip and the strength of the German grip.
It is important when learning to play the drums to properly hold the drumsticks and keep the proper hand orientation with respect to the drum head. While playing the drum it is important to keep the proper hand orientation with respect to the drum head depending on the particular grip. A typical drum stick does not provide any indication to the musician what is his or her orientation or if the drumstick is being properly held. Further, as the musician plays, his or her hand orientation may change without any indication or feedback to the musician. Without consistent practice, bad habits form which may prove difficult to correct or overcome.
SUMMARY
The present invention provides drumsticks for training percussionists to use proper form, which may increase learning speed and enable faster and more efficient drum strokes. Each drumstick includes a tip or bead with a wing extending therefrom. The wing extends beyond the width of the shaft of the drumstick so that the percussionist must strike the drum head with wing extending parallel to the drum head surface to achieve a proper and acceptable sound.
The shaft may include a grip or handle to help the percussionist properly hold the drumstick and resist twisting the drumstick in the user's hands. The grips may be formed for a specific hand (i.e., a left hand stick and a right hand stick) or may be ambidextrous in nature.
The wing may be shaped to encourage the user to position the sticks at the proper angle to each other (i.e., at a 90 degree angle to one another). This also allows the user to visually check to see if the sticks are properly aligned and positioned.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of a pair of drumsticks of the present invention shown at a 90 degree angle to one another.
FIG. 2 is an enlarged top view of the right drumstick of FIG. 1 .
FIG. 3 is a bottom plan view of the drumstick of FIG. 2 .
FIG. 4 is a side view of the drumstick of FIG. 2 viewed in the direction of line 4 - 4 .
FIG. 5 is an end view of the drumstick of FIG. 2 viewed in the direction of line 5 - 5 .
FIG. 6 is an enlarged side view of the top and wing of the drumstick of FIG. 4 at line 6 - 6 .
FIG. 7 is a perspective side view of the drumsticks of FIG. 2 viewed in the direction of line 7 - 7 .
FIG. 8 is a perspective view of the drumsticks shown with respect to a drum head.
FIG. 9 is a drumstick of FIG. 5 shown rotated to the right with respect to a drum head.
FIG. 10 is the drumstick of FIG. 5 shown rotated to the left with respect to the drum head.
FIG. 11 is the drumstick of FIG. 5 shown properly aligned with respect to the drum head.
FIG. 12 is a partial view of the drumsticks of FIG. 1 shown rotated outwardly.
FIG. 13 is a partial view of the drumsticks of FIG. 1 shown rotated inwardly.
FIG. 14 is a partial view of the drumsticks of FIG. 1 shown properly positioned.
DETAILED DESCRIPTION
Referring initially to FIGS. 1-8 , drumsticks (individually or as a pair) are generally indicated by reference numeral 20 . As shown in FIGS. 1 and 8 , drumsticks 20 are arranged as right and left drumsticks, which are mirror images of each other. Because the features of each drumstick individually in the preferred embodiment are identical, the drumsticks will generally be described below with respect to only one of the drumsticks, namely, the right drumstick.
Drumstick 20 includes a tip or bead 22 , a shoulder 24 , a shaft 26 , a grip or handle 28 and a butt 30 . A wing or tab 32 is secured to the tip 22 . The wing 32 is generally trapezoidally shaped with an elongated inside edge 34 . The wing 32 is secured to the tip 22 near the elongated inside edge 34 , and includes a leading edge 35 and a trailing edge 36 which are generally perpendicular to a longitudinal axis 42 of the shaft 26 . The elongated inside edge 34 is generally oriented at a 45-degree angle to the longitudinal axis 42 of the shaft 26 . The elongated inside edge extends to an inner tip or corner 40 . The trailing edge 36 extends from the tip 22 to an outer tip 38 .
The wing 32 is mounted at a slight angle to the longitudinal axis 42 so that when the tip 22 of drumstick 20 is resting on or striking the surface 46 of the drum head 48 , the plane of the wing 32 may be parallel to the drum head surface 46 . This parallel orientation of the wing 32 with respect to the surface 46 also aids in properly adjusting the height of the drum head 48 for the user. If the drum head 48 is too low, the leading edge 35 of the wing 32 may strike the surface 46 and the wing 32 will not be parallel to the surface 46 . In the preferred embodiment, the wing 32 is mounted at an angle of six degrees. The wing 32 may be integrally formed with the drumstick 20 as shown in the figure or may be removably or permanently attached to the tip 22 .
The handle or grip 28 is formed with the shaft 26 and positioned at approximately the center of mass of the drumstick 20 so that when gripped the drumstick 20 is balanced in the user's hand. The handle 28 includes a ridge 50 separating an index finger indentation 52 and a thumb indentation 54 . The handle 28 provides a natural positioning of the user's hand, which is also the proper grip for the drumstick 20 . The handle 28 provides an ergonomic conformance to the user's hand. As shown, the handle 28 is positioned to correspond to the American grip. It should be understood that the handle 28 may be positioned to correspond to the French or German grips. In a preferred embodiment, the handle 28 is molded with the shaft 26 resulting in a set of drumsticks 20 configured to correspond to a particular grip. However, a separate grip may be adapted to be attached or releasably positioned on the shaft 26 of the drumstick 20 allowing the user to add a handle 28 to a standard drumstick, for example.
Referring to FIGS. 9-11 , when striking the surface 46 of drum head 48 , it is desirable for the user to position his or her hands properly not only as to the location gripped along the shaft 26 , but also with respect to the orientation of the user's hands. If rotated too far outwardly, striking the drum head surface 46 lacks power. When the user's hands are rotated outwardly, the outer tip 38 of the wing 32 may strike the surface 46 at the same time or before the tip 22 of the drumstick 20 (see FIG. 9 ). Not only is the sound produced not clear or as crisp as it would be if only the tip 22 strikes the surface 46 ( FIG. 11 ), the user may feel a slight twist or torque about the longitudinal axis 42 of the shaft 26 urging the user to rotate his or her hand to the proper orientation.
Likewise, if the user rotates his or her hands inwardly, striking the drum head surface 46 lacks the precision and finesse. When the user's hands are rotated inwardly, the inner tip 40 of wing 32 may strike the drumhead surface 46 at the same time or before the tip 22 (see FIG. 10 ). Not only is the sound produced not clear or as crisp as it would be if only the tip 22 strikes the surface 46 ( FIG. 11 ), the user may feel a slight twist or torque about the longitudinal axis 42 of the shaft 26 urging the user to rotate his or her hand to the proper orientation.
Referring to FIGS. 12-14 , the wings 32 of the drumsticks 20 also help the user maintain the proper 90-degree angle to one another (see FIG. 14 ). If the user has his or her elbows positioned too far from his or her sides, which may result in fatigue and inability to quickly and accurately strike other drums or cymbals (not shown), the elongated inside edges 34 will not be parallel providing a visual indication to the user and/or instructor (see FIG. 12 ). Likewise, if the user has his or her elbows positioned too close to his or her sides, which may result in interference and not being able to strike the drum surface quickly and accurately, the elongated inside edges 34 will not be parallel, again providing a visual indication to the user and/or instructor ( FIG. 13 ).
It should be understood that the advantages of the wing 32 and grip 28 may be gained individually or in combination. For example, drumsticks 20 with wings 32 attached to the tips 22 may be used to teach the user the proper positioning of his or her hands, wrists and arms with respect to the drum or other surface. The grips 28 attached to the shafts 26 of the drumsticks 20 may be used to teach the user the proper location to hold the drumsticks 20 and the proper hand and finger orientation. The grip 28 may be rotatable or adjustable to accommodate the different matched grips. For a fixed grip 28 , the wing 32 attached to the tip 22 may be rotatable to also accommodate the different matched grips. Other configurations of wing 32 may be contemplated which provide auditory, tactile and/or visual indications to the user and/or instructor within the scope of this invention. Other orientations and configurations of the wing 32 may also be used to address specific rotation and orientation issues of a particular student.
Accordingly, it should be understood that while certain forms of the invention have been illustrated and described, it is not limited thereto except insofar as such limitations are included in the following claims.
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The present invention provides drumsticks for training percussionists to use proper form, which may increase learning speed and enable faster and more efficient drum strokes. Each drumstick includes a tip or bead with a wing extending therefrom. The wing extends beyond the width of the shaft of the drumstick so that the percussionist must strike the drum head with wing extending parallel to the drum head surface to achieve a proper and acceptable sound. A grip is also provided to properly orient the user's hands for the matched grip variation desired.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a semiconductor image sensor, and more particularly to a semiconductor image sensor which is provided with a photosensing and accumulation region of a hook structure.
2. Description of the Prior Art
Semiconductor image sensors that have heretofore been employed are mostly the MOS type and the CCD type. The MOS type image sensor permits simple peripheral circuit arrangements and allows ease in incorporating peripheral circuits and a scanning circuit into the sensor body but, on the other hand, it has the disadvantages of large switching noise and an excessive video line capacitance which leads to lowered sensitivity when it fabricated for multibit operations. In contrast thereto, the CCD type image sensor has high sensitivity and hence can be used at low light levels and, in terms of its arrangement, permits fabrication for multibit operations; in practice, however, when it is constructed for multibit operations, its drive circuit becomes complicated and complexity is introduced in its manufacturing process and, in addition, a high degree of stability is needed in operation.
Recently a novel image sensor which is free from such defects has been proposed by the present inventors. Which image sensor will hereinafter be referred to as the prior art image sensor. The prior art image sensor achieves (1) wide dynamic range, (2) high sensitivity, (3) low noise and (4) high image clarity by the provision of a photosensing and accumulation region of a hook structure. One of its striking features is non-destructive readout of optical information by a carrier storage effect which is characteristic of the hook structure.
In the photosensing and accumulation portion of an example of the abovesaid image sensor, there is formed a hook structure which comprises a low resistivity first region of a first conductivity type, a high resistivity second region, a low resistivity third region of a second conductivity type reverse from the first one and a low resistivity fourth region of the first conductivity which are sequentially formed one on another in a semiconductor substrate inwardly thereof from its surface; namely, a hook structure is constituted by, for example, an n + region, a p - region, a p + region and an n + region. Of these regions, only the p + and n + regions on the side of the substrate are isolated by an insulating isolation region in a lateral direction to form a plurality of cells, thereby defining a pn junction. That is, the n + and p - regions on the side of the surface of the substrate assembly are common to the cells. A transparent electrode is formed on the outer n + region and, on the other hand, a readout transistor is connected to the inner n + region. The substrate is irradiated by light through the transparent electrode which is supplied with a positive voltage.
Electrons of electron-hole pairs which are created by the optical irradiation in the vicinity of the substrate surface, are immediately absorbed by the transparent electrode supplied with the positive voltage but holes are accelerated by the electric field to flow across the p - region into the inner p + region. Between the p + region and the inner n + region is formed a pn junction having a predetermined barrier voltage. The barrier prevents the holes having flowed into the p + region further flow into the inner n + region. In consequence, the holes are accumulated in a potential well of the hook structure formed in this p + region. As the accumulation of the holes proceeds, the barrier voltage of the pn junction drops, resulting in flowing out of electrons from the inner n + region towards the p - region across the pn junction. The electrons are accelerated to flow through the p - region and the outer n + region and absorbed into the transparent electrode supplied with the positive voltage. As a result of this, the floating inner n + region from which the electrons have flowed out is charged positive to raise its potential. The increased potential of this n + region is read out by the aforesaid readout transistor.
The prior art image sensor possesses the above-described many advantages over the conventional MOS type and CCD type image sensors but has some problems to be solved for enhancement of light receiving sensitivity, operation speed and so forth.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to improve the light receiving sensitivity of the prior art image sensor.
Another object of the present invention is to increase the operation speed of the prior art image sensor.
Another object of the prior art is to enhance resolution by reducing crosstalk between adjacent cells.
Yet another object of the present invention is to reduce noise without lowering sensitivity.
The abovesaid objective can be achieved by providing a semiconductor image sensor which comprises a low resistivity first region of a first conductivity type, a high resistivity second region, a low resistivity third region of a second conductivity type, a low resistivity fourth region of the first conductivity type, the first to fourth regions being sequentially formed one on another in a single semiconductor substrate inwardly thereof from its surface, an insulating isolation region for isolating the third and fourth regions in a lateral direction, a fifth region vertically extending into the second region from that portion of the insulating isolation region facing towards the first region, electrode means disposed in contact with the first region, and readout means connected to the fourth region.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(a) and 1(b) are respectively a longitudinal sectional view and a cross sectional view illustrating a preferred embodiment of the present invention;
FIG. 2(a) is an equivalent circuit of one cell of the device shown in FIG. 1(a) FIG. 2(b) being like FIG. 2(a) but showing eight cells;
FIG. 3 is an energy diagram of a hook structure in the embodiment of FIG. 1;
FIG. 4 is a sectional view illustrating another embodiment of the present invention; and
FIGS. 5(a) to 5(e) show, in section, a sequence of steps involved in the manufacture of the device depicted in FIG. 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates in section an embodiment of the present invention, FIG 1(a) being a sectional view parallel to a direction normal to a semiconductor substrate 10 (which direction will hereinafter be referred to as the vertical direction) and FIG. 1(b) a sectional view parallel to a direction tangent to the surface of the substrate 10 (which direction will hereinafter be referred to as the lateral direction). The device of this embodiment has such an image sensor structure that a number of photoelectric conversion cells separated by insulating isolation regions 6 are arranged in a matrix form in the single semiconductor substrate 10 as of silicon. Each cell is composed of a photosensing region and a readout transistor, which are formed one on the other in the vertical direction to provide very compact structure.
The photosensing region of each cell is formed by an n + -p - -p + -n + hook structure composed of an n + region 1, a p - region 2, a p + region 3 and an n + region 4 and an n region 5 which taperingly projects towards the n + region 1 from that portion of the insulating isolation region 6 facing the n + region 1. An electrode 7 formed on the surface of the n + region 1 is supplied with a positive pulse voltage Vs (a write pulse) of a proper width. The readout transistor is constituted by an n + drain region 9, a p channel region 8, the n + source region 4, a drain electrode 9' and a gate electrode 8'. To the drain electrode 9' and the gate electrode 8' are respectively connected a bit line 11 and a word line 12. The bit line 11 is formed of metal such as aluminum, or semiconductor such as doped silicon. The word line 12 is formed of a silicide of high melting point metal such is molybdenum, tungsten, titanium or the like, that is, MoSi 2 , WSi 2 , TiSi 2 or the like, or semiconductor such as doped silicon. The electrode 7 is a transparent electrode which is formed of a transparent material such as polysilicon, SnO 2 , InO 2 or the like, or a thin metal film. An insulating layer 13 serves as a gate insulating layer and an insulating layer 14 insulates the bit line 11 and the word line 12 from each other.
FIG. 2(a) shows an equivalent circuit of a unit cell made up of the photosensing region and the readout transistor as described above. In the photosensing region, the n + region 1 and the high resistivity p - and p + regions 2 and 3 constitute a (p + p - nt) diode D1 similar to a pin diode and the p + region 3 and the n + region 4 form a diode D2. The p - region 2 may be either an i or n - region so long as it is a high resistivity region. Since the high resistivity p - region 2 is sufficiently long in the vertical direction, the junction capacitance of the diode D1 is sufficiently small as compared with the junction capacitance Cf of the diode D2 and a reverse bias resistance of the diode D1; hence it can be omitted from the equivalent circuit. On the other hand, the n + drain region 9, the p channel region 8 and the n + source region 4 from an electrostatic induction transistor Q1 for readout use. FIG. 2(b) exemplifies the connection of eight such cells.
In the device of FIG. 1, when applying the positive voltage Vs (a write pulse), the pn junction formed between the n region 5 and the p - region is forwardly biased, permitting elections to flow out of the n region 5 into the p - region 2. The electrons are accelerated to flow through the p - region 2 into the n + region and thence they are absorbed by the electrode 7. The floating n region 5 from which the electrons have flowed out is charged positive.
FIG. 3 shows an energy diagram of the photosensing region when the positive voltage Vs is applied to the electrode 7. A depletion layer is formed in the high resistivity p - region 2. This corresponds to reverse biasing of the pin diode (to be exact, a p + p - n + diode) D1 in the equivalent circuit of FIG. 2(a). In a preferred embodiment of the present invention, the thickness of the p - region 2, the impurity concentration and the value of the voltage Vs are selected so that the p - region 2 may be depleted throughout it. This is set forth in detail in prior patent application U.S. Ser. Nos. 254,046 and 265,383 and Japanese Patent Application No. 60316/80. In FIG. 3, a pn junction having a fixed barrier voltage is formed between the p + region 3 and the n + region 4 but since the positive voltage applied to the electrode 7 is mostly fed to the high resistivity p - region 2, the forward bias to the pn junction is limited to a very small value.
When the device is illuminated through the transparent electrode 7 from the back of the substrate 10 while the positive voltage is being applied as described above, pair creation of electrons and holes takes place in the p - region 2 near the n + region 1. The electrons generated are immediately absorbed into the electrode 7, whereas the holes are accelerated by the electric field to flow across the p - region 2 into the p + region 3 wherein they are accumulated. At this time, since the n region 5 is charged positive, the holes travelling near the n region 5 is repelled by it to be deflected towards the central portion of the p + region 3 as indicated by the broken line in FIG. 1(a). In this way, the holes generated in the peripheral portion of the cell are focused to the central portion of the p + region 3 through the lens-like action of the n region 5. A detailed description will be given later of the effect by this focusing action.
Now, let it be assumed that the quantum efficiency is 1 in a one-dimensional model. Letting unit charge, the velocity of light, the photon density and the time after the start of illumination be represented by q, C, S(t) (photons/cm 3 ) and t, respectively, the amount of positive charges by holes per unit area which are accumulated in the p + region 3 is given by ##EQU1## By such accumulation of the holes or the positive charges in the p + region 3, the barrier voltage of the pn junction between the p + region 3 and the n + region 4 drops by ΔV=ΔQ/Cf. This corresponds to forward biasing of the diode D2 by ΔV in the equivalent circuit of FIG. 2.
Consequently, electrons in the n + region 4 flow out therefrom into the p - region 2 across the p + region 3. The electrons are accelerated to pass through the p - region 2 and the n + region 1, thereafter being absorbed into the electrode 7 supplied with the positive voltage. As a result of this, the n + region 4 in the floating state is charge positive by the amount of charges of the electrons having flowed out therefrom, causing a gradual increase in the barrier voltage of the pn junction formed between the n + region 4 and the p + region 3. This corresponds to gradual cancellation of the forward bias ΔV of the diode D2 in response to the flowing out of the electrons in the equivalent circuit of FIG. 2(a). Such charging of the n + region 4 stops when the amount of positive charges in the n + region 4, which decreases as the electrons flows out therefrom, becomes equal to the amount of charges of the holes accumulated in the p + region. At this time, the barrier potential becomes equal to a value in the state of thermal equilibrium before the accumulation of the holes and and the potential of the n + region 14 rises higher by ΔV than that before the hole accumulation.
The voltage of the n + region 4 thus raised is read out by the readout transistor Q1 on the bit line 11. In other words, the word line 12 in FIG. 1(a) is opened to turn ON the readout transistor Q1, by which electrons flow out of the n + region 9 into the n + region 4 across the p region 8, reading out the positive voltage on the bit line 11. The positive charges stored in the n + region 4 before the readout operation are neutralized by the charges of electrons flowing into the n + region 4 during the readout and when the readout transistor Q1 is turned OFF, the amount of positive charges in the n + region 4 becomes small to some extent. This value is dependent upon the amount of charges stored before the readout, the amount of charges accumulated during the readout and combinations of various readout conditions. No matter what the value may be, if the amount of positive charges accumulated in the n + region 4 is smaller than the amount of positive charges of holes accumulated in the p + region 3, the barrier voltage drops by the value corresponding to the division of the difference between the amounts of charges in the both regions by the junction Cf and, as a result, electrons flow out of the n + regions across p + region 3 into the electrode 7 supplied with the positive voltage. This flowing out of electrons continues until the amount of positive charges in the n + region 4 becomes equal to the amount of positive charges of holes accumulated in the p + region 3. In such a device of the present invention, information once destructed (the increased voltage of the n + region 4) by the readout is automatically regenerated.
In order that such regeneration may be complete, it is desirable, of course, that the holes once accumulated in the p + region 3 are not extinguished nor do they flow out therefrom, in particular, even if the barrier voltage between the p + region 3 and the n + region 4 is low, the holes accumulated in the p + region 3 do not flow out therefrom into the n + region 4. In other words, it is desirable that a current crossing the junction during write and during regeneration after readout is occupied by an electron current as much as possible. An ordinary method for the above is common to a method for improving the emitter injection efficiency of a bipolar transistor and some of its specific means are discussed in detail in the aforesaid prior applications.
In the device of the present invention, information once written is not extinguished by readout as described above. For the extinction of the information, the present invention employs such an arrangement that the polarity of the voltage to the electrode 7 is inverted, by which the holes accumulated in the n + region 3 are absorbed into the electrode 7 across the p - region 2, or electrons are flowed from the electrode 7 into the p + region 3 across the p - region 2. It is to employ such an arrangement that a transistor for short-circuiting use is built in the substrate 10.
Since the increased voltage ΔV of the n + region 4 is inversely proportional to the junction capacitance Cf between the regions 3 and 4, it is desirable to minimize the junction capacitance Cf for increasing the readout voltage per quantity of incident light, that is, the light receiving sensitivity. As the junction capacitance decreases, the charge and discharge time constants of the junction also diminish, improving the light recovery sensitivity and permitting high-speed operation. For reducing the junction capacitance Cf, the junction area must be decreased ultimately. The reason is that the measure of lowering the impurity concentration has its limit. As shown in FIG. 1(a), the light receiving area of each cell is proportional to L1 and the junction area is proportional to L2. In conventional devices, if the junction area (∝ L2) is decreased while retaining the quantity of light received per cell or the light receiving area (∝ L1) unchanged, then holes generated in the surface portion corresponding to the difference in area {∝(L1-L2)} collide against the tip of the insulating isolation region 6 and captured by a capture level of an interface, and they hence cannot reach the p + region 3 or they are delayed in arrival. Further, in the conventional devices, holes created in the vicinity of the boundary between cells flow into adjacent ones of the cells, causing blurring of an image in the neighborhood of the boundary.
In the device of the present invention, since the floating n region 5 is always charged positive, holes travelling near the region 5 is repelled by it to be deflected towards the center of the cell as indicated by the broken line in FIG. 1(a). In other words, an electrical lens is formed by the n region 5.
On account of such an electric field lens effect, it is possible to reduce the area (∝ L2) of the p + region 3 while retaining the light receiving area (∝ L1) unchanged, for example, by increasing the width of the insulating isolation region 6 in the lateral direction in FIG. 1(a). As a result of this, the junction capacitance Cf can be decreased while holding unchange the amount of light received by each cell. This enables improvement of the light receiving sensitivity and speeding up of operation as well as marked reduction of defocusing of an image which is caused by flowing out of holes from each cell into adjacent ones of them.
Further, the present invention has the following effect: A noise input can be minimized when lowering the bias voltage Vs to hold charges in the floating p + region 3 and the n + region 4 after accumulating therein the charges by illuminating the device while applying the bias voltage Vs of such a value that substantially the entire area of the p - region 2 can be depleted. By lowering the bias voltage Vs, its electric field in the vicinity of the accumulation region is diminished to weaken the lens action of the n region 5 and, consequently, there is no action of leading a noise input to the accumulation region. Moreover, carriers of the noise input to the accumulation region are proportional to the area of an entrance, so that the smaller the accumulation region is, the more the noise input when holding the charges decreases.
As described above, the semiconductor image sensor of the present invention which is provided with the n region 5 having the lens action possesses the advantage of reducing noise without impairing sensitivity.
While in the foregoing the present invention has been described as being applied to a semiconductor image sensor having an n + -p - -p + -n + hook structure, it is also possible, of course, to employ a p + -n - -p + hook structure in which the respective regions are reverse in polarity from those of the above hook structure. In this case, the polarity of the readout transistor Q 1 is inverted. Further, the readout transistor may be a known one.
FIG. 4 illustrates in section another embodiment of the present invention, in which the regions identified by the same reference numerals as those in FIG. 1 are the same regions as in FIG. 1. The image sensor of this embodiment differs from the embodiment of FIG. 1 in that each cell is not provided the readout transistor in the same semiconductor substrate but is composed of the photosensing region alone. In addition, discrete small electrodes 17 are deposited on the back of the substrate 10 instead of forming the transparent electrode over the entire area thereof. As the operation of this embodiment is exactly the same as that of the photosensing region of the embodiment shown in FIG. 1, no detailed description will be repeated. The positive voltage induced in the n + region 4 in proportion to the quantity of light received is read out via an electrode 16.
FIG. 5 illustrates in section a sequence of steps involved in the manufacture of the image sensor depicted in FIG. 4. The manufacture starts with the formation of the n region 5 in a p - silicon substrate 2 by means of selective diffusion or ion implantation thereinto, as shown in FIG. 5(a). Then a portion of the n region 5 is oxidized as by selective oxidation to form the insulating isolation region 6 (FIG. 5(b)). Next, a p type impurity is diffused in large quantities into the silicon substrate to form the p + region 3 (FIG. 5(c)). Therefore, an n type impurity is diffused in large quantities into the silicon substrate 2 from its both sides to form the n + regions 1 and 4 (FIG. 5(d)). Finally, the electrodes 16 and 17 are deposited as by evaporation.
The embodiments of FIGS. 1 and 4 are arranged so that holes created by illumination are accumulated in the hook-structured potential well but it is also possible to employ such an arrangement that electrons generated by illumination are accumulated in the hook-structured potential well by inverting all of the conductivity types of the regions 1 to 5 and the polarity of the applied voltage mentioned in the foregoing. In FIGS. 1 and 4, the p - region 2 is required only to be a high resistivity region as referred to previously and its conductivity type is arbitrary.
The readout transistor such as an SIT, FET, JFET or the like may be built in the substrate as shown in FIG. 1, or may be provided outside of the substrate as depicted in FIG. 4.
As has been described in the foregoing, the image sensor of the present invention is equipped with an equivalent electric field lens mechanism capable of decreasing the junction area of the hook structure while retaining the light receiving area unchanged; hence, the device of the present invention possesses the advantages of markedly increased light receiving sensitivity, operation speed and image clarity as well as the effect that noise can be reduced without impairing sensitivity.
It will be apparent that many modifications and variations may be effected without departing from the scope of the novel concepts of this invention.
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A semiconductor image sensor which comprises a plurality of image sensor cells, each having a photosensing and accumulation region of an n + -p - -(i)-p + -n + (or p + -n - -(i)-n + -p + ) hook structure which is formed by sequentially forming its respective regions in a semiconductor substrate inwardly thereof from its surface. The photosensing and accumulation regions are isolated by insulating isolation regions from adjacent ones of them. A tapering conductive region, which acts as an electric field lens on charged carriers, is formed to extend into a high resistivity layer of the photosensing region from the end face of each insulating isolation region on the side of the semiconductor substrate.
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This application is a continuation-in-part patent application of patent application Ser. No. 687,342 filed Apr. 18, 1991, now U.S. Pat. No. 3,158,617.
BACKGROUND OF THE INVENTION
The present invention relates to a class of hydrochlorofluorocarbons which have 3 to 5 carbon atoms, have 1 to 2 chlorine atoms, and have OH rate constants from about 8 to about 25 cm 3 /molecule/sec×10-14.
Vapor degreasing and solvent cleaning with fluorocarbon based solvents have found widespread use in industry for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
In its simplest form, vapor degreasing or solvent cleaning consists of exposing a room-temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.
For soils which are difficult to remove, where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the cleaning of metal parts and assemblies must be done efficiently and quickly, the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part. In addition, the part can also be sprayed with distilled solvent before final rinsing.
Vapor degreasers suitable in the above-described operations are well known in the art. For example, Sherliker et al. in U.S. Pat. No. 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancilliary equipment.
Cold cleaning is another application where a number of solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with rags or similar objects soaked in solvents.
In cold cleaning applications, the use of the aerosol packaging concept has long been found to be a convenient and cost effective means of dispensing solvents. Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquefied gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve. The propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems.
Chlorofluorocarbon solvents, such as trichlorotrifluoroethane, have attained widespread use in recent years as effective, nontoxic, and nonflammable agents useful in degreasing applications and other solvent cleaning applications. Trichlorotrifluoroethane has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts and the like. Trichlorotrifluoroethane has two isomers: 1,1,2-trichloro-1,2,2-trifluoroethane (known in the art as CFC-113) and 1,1,1-trichloro-2,2,2-trifluoroethane (known in the art as CFC-113a). CFC-113 has a boiling point of about 470° C. and has been found to have satisfactory solvent power for greases, oils, waxes, and the like.
Another commonly used solvent is chloroform (known in the art as HCC-20) which has a boiling point of about 630° C. Perchloroethylene is a commonly used dry cleaning and vapor degreasing solvent which has a boiling point of about 121° C. These compounds are disadvantageous for use as solvents because they are toxic; also, chloroform causes liver damage when inhaled in excess.
Although chlorine is known to contribute to the solvency capability of a compound, fully halogenated chlorofluorocarbons and hydrochlorofluorocarbons are suspected of causing environmental problems in connection with the earth's protective ozone layer. Thus, the art is seeking new compounds which do not contribute to environmental problems but yet provide the solvency properties of CFC-113.
Chlorofluorocarbons (CFCS) such as CFC-113 are suspected of causing environmental problems in connection with the ozone layer. Under the Clean Air Act, CFC-113 is being phased-out of production.
In response to the need for stratospherically safe materials, substitutes have been developed and continue to be developed. Research Disclosure 14623 (June 1978) reports that 1,1-dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) is a useful solvent for degreasing and defluxing substrates. In the EPA "Findings of the Chlorofluorocarbon Chemical Substitutes International Committee", EPA-600/9-88-009 (April 1988), it was reported that HCFC-123 and 1,1-dichloro-1-fluoroethane (known in the art as HCFC-141b) have potential as replacements for CFC-113 as cleaning agents.
The problem with these substitutes is that they have a long atmospheric lifetime as determined by their reaction with OH radicals in the troposphere. Table I below contains the OH rate constants and corresponding atmospheric lifetimes for these substitutes. In Table I, Exp K OH stands for experimental K OH rate constant, Est K OH stands for estimated K OH rate constant, Exp Life stands for experimental lifetime, and Est Life stands for estimated lifetime. The unit on the rate constant is cm 3 /molecule/sec×10-14 and the unit on the lifetime is years.
TABLE I______________________________________ Exp Est Exp EstNumber Formula K.sub.OH K.sub.OH Life Life______________________________________HCFC-123 CHCl.sub.2 CF.sub.3 3.7 2.96 2.0 2.6HCFC-124 CF.sub.3 CHClF 1.0 1.00 7.5 7.5HCFC-141b CFCl.sub.2 CH.sub.3 0.75 2.10 10.1 3.6HCFC-142b CF.sub.2 ClCH.sub.3 0.38 2.10 19.9 6HCFC-225ca CF.sub.3 CF.sub.2 CHCl.sub.2 2.49 3.30 2.3 2.3HCFC-225cb CClF.sub.2 CF.sub.2 CHClF 0.91 3.86 2 1.96HCC-140 CCl.sub.3 CH.sub.3 1.2 1.21 6.3 6.3______________________________________
It would be desirable to have substitutes with OH rate constants of at least about 8 cm 3 /molecule/sec×10 -14 which equates to an atmospheric lifetime of 12 months or less.
If the OH rate constant of a compound is too high, the compound is a VOC (Volatile Organic Compound) because it is so reactive that it forms carbon dioxide which contributes to global warming. Thus, it would be desirable to have substitutes with OH rate constants of 25 cm 3 /molecule/sec×10 -14 or less which equates to an atmospheric lifetime of at least 4 months.
Commonly assigned U.S. Pat. No. 4,947,881 teaches a method of cleaning using hydrochlorofluoropropanes having 2 chlorine atoms and a difluoromethylene group. European Publication 347,924 published Dec. 27, 1989 teaches hydrochlorofluoropropanes having a difluoromethylene group. International Publication Number WO 90/08814 published Aug. 9, 1990 teaches azeotropes having at least one hydrochlorofluoropropane having a difluoromethylene group.
A wide variety of consumer parts is produced on an annual basis in the United States and abroad. Many of these parts have to be cleaned during various manufacturing stages in order to remove undesirable contaminants. These parts are produced in large quantities and as a result, substantial quantities of solvents are used to clean them.
Thus, substitutes having OH rate constants between about 8 and about 25 cm 3 /molecule/sec×10 -14 and which are useful in many applications including as solvents are needed in the art.
SUMMARY OF THE INVENTION
Straight chain and branched chain hydrochlorofluorocarbons having 3 to 5 carbon atoms and 1 or 2 chlorine atoms total over 1100 compounds. Out of this over 1100 compounds, I was surprised to find a class of 88 hydrochlorofluorocarbons having OH rate constants from about 8 to about 25 cm 3 /molecule/sec×10 31 14.
The OH rate constant can be determined by any method known in the art. For example, see Atkinson, "Kinetics and Mechanisms of the Gas-Phase Reactions of the Hydroxyl Radical with Organic Compounds under Atmospheric Conditions", Chem. Rey, 86, 69 (1986) and Taylor et al., "Laser Photolysis/Laser-Induced Fluorescence Studies of Reaction Rates of OH with CH 3 Cl, CH 2 Cl 2 , and CHCl 3 over an Extended Temperature Range", Int. J. of Chem, Kinetics 21, 829 (1989).
The straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention are listed in Table II below. The unit on the calculated K OH is cm 3 /molecule/sec×10 -14 and the unit on the calculated lifetime is years in Table II.
TABLE II______________________________________Number Chemical Formula K.sub.OH Lifetime______________________________________HCFC-234aa CF.sub.2 HCCl.sub.2 CF.sub.2 H 24.5 0.30HCFC-234ab CFH.sub.2 CCl.sub.2 CF.sub.3 11.9 0.64HCFC-234ba CF.sub.2 HCFClCFClH 22.9 0.33HCFC-234bb CF.sub.3 CFClCClH.sub.2 9.5 0.80HCFC-234bc CFH.sub.2 CFClCF.sub.2 Cl 13.1 0.58HCFC-234fa CF.sub.2 ClCH.sub.2 CF.sub.2 Cl 8.2 0.92HCFC-234fb CF.sub.3 CH.sub.2 CFCl.sub.2 8.2 0.92HCFC-243ea CFClHCFHCFClH 19.1 0.40HCFC-243ec CF.sub.2 ClCFHCClH.sub.2 8.4 0.90HCFC-244ba CFH.sub.2 CFClCF.sub.2 H 12.0 0.63HCFC-244da CF.sub.2 HCClHCF.sub.2 H 11.85 0.64HCFC-244db CF.sub.3 CClHCFH.sub.2 9.3 0.81HCFC-244ea CF.sub.2 HCFHCFClH 11.9 0.64HCFC-244eb CF.sub.3 CFHCClH.sub.2 10.5 0.72HCFC-244ec CFH.sub.2 CFHCF.sub.2 Cl 10.1 0.75HCFC-244fa CFClHCH.sub.2 CF.sub.3 8.5 0.89HCFC-244fb CF.sub.2 HCH.sub.2 CF.sub.2 Cl 9.15 0.83HCFC-252dc CH.sub.3 CClHCF.sub.2 Cl 15.3 0.49HCFC-252ec CH.sub.3 CFHCCl.sub.2 F 8.6 0.88HCFC-253ba CFH.sub.2 CFClCFH.sub.2 17.7 0.43HCFC-253bb CH.sub.3 CFClCF.sub.2 H 13.8 0.55HCFC-253ea CF.sub.2 HCFHCClH.sub.2 14.5 0.52HCFC-253eb CClFHCFHCFH.sub.2 16.5 0.46HCFC-253ec CH.sub.3 CFHCF.sub.2 Cl 8.0 0.95HCFC-253fa CF.sub.2 HCH.sub.2 CFClH 14.5 0.52HCFC-253fc CFH.sub.2 CH.sub.2 CF.sub.2 Cl 11.5 0.66HCFC-262fa CF.sub.2 HCH.sub.2 CClH.sub.2 14.99 0.50HCFC-262fb CFH.sub.2 CH.sub.2 CFClH 17.8 0.43HCFC-271b CH.sub.3 CFClCH.sub.3 9.95 0.76HCFC-271d CH.sub.3 CClHCFH.sub.2 19.44 0.39HCFC-271fb CH.sub.3 CH.sub.2 CFClH 9.98 0.76______________________________________
This present class with its OH rate constants between about 8 to about 25 cm 3 /molecule/sec×10 -14 unexpected. I discovered this when I compared isomers having the same --CAB--group wherein --CAB-- is --CCl 2 --, --CH 2 --, --CClH--, --CClF--, and --CHF--as the covered compound. I found that the isomers had OH rate constants less than 8 or greater than 25 cm 3 /molecule/sec×10 -14 . For example, CFClHCFHCFClH and CF 2 ClCFHCClH 2 of the present invention have K OH values of 19.1 and 8.4 cm 3 /molecule/sec×10 -14 respectively as shown in Table II. In contrast, the isomers, CF 2 HCFHCCl 2 H and CCl 2 FCFHCFH 2 , have K OH values of 31.3 and 30.0 cm 3 /molecule/sec×10 -14 respectively as shown in Table VII, and thus, are VOCs.
Also, CFH 2 CFClCF 2 H of the present invention has a K OH of 12.0 cm 3 /molecule/sec×10 -14 as shown in Table II. In contrast, the isomer, CF 3 CFClCH 3 , has a K OH of 1.8 cm 3 /molecule/sec×10 -14 as shown in Table VII, and thus, has a long atmospheric lifetime. The isomers, CFH 2 CCl 2 CFH 2 and CH 3 CCl 2 CF 2 H, have K OH values of 49.33 and 34.14 cm 3 /molecule/sec×10 -14 respectively as shown in Table VII and thus, are VOCs.
Additionally, CH 3 CFHCCl 2 F of the present invention has a K OH of 8.6 cm 3 /molecule/sec×10 -14 as shown in Table II. In contrast, the isomers, CClH 2 CFHCClFH and CFH 2 CFHCCl 2 H, have K OH values of 31.8 and 39.57 cm 3 /molecule/sec×10 -14 respectively as shown in Table VII, and thus, are VOCs.
Additionally, CF 2 HCH 2 CClH 2 and CFH 2 CH 2 CFClH of the present invention have K OH values of 14.99 and 17.8 cm 3 /molecule/sec×10 -14 respectively as shown in Table II. In contrast, the isomer, CF 2 ClCH 2 CH 3 , has a K OH of 2.9 cm 3 /molecule/sec×10 -14 as shown in Table VII, and thus, has a long atmospheric lifetime. Additionally, CH 3 CH 2 CFClH of the present invention has a K OH of 9.98 cm 3 /molecule/sec×10 -14 as shown in Table II. In contrast, the isomer, CFH 2 CH 2 CClH 2 , has a K OH value of 35.8 cm 3 /molecule/sec×10 -14 as shown in Table VII, and thus, is a VOC.
Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention.
For example, Haszeldine, Nature 165, 152 (1950) teaches the reaction of trifluoroiodomethane and acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. By using 3,3,3-trifluoropropyne as a starting material, CF 3 CFClCClH 2 (HCFC-234bb) may be prepared as follows. Commercially available trifluoromethyl iodide may be reacted with acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. The 3,3,3-trifluoropropyne may then be reacted with commercially available hydrogen fluoride to form 2,3,3,3-tetrafluoro-1-propene which is then chlorinated to form 1,2-dichloro-2,3,3,3-tetrafluoropropane.
CF 2 ClCFHCClH 2 (HCFC-243ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be dehydrohalogenated to form 1,3-dichloro-1-propyne. The 1,3-dichloro-1-propyne may then be fluorinated to form 1,3-dichloro-1,2-difluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-1,1,2-trifluoropropane.
CFH 2 CFClCF 2 H (HCFC-244ba) may be prepared as follows. Commercially available 1,3-difluoro-2-propanol may be dehydrated to form 1,3-difluoro-1-propene which may then be dehydrohalogenated to form 3-fluoro-1-propyne. The 3-fluoro-1-propyne may then be fluorinated, chlorinated, and fluorinated to form 1,1,2,3-tetrafluoro-2-chloropropane.
CFH 2 CFHCF 2 Cl (HCFC-244ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1-dichloro-3-fluoro-1-propene which may then be dehydrohalogenated to form 1-chloro-3-fluoro-1-propyne. The 1-chloro-3-fluoro-1-propyne may then be fluorinated to form 1-chloro-1,2,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3-tetrafluoropropane.
CFClHCH 2 CF 3 (HCFC-244fa) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1,1,2,3-pentafluoropropane. The 1,1,1,2,3-pentafluoropropane may then be dehydrohalogenated to form 1,3,3,3-tetrafluoro-1-propene which may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3,3-tetrafluoropropane.
CF 2 HCH 2 CF 2 Cl (HCFC-244fb) may be prepared as follows. Commercially available 2,2,3,3-tetrafluoro-1-propanol may be fluorinated to form 1,1,1,2,2,3-hexafluoropropane which may then be dehydrohalogenated to form 1,3,3-trifluoro-1-propyne. The 1,3,3-trifluoro-1-propyne may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,3,3-tetrafluoropropane.
CH 3 CFClCF 2 H (HCFC-253bb) may be prepared as follows. Commercially available 1,2-dibromopropane may be dehydrohalogenated to form propyne. The propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1,1,2-trifluoropropane.
CH 3 CFHCF 2 Cl (HCFC-253ec) may be prepared as follows. Commercially available 1,2-dichloropropane may be dehydrohalogenated to form 1-chloro-1-propene which may then be dehydrogenated to form 1-chloro-1-propyne. The 1-chloro-1-propyne may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1-fluoro1-propene which may then be fluorinated to form 1-chloro-1,1,2-trifluoropropane.
The preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF 2 ClCFHCClH 2 , CFH 2 CFClCF 2 H, CFH 2 CFHCF 2 Cl, CFClHCH 2 CF 3 , CF 2 HCH 2 CF 2 Cl, CH 3 CFClCF 2 H, and CH 3 CFHCF 2 Cl.
The straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention are listed in Table III below. The unit on the calculated K OH is cm 3 /molecule/sec×10 -14 and the unit on the calculated lifetime is years in Table III below.
TABLE III______________________________________Number Chemical Formula K.sub.OH Lifetime______________________________________HCFC-3541cd CH.sub.3 CClHCF.sub.2 CF.sub.2 Cl 12.8 0.59HCFC-354mbd CH.sub.3 CClHCFClCF.sub.3 11.9 0.63HCFC-355lcf CFH.sub.2 CH.sub.2 CF.sub.2 CF.sub.2 Cl 12.0 0.63HCFC-355lec CH.sub.3 CF.sub.2 CFHCF.sub.2 Cl 12.8 0.59HCFC-355lef CF.sub.2 HCH.sub.2 CFHCF.sub.2 Cl 15.6 0.48HCFC-355lff CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.2 Cl 10.4 0.73HCFC-355mbf CFH.sub.2 CH.sub.2 CFClCF.sub.3 11.5 0.66HFFC-355mcf CF.sub.3 CF.sub.2 CH.sub.2 CClH.sub.2 8.93 0.85HCFC-355mdc CH.sub.3 CF.sub.2 CClHCF.sub.3 12.0 0.63HCFC-355mdf CF.sub.2 HCH.sub.2 CClHCF.sub.3 14.3 0.53HCFC-355meb CH.sub.3 CFClCFHCF.sub.3 11.8 0.64HCFC-355med CFH.sub.2 CClHCFHCF.sub.3 14.1 0.54HCFC-355mfb CFH.sub.2 CFClCH.sub.2 CF.sub.3 15.9 0.48HCFC-355mfc CF.sub.3 CH.sub.2 CF.sub.2 CClH.sub.2 13.2 0.57HCFC-355mfd CF.sub.2 HCClHCH.sub.2 CF.sub.3 14.9 0.51HCFC-355mfe CFClHCFHCH.sub.2 CF.sub.3 15.1 0.50HCFC-355pcb CH.sub.3 CFClCF.sub.2 CF.sub.2 H 15.7 0.48HCFC-355rcc CH.sub.3 CF.sub.2 CF.sub.2 CFClH 15.2 0.50HCFC-363lbfs CH.sub.3 CH.sub.2 CClFCF.sub.2 Cl 13.4 0.56HCFC-364med CH.sub. 3 CClHCFHCF.sub.3 15.0 0.50HCFC-364mff CFClHCH.sub.2 CH.sub.2 CF.sub.3 15.5 0.49HCFC-373lef CH.sub.3 CH.sub.2 CFHCF.sub.2 Cl 9.11 0.83HCFC-373mfd CH.sub.3 CClHCH.sub.2 CF.sub.3 14.3 0.53HCFC-373mff CF.sub.3 CH.sub.2 CH.sub.2 CClH.sub.2 13.2 0.57HCFC-391rff CH.sub.3 CH.sub.2 CH.sub.2 CFClH 10.3 0.73HCFC-391sbf CH.sub.3 CH.sub.2 CFClCH.sub.3 14.2 0.53______________________________________
Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
For example, R. N. Haszeldine et al., "Addition of Free Radicals to Unsaturated Systems. Part XIII. Direction of Radical Addition to Chloro-1:1-difluoroethylene", J. of Amer. Chem. Soc., 2193 (1957) teach the reaction of trifluoroiodomethane with chloro-1:1-difluoroethylene to prepare 3-chloro-1:1:1:2:2-pentafluoro-3-iodopropane which is then chlorinated to form 1,1-dichloro-2,2,3,3,3-pentafluoropropane (known in the art as HCFC-225ca). This known method can be modified to form CF 3 CF 2 CH 2 CClH 2 (HCFC-355mcf) as follows. Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1,1,2,2-pentafluoro-4-iodobutane which is then chlorinated to form 1,1,1,2,2-pentafluoro-4-chlorobutane.
CH 3 CF 2 CFHCF 2 Cl (HCFC-355lec) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may then be dehydrohalogenated to form 1-chloro-3,3-difluoro-1-butene. The 1-chloro-3,3-difluoro-1-butene may then be dehydrogenated to form 1-chloro-3,3-difluoro-1-propyne which may then be fluorinated to form 1-chloro-1,2,3,3-tetrafluoro-1-butene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3,3-pentafluorobutane.
CF 3 CH 2 CH 2 CF 2 Cl (HCFC-355lff) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butyne. The hexafluoro-2-butyne may be hydrogenated to form 1,1,1,4,4,4-hexafluorobutane which may be chlorinated to form 1-chloro-1,1,4,4,4-pentafluorobutane.
CFH 2 CH 2 CFClCF 3 (HCFC-355mbf) may be prepared as follows. Commercially available 1,4-dichloro-2-butyne may be reacted with commercially available hydrogen fluoride to form 1,4-dichloro-2-fluoro-2-butene which may be fluorinated to form 1,2,4-trifluoro-2-butene. The 1,2,4-trifluoro-2-butene may be reacted with commercially available hydrogen chloride to form 2-chloro-1,2,4-trifluorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, and fluorinated to form 2-chloro-1,1,1,2,4-pentafluorobutane.
CH 3 CF 2 CClHCF 3 (HCFC-355mdc) may be prepared as follows. Commercially available 3,4-dichloro-1-butene may be dehydrogenated to form 3,4-dichloro-1-butyne which may be reacted with commercially available hydrogen fluoride to form 1,2-dichloro-3,3-difluorobutane. The 1,2-dichloro-3,3-difluorobutane may be dehydrogenated to form 1,2-dichloro-3,3-difluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,3,3-tetrafluorobutane. The 2-chloro-1,1,3,3-tetrafluorobutane may be dehydrogenated to form 2-chloro-1,1,3,3-tetrafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,1,3,3-pentafluorobutane.
CH 3 CFClCFHCF 3 (HCFC-355meb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-1-butene. The 3-chloro-1,3-difluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4-tetrafluorobutane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-1-butene. The 3-chloro-1,1,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4,4-pentafluorobutane.
CH 3 CFClCF 2 CF 2 H (HCFC-355pcb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrogenated to form 3-chloro-1,2,3-trifluoro-1-butene. The 3-chloro-1,2,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,3,4,4-pentafluorobutane.
CH 3 CF 2 CF 2 CFClH (HCFC-355rcc) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may be dehydrogenated to form 1-chloro-2,3,3-trifluoro-1-butene. The 1-chloro-2,3,3-trifluoro-1-butene may be fluorinated to form 1-chloro-1,2,2,3,3-pentafluorobutane.
CH 3 CClHCFHCF 3 (HCFC-364med) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-2-fluorobutane which may be dehydrohalogenated to form 1,3-dichloro-1-butene. The 1,3-dichloro-1-butene may be fluorinated to form 2-chloro-3,4,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,1-difluoro-1-butene. The 3-chloro-1,1-difluoro-1-butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafluorobutane.
The preferred straight chain hydrochlorofluorocarbons having 4 carbon atoms are CH 3 CF 2 CFHCF 2 Cl, CF 3 CH 2 CH 2 CF 2 Cl, CFH 2 CH 2 CFClCF 3 , CH 3 CF 2 CClHCF 3 , CH 3 CFClCFHCF 3 , CH 3 CFClCF 2 CF 2 H, CH 3 CF 2 CF 2 CFClH, and CH 3 CClHCFHCF 3 .
The branched chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention are listed in Table IV below. The unit on the calculated K OH is cm 3 /molecule/sec×10 31 14 and the unit on the calculated lifetime is years in Table IV below.
TABLE IV______________________________________Number Chemical Formula K.sub.OH Lifetime______________________________________HCFC-345kms CH.sub.3 C(CF.sub.3)FCFCl.sub.2 9.11 0.83HCFC-345lls CH.sub.3 C(CF.sub.2 Cl)FCF.sub.2 Cl 9.11 0.83HCFC-355lms CH.sub.3 C(CF.sub.3)HCF.sub.2 Cl 8.3 0.91HCFC-355mop CF.sub.2 HC(CClH.sub.2)HCF.sub.3 14.5 0.52HCFC-355mps CH.sub.3 C(CF.sub.2 H)ClCF.sub.3 15.3 0.50HCFC-355mrs CH.sub.3 C(CFClH)FCF.sub.3 15.1 0.50HCFC-373mss CH.sub.3 C(CH.sub.3)ClCF.sub.3 13.4 0.56______________________________________
Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
CH 3 C(CF 3 )HCF 2 Cl (HCFC-355lms) may be prepared as follows. Commercially available 1-chloro-2-methylpropane may be fluorinated to form 1-chloro-1,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 1-chloro-1-fluoro-2-methylpropene. The 1-chloro-1-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3,3-difluoro-2-methylpropene. The 3-chloro-3,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrogenated to form 3-chloro-1,3,3-trifluoro-2-methylpropene. The 3-chloro-1,3,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene. The 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,3,3,3-pentafluoro-2-methylpropane.
CH 3 C(CF 2 H)ClCF 3 (HCFC-355mps) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1,1,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3,3-difluoro-2-methylpropene. The 3,3-difluoro-2-methylpropene may be fluorinated to form 1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 1,3,3-trifluoro-2-methylpropene. The 1,3,3-trifluoro-2-methylpropene may be fluorinated to form 1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-methylpropene. The 1,1,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1,2-dichloro-1,1,4,4-tetrafluoro-2-methylpropane which may be fluorinated to form 2-chloro-1,1,1,3,3-pentafluoro-2-methylpropane.
CH 3 C(CFClH)FCF 3 (HCFC-355mrs) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3-fluoro-2-methylpropene. The 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-2-methylpropene. The 3-chloro-1,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-2-methylpropene. The 3-chloro-1,1,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3,3,3-pentafluoro-2-methylpropane.
The preferred branched hydrochlorofluorocarbons having 4 carbon atoms are CH 3 C(CF 3 )HCF 2 Cl, CH 3 C(CF 2 H)ClCF 3 , and CH 3 C(CFClH)FCF 3 .
The branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention are listed in Table V below. The unit on the calculated K OH is cm 3 /molecule/sec×10 -14 and the unit on the calculated lifetime is years in Table V below.
TABLE V______________________________________Number Chemical Formula K.sub.OH Lifetime______________________________________HCFC-356mlfq CFH.sub.2 CH.sub.2 C(CF.sub.2 Cl)FCF.sub.3 12.0 0.63HCFC-357lcsp CF.sub.2 ClCF.sub.2 C(CH.sub.3)FCF.sub.2 H 15.1 0.50HCFC-357lsem CF.sub.3 CFHC(CH.sub.3)FCF.sub.2 Cl 14.6 0.52HCFC-357mbsp CF.sub.3 CFClC(CH.sub.3)FCF.sub.2 H 15.0 0.50HCFC-357mcpo CF.sub.3 CF.sub.2 C(CF.sub.2 H)HCClH.sub.2 14.7 0.51HCFC-357mcsp CF.sub.3 CF.sub.2 C(CH.sub.3)ClCF.sub.2 H 13.7 0.55HCFC-357mcsr CF.sub.3 CF.sub.2 C(CH.sub.3)FCFClH 15.1 0.50HCFC-357mlcs CH.sub.3 CF.sub.2 C(CF.sub.2 Cl)HCF.sub.3 10.7 0.71HCFC-357mmbs CH.sub.3 CFClC(CF.sub.3)HCF.sub.3 9.5 0.80HCFC-357mmel CF.sub.2 ClCHFC(CH.sub.3)FCF.sub.3 14.3 0.53HCFC-357mmfo CH.sub.2 ClCH.sub.2 C(CF.sub.3)FCF.sub.3 8.8 0.86HCFC-357mmfq CFH.sub.2 CH.sub.2 C(CF.sub.3)ClCF.sub.3 11.5 0.66HCFC-357mmfr CFClHCH.sub.2 C(CF.sub.3)HCF.sub.3 14.0 0.54HCFC-357mofm CF.sub.3 CH.sub.2 C(CClH.sub.2)FCF.sub.3 14.1 0.54HCFC-357msem CF.sub.3 CFHC(CH.sub.3)ClCF.sub.3 13.0 0.57HCFC-358mcsr CF.sub.3 CF.sub.2 C(CH.sub.3)FCClFH 13.8 0.55HCFC-366mmds CH.sub.3 CClHC(CF.sub.3)HCF.sub.3 12.8 0.59HCFC-366mmfo CClH.sub.2 CH.sub.2 C(CF.sub.3 )HCF.sub.3 13.2 0.57HCFC-375lcss CF.sub.2 ClCF.sub.2 C(CH.sub.3)FCH.sub.3 10.7 0.71HCFC-375mbss CF.sub.3 CFClC(CH.sub.3)FCH.sub.3 10.7 0.71HCFC-393less CF.sub.2 ClCFHC(CH.sub.3)HCH.sub.3 12.1 0.62HCFC-393mdss CF.sub.3 CClHC(CH.sub.3)HCH.sub.3 10.0 0.76HCFC-393sfms CH.sub.3 CH.sub.2 C(CF.sub.3)ClCH.sub.3 13.0 0.58HCFC-3-11-1rfss CFClHCH.sub.2 C(CH.sub.3)HCH.sub.3 13.4 0.56______________________________________
Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention.
CFH 2 CH 2 C(CF 2 Cl)FCF 3 (HCFC-356mlfq) may be prepared as follows. Commercially available 1,4-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,4-dichloro-2-trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form 1,4-dichloro-3-trifluoromethyl-1-butene. The 1,4-dichloro-3-trifluoromethyl-1-butene may be hydrogenated to form 1,4-dichloro-2-trifluoromethylbutane which may be fluorinated to form 1-chloro-2-trifluoromethyl-4-fluorobutane. The 1-chloro-2-trifluoromethyl-4-fluorobutane may be dehydrogenated to form 1-chloro-2-trifluoromethyl-4-fluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane. The 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane may be dehydrohalogenated to form 1-chloro-2-trifluoromethyl-1,4-difluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,1,2,4-tetrafluorobutane.
CF 3 CFHC(CH 3 )FCF 2 Cl (HCFC-3571sem) may be prepared as follows. Commercially available 1,4-dichloro-2-butene may be reacted with commercially available iodomethane to form 1,4-dichloro-3-iodo-2-methylbutane which may be dehydrohalogenated to form 1,4-dichloro-3-methyl-1-butene. The 1,4-dichloro-3-methyl-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4-trifluorobutane which may be dehydrohalogenated to form 1,1-difluoro-3-methyl-4-chloro-1-butene. The 1,1-difluoro-3-methyl-4-chloro-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4,4-tetrafluorobutane which may be dehydrogenated to form 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1-butene. The 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,2,3,4,4,4-hexafluorobutane which may be dehydrohalogenated to form 1-chloro-2-methyl-1,3,4,4,4-pentafluoro-1-butene. The 1-chloro-2-methyl-1,3,4,4,4-pentafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
CF 3 CFClC(CH 3 )FCF 2 H (HCFC-357mbsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-2-methyl-1,1,1,4,4,4-hexafluoropropane which may be fluorinated to form 2-methyl-3-chloro-1,1,1,2,3,4,4-heptafluorobutane. The 2-methyl-3-chloro-1,1,1,2,3,4,4-heptafluorobutane may be dehalogenated to form 3-chloro-2-methyl-1,1,3,4,4,4-hexafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
CF 3 CF 2 C(CH 3 )ClCF 2 H (HCFC-357mcsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with iodomethane to form 2-methyl-2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 2-methyl-1,1,3,3,4,4,4-heptafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-2-methyl-1,1,3,3,4,4,4-heptafluorobutane.
CH 3 CF 2 C(CF 2 Cl)HCF 3 (HCFC-357mlcs) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,3-dichloro-2-trifluoromethyl-3-iodobutane which may be fluorinated to form 1,3,3-trifluoro-2-trifluoromethylbutane. The 1,3,3-trifluoro-2-trifluoromethylbutane may be dehydrogenated to form 1,3,3-trifluoro-2-trifluoromethyl-1-butene which may be fluorinated to form 1,1,2,3,3-pentafluoro-2-trifluoromethylbutane. The 1,1,2,3,3-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-trifluoromethyl-1-butene which may be reacted with commercially available hydrogen chloride to form 1-chloro-1,1,3,3-tetrafluoro-2-trifluoromethylbutane.
CH 3 CFClC(CF 3 )HCF 3 (HCFC-357mmbs) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 3-trifluoromethyl-1,1,2,3,4,4,4-heptafluoro-1-butene which may be hydrogenated to form 2-trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluoro-1-butene which may be hydrogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluorobutane. The 3-trifluoromethyl-1,2,3,4,4,4-hexafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-2,3,4,4,4-pentafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2-trifluoromethyl-1,1,1,2,3-pentafluorobutane. The 3-chloro-2-trifluoromethyl-1,1,1,2,3-pentafluorobutane may be dehalogenated to form 3-chloro-2-trifluoromethyl-1,1,3-trifluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-trifluoromethyl-1,1,1,3-tetrafluorobutane.
CF 2 ClCHFC(CH 3 )FCF 3 (HCFC-357mmel) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methylperfluorobutane. The 2-methylperfluorobutane may be dehalogenated to form 1,1,2,3,4,4,4-heptafluoro-3-methyl-1-butene which may be reacted with commercially available hydrogen chloride to form 4-chloro-1,1,1,2,3,4,4-heptafluoro-2-methylbutane.
The method of R. N. Haszeldine et al., supra, can be modified to form CH 2 ClCH 2 C(CF 3 )FCF 3 (HCFC-357mmfo) as follows. Commercially available perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trifluoromethyl-1,1,1,2-tetrafluoro-4-iodobutane which may then be chlorinated to form 2-trifluoromethyl-1,1,1,2-tetrafluoro-4-chlorobutane.
CFH 2 CH 2 C(CF 3 )ClCF 3 (HCFC-357mmfq) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be fluorinated to form 2-chloro-2-trifluoromethyl-perfluorobutane. The 2-chloro-2-trifluoromethyl-perfluorobutane may be dehalogenated to form 3-chloro-3-trifluoromethyl-1,1,2,4,4,4-hexafluoro-l-butene which may be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,3,4,4-hexafluorobutane. The 2-chloro-2-trifluoromethyl-1,1,1,3,4,4-hexafluorobutane may be fluorinated to form 3-chloro-3-trifluoromethyl-1,4,4,4-tetrafluoro-1-butene which may then be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,4-tetrafluorobutane.
CF 3 CFHC(CH 3 )ClCF 3 (HCFC-357msem) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be chlorinated to form 2,3,3-trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane. The 2,3,3-trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane may be dehalogenated to form 3-chloro-1,1,1,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane. The 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane may be dehydrohalogenated to form 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane.
CF 3 CF 2 C(CH 3 )FCClFH (HCFC-358mcsr) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methyl-perfluorobutane. The 2-methyl-perfluorobutane may be dehalogenated to form 2-methyl-perfluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 1,1,2,3,3,4,4,4-octafluoro-2-methylbutane. The 1,1,2,3,3,4,4,4-octafluoro-2-methylbutane may be dehalogenated to form 1,3,3,4,4,4-hexafluoro-2-methyl-1-butene which may be chlorinated to form 1,2-dichloro-1,3,3,4,4,4-hexafluoro-2-methylbutane. The 1,2-dichloro-1,3,3,4,4,4-hexafluoro-2-methylbutane may be dehydrohalogenated to form 1-chloro-1,3,3,4,4,4-hexafluoro-2-methyl-1-butene which may be reacted with commercially available hydrogen fluoride to form 1-chloro-1,2,3,3,4,4,4-heptafluoro-2-methylbutane.
CH 3 CClHC(CF 3 )HCF 3 (HCFC-366mmds) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-1,1,1,4,4,4-hexafluoro-2-methyl-2-butene. The 3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethyl-2-butene may be hydrogenated to form 3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be dehydrohalogenated to form 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl-1-butene. The 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl-1-butene may be hydrogenated to form 3-iodo-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-chloro-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-1,4,4,4-tetrafluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1,4-tetrafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4-tetrafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-4,4,4-trifluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1-trifluoro-2-trifluoromethylbutane.
The preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH 2 CH 2 C(CF 2 Cl)FCF 3 , CF 3 CFHC(CH 3 )FCF 2 Cl, CF 3 CFClC(CH 3 )FCF 2 H, CF 3 CF 2 C(CH 3 )ClCF 2 H, CH 3 CF 2 C(CF 2 Cl)HCF 3 , CH 3 CFClC(CF 3 )HCF 3 , CF 2 ClCHFC(CH 3 )FCF 3 , CH 2 ClCH 2 C(CF 3 )FCF 3 , CFH 2 CH 2 C(CF 3 )ClCF 3 , CF 3 CFHC(CH 3 )ClCF 3 , CF 3 CF 2 C(CH 3 )FCClFH, and CH 3 CClHC(CF 3 )HCF 3 .
Other advantages of the invention will become apparent from the following description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Known solvents may be blended with the hydrochlorofluorocarbons of the present invention. Examples of useful known solvent are listed in Table VI below.
TABLE VI______________________________________Number Chemical Formula______________________________________HCFC-234cc CF.sub.2 ClCF.sub.2 CClH.sub.2HCFC-234cd CH.sub.2 FCF.sub.2 CFCl.sub.2HCFC-244ca CF.sub.2 HCF.sub.2 CClH.sub.2HCFC-244cb CFH.sub.2 CF.sub.2 CFClHHCFC-253ca CFH.sub.2 CF.sub.2 CClH.sub.2HCFC-253cb CH.sub.3 CF.sub.2 CFClH______________________________________
HCFC-234cc may be formed by any known method such as the reaction of 1,1,1,2,2,3-hexachloropropane with antimony pentachloride and hydrogen fluoride at 100° C. HCFC-234cd may be formed by any known method such as the reaction of 1,1,1-trichloro-2,2,3-trifluoropropane with antimony pentachloride and hydrogen fluoride at 120° C.
HCFC-244ca may be formed by any known method such as the reaction of 1,1,2,2,3-pentachloropropane with antimony pentachloride and hydrogen fluoride at 100° C. HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1,1,2,2-tetrafluoropropane with cesium fluoride and tetrabutylammonium bromide at 150° C.
HCFC-253ca may be formed by any known method such as the reaction of 1,2,3-trichloro-2-fluoropropane with niobium pentachloride and hydrogen fluoride at 100° C. HCFC-253cb may be formed by any known method such as the reaction of 1,1,2,2-tetrachloropropane with tantalum pentafluoride and hydrogen fluoride at 130° C.
The present hydrochlorofluorocarbons may be used as solvents in vapor degreasing, solvent cleaning, cold cleaning, dewatering, dry cleaning, defluxing, decontamination, spot cleaning, aerosol propelled rework, extraction, particle removal, and surfactant cleaning applications. In these uses, the object to be cleaned is immersed in one or more stages in the liquid and/or vaporized solvent or is sprayed with the liquid solvent. Elevated temperatures, ultrasonic energy, and/or agitation may be used to intensify the cleaning effect.
The present hydrochlorofluorocarbons are also useful as blowing agents, Rankine cycle and absorption refrigerants, and power fluids and especially as refrigerants for centrifugal refrigeration chillers.
The present invention is more fully illustrated by the following non-limiting Examples.
COMPARATIVES
The hydrochlorofluorocarbons having 3 carbon atoms and 1 or 2 chlorine atoms in Table VII below are isomers of the compounds of the present invention. As discussed above, these compounds have OH rate constants which are less than 8 cm 3 /molecule/sec×10 -14 or greater than 25 cm 3 /molecule/sec×10 -14 . The unit on the K OH is cm 3 /molecule/sec×10 -14 and the unit on the lifetime is years in Table VII below.
TABLE VII______________________________________Number Chemical Formula K.sub.OH Lifetime______________________________________HCFC-243eb CF.sub.2 HCFHCCl.sub.2 H 31.3 0.24HCFC-243ed CCl.sub.2 FFHCFH.sub.2 30.0 0.25HCFC-244bb CF.sub.3 CFClCH.sub.3 1.8 4.20HCFC-252aa CFH.sub.2 CCl.sub.2 CFH.sub.2 49.33 0.15HCFC-252ab CH.sub.3 CCl.sub.2 CF.sub.2 H 34.14 0.22HCFC-252ea CClH.sub.2 CFHCClFH 31.8 0.24HCFC-252eb CFH.sub.2 CFHCCl.sub.2 H 39.57 0.19HCFC-262fc CF.sub.2 ClCH.sub.2 CH.sub.3 2.9 2.61HCFC-271fa CFH.sub.2 CH.sub.2 CClH.sub.2 35.8 0.21______________________________________
EXAMPLES 1-85
Each solvent listed in Tables II through V is added to mineral oil in a weight ratio of 50:50 at 27° C. Each solvent is miscible in the mineral oil.
Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
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The present invention provides hydrochlorofluorocarbons having 3 to 5 carbons atoms, 1 to 2 chlorine atoms, and an OH rate constant from about 8 to about 25 cm 3 /molecule/sec×10 -14 . The hydrochlorofluorocarbons are useful as solvents and blowing agents.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 08/601,238, filed Feb. 14, 1996, now U.S. Pat. No. 5,632,825 which is a continuation of Ser. No. 08/253,746, filed Jun. 3, 1994, now U.S. Pat. No. 5,544,859, issued Aug. 13, 1996, both of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
This invention generally relates to lead containing materials and products which are resistant to leaching lead into potable water systems used for human consumption and methods for the production thereof.
BACKGROUND OF THE INVENTION
Potable water systems are comprised of numerous components including pipe and plumbing fixtures such as faucets, valves, couplings, and pumps which both store and transport water. These components have traditionally been made of copper-based cast and wrought alloys with lead dispersed therein in amounts between 1-9% by weight. The lead allows these components to be more easily machined into a final product which has both a predetermined shape yet acceptable strength and watertight properties.
The lead used to improve the machinability of these copper alloy materials has been proven to be harmful to humans when consumed as a result of the lead leaching into potable water. This damage is particularly pronounced in children with developing neural systems. To reduce the risk of exposure to lead, federal and state governments now regulate the lead content in potable water by requiring reductions in the amount of lead which can leach from plumbing fixtures. A variety of strategies have been developed to address this problem. For example, simply reducing the amount of lead in plumbing fixtures has been attempted. However, such low lead content alloys are difficult to machine.
Another strategy is to develop specific alloys such as that disclosed in U.S. Pat. No. 4,879,094 to Rushton. The patent describes an alloy which contains 1.5-7% bismuth, 5-15% zinc, about 1-12% tin and the balance copper. This copper alloy is capable of being machined, but must be cast and not wrought. This is undesirable since a wrought alloy may be extruded or otherwise mechanically formed into shape. It is thus not necessary to cast objects to a near finished shape. Further, wrought alloy feed stock is more amenable to high speed manufacturing techniques and generally has lower associated fabrication costs than cast alloys.
A copper based machinable alloy with a reduced lead content or which may be lead free was disclosed by McDivitt in U.S. Pat. No. 5,137,685. This alloy contains from about 30-58% by weight zinc, 0-5% weight of bismuth, and the balance of the alloy being copper. This alloy is expensive to produce, however, based both on the cost of the bismuth as compared to lead, and further since the bismuth must be thoroughly mixed within the matrix of the copper alloy material.
Despite the developments made in the area of reduced lead leaching into potable water systems, there remains a need to provide a material which is less susceptible to leaching lead into potable water systems, yet which utilizes the inherent benefits of copper alloys that contain lead.
SUMMARY OF THE INVENTION
This discovery is accomplished by an apparatus for conducting the flow of a fluid. The apparatus comprises a solid body piece having a conduit surface that defines a conduit volume through which the flow of a fluid may be directed. The body piece comprises a first solid phase, which is a continuous phase, and a second solid phase of dispersoids comprised of lead dispersed in the first solid phase. A plurality of the dispersoids are present adjacent the conduit surface of the solid body piece.
The apparatus further includes a coating at or proximate to the conduit surface which comprises multiple distinct occurrences of coating material. At least a portion the occurrences being interposed between at least a portion of the conduit volume and at least a portion of the plurality of dispersoids.
The invention further includes an article useful in fluid storage and transportation with a composition comprising an interior portion having a metal matrix comprising greater than about fifty weight percent copper. The interior portion does not have any exposed surface. The article additionally has a perimeter portion integral with the interior portion and an exposed surface that may be in contact with a fluid. The perimeter portion has dispersoids comprising lead dispersed throughout a metal matrix which comprises greater than about fifty weight percent copper.
The article further includes a coating in the perimeter portion comprised of a metal coating material. The coating has a top side and a bottom side, the top side forming a part of the exposed surface and the bottom side being adjacent to at least one dispersoid in said perimeter portion. The coating substantially physically separates the lead in at least one dispersoid from the exposed surface, although additional metal coating materials may be found beyond the exposed surface and within the dispersoid.
The invention further includes a solid material useful in water service. The material comprises an interior matrix phase which comprises copper, an exterior surface, and a dispersed phase of particles consisting essentially of lead. The lead is dispersed in the interior matrix with a plurality of the lead particles adjacent the exterior surface. The material additionally has a non-continuous coating material at the exterior surface which substantially physically separates the lead in at least a portion of the plurality of lead particles from the exposed surface.
The invention further includes an article for use in fluid containment and transportation. The article comprises a flow directing piece shaped to provide a fluid flow conduit, the flow directing piece having an exterior surface. The interior surface includes a fluid contact surface adjacent the fluid flow conduit. The apparatus further includes a perimeter portion in the flow directing piece which comprises the exterior surface. The perimeter portion extends to a depth smaller than about 100 microns into the body portion from the surface of the exterior portion. The perimeter portion may comprise lead. The apparatus flow directing piece further includes an interior portion which is surrounded by the exterior portion, the interior portion comprising lead. The flow directing piece further includes a lead leach inhibitor, the perimeter portion having an average concentration of lead leach inhibitor that is greater than the average concentration of lead leach inhibitor in the interior portion.
The invention further includes a copper-based metal composition. The composition comprises greater than about 50 weight percent copper, from about one weight percent to about ten weight percent lead, and less than about 0.005 weight percent of a lead leach inhibitor metal selected from the group comprising copper, bismuth, tin, and other metals which are more electropositive than lead.
The invention further includes a method for preparing the surface of a copper-containing article. The article comprises a solid continuous phase comprising copper and a solid non-continuous phase of dispersoids comprising lead dispersed in the continuous phase. The article has an exposed surface, wherein the continuous phase and a plurality of the dispersoids forms at least a part of the exposed surface. The method includes covering at least a portion of the lead in the plurality of dispersoids with a non-continuous coating phase.
As the aforementioned embodiments of the invention disclose, lead containing copper-based alloys may be effectively treated to prevent lead from leaching into water systems. This treatment may be done efficiently and in a cost effective manner utilizing conventional alloys. Other objects and advantages of the invention will become apparent upon reading the following detailed description and appended claims, and upon reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a cross-sectional view of a pipe or plumbing fixture capable of storing or transporting potable water or other fluids.
FIG. 2 is an expanded cross-sectional view depicting the conduit surface, perimeter portion, first solid phase, second solid phase, and non-continuous surface coating.
FIGS. 3-6 illustrate quantitative test data obtained from experiments performed on treated and non-treated copper alloy test fixtures.
It should be understood that the drawings are not to scale, and that the invention is not necessarily limited to the particular embodiments illustrated herein.
DETAILED DESCRIPTION
The present invention is used for conducting the flow of fluids such as water, while inhibiting the leaching of lead into the fluid. The invention may include pipes, valves, faucets, pumps and other commonly known plumbing fixtures. The materials typically used in the production of these plumbing fixtures include copper alloys, such as brass, which have lead dispersed throughout the alloy material. The materials are characterized in that lead which is exposed to the water transportation surface of the apparatus is selectively coated with a non-continuous surface coating which substantially precludes lead from leaching into the water.
One embodiment of the present invention is an apparatus for conducting the flow of fluid. The apparatus includes a solid body piece 2 having a non-continuous surface coating 12. The flow directing or solid body piece 2 is shaped such that it has a conduit surface 4 which defines a conduit volume 6. The conduit volume 6 is the space through which the apparatus is designed to have fluid flow. For example, in the instance where the apparatus is a pipe, the conduit surface 4 is the inside surface of the pipe, which contacts water flowing through the pipe on the fluid contact or conduit surface 4.
The solid body piece 2 includes a first continuous solid phase 8 and a second solid phase 10 of dispersoids within the first continuous solid phase 8. For instance, in the case of a brass pipe having lead dispersoids throughout the brass, the brass is the first continuous solid phase 8 and the lead constitutes the second solid phase of dispersoids 10.
The first continuous solid phase 8 is typically metal and more typically comprises copper. For example, the first continuous solid phase 8 can be a copper alloy and can contain over 50% by weight of copper. Such copper alloys can be brass including Cu/Zn/Si; Mn bronze; leaded Mn bronze and a variety of bronzes including Cu/Sn; Cu/Sn/Pb; Cu/Sn/Ni; Cu/Al; and other high copper alloys containing 94-98.5 weight percent Cu and 0.02 weight percent lead. The alloys typically include between about 50 weight percent and about 98.5 weight percent Cu, more preferably between about 53.5 weight percent and about 94 weight percent Cu and more preferably between about 60 weight percent and about 82 weight percent Cu. In a preferred embodiment of the present invention, a continuous solid body phase comprised of about 57%-82% copper, 0.2% tin, 7%-41% zinc, 2%-8% lead, and trace amounts of iron, antimony, nickel, sulfur, phosphorous, aluminum and silicon is used.
The second solid phase of dispersoids 10 comprise lead. The lead dispersoids are dispersed in the first continuous solid phase 8 and a plurality are adjacent the fluid contact or conduit surface 4. Thus, while the lead dispersoids are contained throughout the interior matrix of the first continuous solid phase 8, some portion can be exposed on the fluid contact or conduit surface 4. Therefore, untreated solid body pieces 2 having lead exposed to fluids flowing throughout the conduit volume 6 allow for the leaching of lead into the fluid, which may contaminate the fluid. Typically, lead dispersoids approximately comprise 1-9% by weight of the solid body piece 2 and more typically 3-5%. In one embodiment, the second solid phase of dispersoids 10 consists essentially of lead. The plurality of lead dispersoids allows the solid body piece 2 to be machined more easily and allows for the use of wrought alloy feed stock rather than cast alloy components. In addition to lead dispersoids, the second solid phase of dispersoids 10 can include dispersoids comprised of elements which can be the same as the non-continuous surface coating 12, i.e., gold, palladium, silver, platinum, tin, copper and bismuth.
In accordance with the present invention, the apparatus also includes a non-continuous surface coating 12 at or proximate to the conduit surface 4 which includes multiple distinct occurrences of a coating material. The occurrences are generally interposed between at least a portion of the conduit volume 6 and at least a portion of the lead dispersoids. In this manner, lead dispersoids are impeded from leaching lead into fluids, such as potable water, which flow through the conduit volume 6. One characteristic of the coating material is that it is effective as a coating of the dispersoids under normal use conditions for normal product lifetimes. Such coating characteristics are typified by the coatings and coating processes discussed below.
The coating of the second solid phase of lead dispersoids 10 inhibits the leaching of lead into fluid which passes through the conduit volume 6 and which otherwise would be in contact with the second solid phase of lead dispersoids 10. In a preferred embodiment of the present invention, at least about 90% of the surface area of the second solid phase of lead dispersoids 10 exposed on the conduit surface 4 are covered by the non-continuous surface coating 12. In a more preferred embodiment, at least about 95% of the second solid phase of lead dispersoids 10 exposed on the conduit surface 4 are covered by the non-continuous surface coating 12 and in a most preferred embodiment 99%.
Although the term "coating" is most commonly used in reference to the covering of a given item or material, the context of the term "coating" is not intended to be so limited with the present invention. That is, the term "coating" is additionally meant to encompass a "substitution" or "cementation" process as well as the formation of a new alloy at the interface of the dispersoids and conduit surface. The "coating" of the dispersoid is thus accomplished with a lead based alloy, a lead salt or a lead substitution product as more thoroughly discussed below.
Thus, in another embodiment of the present invention, as the first and second solid phases of the particular body piece are exposed to a solution containing a metal such as bismuth, tin or copper, individual molecules from the second solid phase of dispersoids are replaced or substituted with a molecule of the given metal. This substitution process at the interface of the conduit volume surface creates a layer of metallic molecules such as tin, bismuth or copper which are "cemented" or bonded to the underlying second solid phase dispersoid molecules, which are most commonly lead. Thus, the outer metallic molecules are bonded, or cemented, to the underlying second solid phase of the dispersoid and hence form a "coating" by inhibiting the dispersoid molecules from leaching into a water source which is in contact with the conduit surface.
In yet another embodiment of the present invention, a new alloy is formed at or in close proximity to the outer surface of the second solid phase dispersoids which are in contact with the conduit volume. This alloy, which is generally lead when referring to lead dispersoids in a second solid phase, may exist immediately on the surface of the dispersoids in contact with the conduit surface or extend into the second solid phase dispersoid. Further, the alloy may not be continuous near the conduit surface since non-bonded metallic molecules such as copper, tin or bismuth may exist independently within or in close proximity to the alloy.
In accordance with the present invention, the non-continuous surface coating 12 can comprise any metal which is more electropositive than lead. For example, the surface coating can comprise a material selected from the group consisting of bismuth, tin, gold, palladium, platinum, silver and copper. Preferably, the non-continuous surface coating 12 comprises material selected from the group consisting of bismuth, copper and tin, or combinations thereof, and most preferably, the coating comprises copper.
The non-continuous surface coating 12 typically has a thickness no less than about 1.2 nanometers, with a preferred thickness no less than about 4 nanometers. It should be recognized, however, that any minimum thickness of non-continuous surface coating which provides adequate lead coverage over the reasonable lifetime of the fixture at an economical cost is acceptable. In a preferred embodiment of the present invention the non-continuous surface coating 12 is comprised of bismuth or copper with a thickness no less than about 4 nanometers.
In another embodiment of the apparatus of the present invention, the solid body piece 2 of the apparatus comprises a perimeter portion 14 which includes the conduit surface 4 and an interior portion 16 which is integral with the perimeter portion 14. The interior portion 16 does not include the conduit surface 4. In this embodiment, the interior portion 16 of the solid body piece 2 typically has a lower concentration of coating material than the perimeter portion 14. Thus, the coating material is not uniformly distributed throughout the solid body piece 2, because typically the coating material is applied directly to the conduit surface 4. In another embodiment, the interior portion 16 of the body piece is substantially free of coating material.
The perimeter portion 14 of the apparatus includes the conduit surface 4 and extends from the conduit surface 4 into the solid body piece 2 a distance less than about 100 microns below the conduit surface 4, and more preferably extends into the body piece a distance less than about 50 microns. Thus, it should be understood that the coating material is not only on the conduit surface 4, but can also extend into the perimeter portion 14 of the apparatus some measurable distance depending on the method of application of the coating material to the apparatus. Furthermore, when an alloy is formed after the second solid phase dispersoids (generally lead) are exposed to a metal solution, the newly formed alloy may extend into the perimeter portion 14 a more extensive distance.
The present invention also includes as another embodiment an article useful for fluid storage and transportation. This article may be used as a pipe, faucet, valve, pump or other plumbing fixture or device for fluid storage and transportation. The article includes an interior portion 16 having no surface exposed to the water or other fluid being stored or transported throughout the article. The interior portion 16 has a metal matrix typically comprising greater than about 50 weight percent Cu, more preferably greater than about 53.5 weight percent Cu, and even more preferably greater than about 60 percent Cu. Other metals comprising lead, tin, iron, silver, palladium, platinum, zinc and bismuth may make up the remainder of the metal matrix of the interior portion 16, depending on the alloy. The interior portion 16 composition will usually comprise between about 1 and about 10 weight percent lead. Lead is typically present as a dispersed solid phase in the matrix of the interior portion 16.
The interior portion 16 is integral to and adjacent to a perimeter portion 14, which has an exposed surface that may be in contact with a fluid being transported or held within the article. For example, the exposed surface of the perimeter portion 14 would be actually wetted by the fluid. The perimeter portion 14 includes dispersoids of lead in a metal matrix which typically comprises greater than about 50 weight percent of copper. Other metals such as lead, zinc, tin and iron may additionally be included in the metal matrix in the form of a copper alloy.
The article of the present invention further includes a coating or lead leach inhibitor comprising a metal coating material in the perimeter portion 14, the coating having both a top side and bottom side. The top side of the coating forms part of the exposed conduit surface 4 while the bottom side is adjacent and overlaps at least one lead dispersoid in the perimeter portion 14. The coating thus substantially physically separates any such lead dispersoids from the exposure to water. This separation effectively prevents lead from leaching into water stored or carried in the article, since the lead dispersoids are not in substantial contact with water at the exposed surface. In a preferred embodiment, the coating material substantially physically separates the coated lead dispersoids for the reasonable expected lifetime of the apparatus.
In a further aspect of the invention, the coating of the lead dispersoids can be non-continuous across the exposed conduit surface 4. Thus, the coating is substantially consistent with the random number and pattern of lead dispersoids which are at the exposed surface. These separate occurrences of coating material are adjacent to a corresponding lead dispersoid in the perimeter portion 14 of the article, and substantially physically separate the corresponding adjacent lead dispersoid from the exposed conduit surface 4. As referenced above, the non-continuous coating preferably covers a substantial portion of the lead dispersoids.
Another embodiment of the present invention is a copper-based material. In a preferred embodiment, the composition comprises greater than about 50 weight percent copper, from about 1 weight percent to about 10 weight percent lead, and up to about 0.005 weight percent of a lead leach inhibitor metal. The lead leach inhibitor metal is typically a metal which is more electropositive than lead and preferably is selected from the group consisting of bismuth, tin, gold, palladium, platinum, silver and combinations thereof. More preferably the lead leach inhibitor metal is bismuth.
In a preferred embodiment of the composition, the copper-based metal composition comprises from about 7 weight percent to about 41 weight percent zinc. In a further embodiment, the copper-based metal composition comprises from about 0.2 to about 0.6 weight percent tin.
Another embodiment of the present invention is a method for preparing the surface of a copper containing material to impede the leaching of lead into water or other fluids. The article may be, for instance a plumbing apparatus which defines a fluid conduit volume 6 for storing or directing the flow of fluids through the apparatus. The plumbing apparatus may include, but is not limited to, pipes, valves, faucets, fittings, and other fixtures commonly known in the art. The composition and structural aspects of the article, which typically includes copper, are the same as that of the apparatus and articles, as broadly described above, but without the coating material or lead leach inhibitor.
The process includes providing the article and covering at least a portion of the lead in the plurality of dispersoids with a non-continuous surface coating phase 12. Thus, the method can include preferentially covering the dispersoids and leaving the continuous phase at the exposed conduit surface 4 of the article substantially uncovered by the coating phase. This method of selectively covering substantially reduces the amount and cost of coating material required to effectively coat the lead dispersoids exposed on the exposed surface as compared to a continuous coating process. For example, in a continuous coating process, the entire surface exposed to fluid is coated, including both the lead dispersoids and non-lead alloys. This continuous coating may be more expensive since a large non-lead surface area is coated unnecessarily. In a preferred embodiment of the invention, typically at least about 90% of the lead dispersoids present at the exposed surface are covered, more preferably about 95% and most preferably 99%. Further, the continuous phase of the exposed surface should remain substantially uncovered with no more than about 20% covered by the coating phase, more preferably less than about 10% covered by the coating phase, and most preferably less than about 1% covered by the coating phase.
The step of covering the dispersoids can comprise removing a layer of a portion of the plurality of dispersoids from the exposed conduit surface 4 to a depth extending into the material and below the exposed surface. For example, the step of removing can be a chemical substitution reaction to substitute a layer of the coating material, such as bismuth, for the layer of lead from an exposed dispersoid.
The layer of lead dispersoids removed typically extends a depth of about 10 microns from the exposed conduit surface 4 into the solid continuous phase, and more preferably about 5 microns. As the layer of a portion of the plurality of dispersoids is removed, at least a portion of the removed layer is replaced with the coating material. The non-continuous coating phase is typically comprised of bismuth, tin, gold, palladium, platinum, silver, or combinations thereof. Preferably, the coating material is comprised of bismuth.
In a preferred embodiment of the present method, the step of covering typically comprises contacting the clean, exposed conduit surface 4 of the material with a solution having dissolved therein a metal selected from the group consisting of bismuth, tin, gold, palladium, platinum or silver and combinations thereof. The concentration of the metal in solution will depend upon the choice of salts and is typically between about 0.25 g/l to 2.0 g/l, and more preferably between about 1.0 g/l and 1.5 g/l. The metal is typically provided in the solution in the form of a nitrate, sulfate or other soluble salt.
The article can be treated to cover the article with a coating phase by immersion in the solution for a sufficient time to adequately coat the article. It will be noted that the process is most efficiently conducted by minimizing the amount of time the article is in contact with the solution. By treating the article in a controlled manufacturing environment, parameters such as the solution concentration levels, temperature, and length of exposure to the article can be closely monitored and controlled. Thus, there is a significant advantage to utilize the disclosed method in a controlled environment as opposed to attempting to coat the articles after installation, where other chemicals and contaminants may be present in the potable water system.
The temperature of the treating solution is typically about 60° C., although the temperature of the solution can range from about 15° C. to just below the boiling point of the solution. Wide variations in the temperature of the treating solution during treatment are unfavorable, however.
By use of the apparatus, articles or methods of the present invention, the leaching of lead from plumbing fixtures into potable water systems is significantly reduced. The effectiveness of the present invention can be quantitatively measured in various ways. For example, as noted above, the percent coverage by a coating material or lead leach inhibitor of lead dispersoids exposed on the surface of a fluid conduit can be measured, for example by electron microscopic techniques. In addition, the effectiveness of the present invention in reduction of lead leaching into water can be quantitatively measured by tests which measure the amount of lead in water which has been allowed to stand in contact with a fixture under standardized conditions. For example, one standardized procedure has been established by the National Sanitation Foundation and is known as the National Sanitation Foundation 61 ("NSF-61") procedures. More specifically, Section 9 of the NSF-61 publication discusses the procedure for testing mechanical plumbing devices and components.
The NSF-61 standardized procedure requires the triplicate testing of mechanical plumbing fixtures, wherein samples are rinsed with tap water at room temperatures, then filled with water at various temperatures for periods of time up to 90 days. The contaminant level of lead which has leached into the water from the fixture is then quantitatively measured to gauge the leach resistance characteristics of the particular plumbing apparatus or fixture. This procedure is discussed in detail below in the Example section.
As an example of the effectiveness of the disclosed invention, untreated wrought brass alloys normally obtain a NSF-61 score of about 10 micrograms/liter when the alloy is exposed to water for a period of 1 day. Thereafter, the concentrations of lead fell within the range of 3-6 micrograms/liter during subsequent days of testing. However, after treating these alloys by exposing the second solid phase of lead dispersoids 10 with a lead leach inhibitor as described herein for 30 minutes, a NSF-61 score typically between about 1-2.5 micrograms/liter was obtained after exposing the fixture to water for a 1 day period. The lead concentrations fell to less than 1 microgram/liter during each of the subsequent days of testing. Typically, after treatment of copper-containing fixtures by the present invention, lead leaching under standardized conditions can be reduced by about 80 percent, more preferably by about 90 percent and more preferably by about 95 percent.
Similarly, typical NSF-61 scores for untreated cast brass ranges from about 50-55 micrograms/liter after exposure to water for 1 day, declining to about 38 micrograms/liter on day 2, and ranging from about 13-25 micrograms/liter for subsequent days of testing. After treatment of these cast brass alloys in a lead leach inhibitor for 30 minutes, a NSF-61 score of less than about 6 micrograms/liter is obtained after exposure to water for 1 day, and less than 2 micrograms/liter in each of the subsequent days. Typically, by treating cast copper-containing brass fixtures by the present invention, lead leaching under standardized conditions can be reduced by about 80 percent, more preferably by about 90 percent and more preferably by about 95 percent.
The following experimental results are provided for purposes of illustration and are not intended to limit the scope of the invention.
EXAMPLES
Example 1
This example illustrates the treatment of various plumbing fixtures according to the present invention. These treatments were conducted using four types of wrought and cast brass components commonly used in plumbing fixtures.
The first brass component was a single handle kitchen ("SHK") specimen containing both wrought and cast components. The second and third components were comprised of wrought brass and included a single handle lavatory ("SHL") and double handle lavatory specimen ("DHL"). The fourth component was a wide spout ("WSP") comprised of cast brass.
The nominal composition of the wrought brass in the tested specimens was comprised of 60.0-63.0 weight percent copper, 2.5-3.7 weight percent lead and the remainder zinc. The nominal composition of the cast brass in the tested specimens was comprised of 78.0-82.0 weight percent copper, 2.3-3.5 weight percent tin, 6.0-8.0 weight percent lead, 7.0-10.0 weight percent zinc, 0.4 weight percent iron, 0.25 weight percent antimony, 1.0 weight percent nickel, 0.08 weight percent sulfur, 0.02 weight percent phosphorous, 0.005 weight percent aluminum and 0.005 weight percent silicon.
Each type of fixture included three samples which were treated according to the embodiments of the present invention and subsequently tested according to NSF-61 standards as described in Example 2.
The fixtures were prepared for treatment by rinsing each component with acetone, followed by immersion in 0.1 normal (N) nitric acid (HNO 3 ) for 30 seconds. The fixtures were subsequently rinsed with deionized water and allowed to air dry prior to testing.
Each set of three fixtures was then immersed for a 30 minute period in a solution prepared by adding 4.64 g/l of bismuth nitrate (Bi(NO 3 ) 3 5H 2 O) and 15 g/l of sodium chloride (NaCl). The solution was prepared by dissolving the salt in an agitated volume of deionized water, maintained at 60° C.
The process tank consisted of a seven gallon polyvinyl pail fitted with an agitator and baffles. The bismuth nitrate and sodium chloride solution was circulated by allowing the process tank to overflow into a reservoir, then pumping fluid from the reservoir back into the process tank. The treatment sequence of the fixtures was as follows: SHL, DHL, WSP and SHK. After the treatment of the HL fixture, two hundred and fifty milliliters (ml) of the bismuth nitrate solution were added to the system to insure against bismuth depletion prior to the treatment of the HHL fixture. Likewise, an additional two hundred and fifty milliliters were added before the treatment of the WSP and KSP fixture treatments, as was 181 ml before the HK fixture treatment to ensure against bismuth depletion. Treatment solution samples were drawn from the virgin treatment solution and after the treatment of each fixture to determine the amount of lead which leached from the fixture into the treatment solution. The results of these tests are tabulated below in Table 1.
TABLE 1______________________________________Residual Accumulation of Lead in Solution SOLUTION DESCRIPTION Pb Content, g/l______________________________________Virgin Solution 0.001 Solution From SHL Fixture 0.001 Solution From DHL Fixture 0.005 Solution from WSP Fixture 0.008 Solution from SHK Fixture 0.047______________________________________
After removing the test fixtures from the bismuth nitrate solution, the specimens were thoroughly rinsed with deionized water and allowed to air dry before being subjected to leachate testing. The lead leachate testing was performed using the standardized NSF-61 leaching tests as discussed below.
Example 2
This example illustrates The NSF-61 testing procedure performed on the fixtures following treatment. This procedure requires that the fixtures are flushed with tap water for 15 minutes, then rinsed with deionized water. The fixtures are then prepared for testing by rinsing with 3 volumes of an extraction water having a pH of 8.0±0.5, alkalinity of 500 ppm, dissolved inorganic carbonate of 122 ppm and 2 ppm of free chlorine in reagent water.
Following the aforementioned fixture preparation, the fixtures are exposed to extraction water at either a cold temperature or hot temperature, depending on the intended use of the fixture. The cold temperature is 23±2° C. (73.4±3.6° F.), while the hot temperature is 60±2° C. (140±3.6° F.) for domestic use or 82±2° C. (180±3.6° F.) for commercial use. For the purposes of this test, each fixture treated was tested with cold extraction water.
On day 1, the fixtures are filled with the extraction water for approximately 2 hours, then the water is dumped and the process repeated for a total of 4 exposures. After dumping the fourth water sample, the fixture is again filled with extraction water and held in the fixture for approximately 16 hours.
On day 2, the water samples are collected and acidified and then tested for lead content in accordance with NSF-61 procedures. Day 1 procedures are then repeated. For the duration of the test, day 1 and day 2 procedures are repeated. The tests may be extended with an exposure sequence of up to 90 days, although only the contaminant levels present in the overnight samples are used to evaluate lead-leaching.
The results of the NSF-61 leaching tests can be seen in FIGS. 3-6, which depict the concentrations of lead leached into the water in micrograms/liter on the Y axis plotted against the days of water exposure on the X axis. Although a total of five fixtures were treated and subsequently tested in accordance with NSF-61 procedures, only four figures were generated since the SHK and KSP fixtures were assembled prior to NSF-61 leaching tests. As the figures depict, the copper alloy specimens treated by the bismuth nitrate solution are compared with non-treated samples.
As the test data indicates, the amount of lead leaching into water from copper-alloy fixtures is significantly reduced following the bismuth treatment. Typically, the amount of lead leaching into water is reduced about 90 percent, and more preferably reduced about 95 percent.
While the invention has been described in combination with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations as fall within the spirit and broad scope of the appended claims.
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A copper alloy plumbing fixture containing interdispersed lead particles coated non-continuously on a water contact surface to resist the leaching of lead into potable water systems. The leach resistant fixture is prepared by immersing conventional copper alloys in a bismuth nitrate solution, selectively and non-continuously coating the lead dispersoid particles on the water contact surface with bismuth, tin or copper.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is in the broad field of information technology, and pertains more particularly to providing information to customers shopping in brick-and-mortar retail establishments, the information pertaining to products and services for sale.
2. Description of Related Art
As information proliferates at an ever-increasing pace, one of the greatest areas of need in information technology is in the area of ways to find needed information, as described briefly above, and this is an area served in one important aspect by search engines and associated systems that enable users to find information, such as in web pages in the Internet network. Search systems and search engines are a particular focus in embodiments of the present invention.
A goal of most search engines is to make it possible for users to easily find and/or access relevant data on the world wide web (WWW). Relevance is always of great importance, and is perhaps best judged by the person looking for the information.
A key subsystem of most known search engines is a system for crawling the Web and collecting information, known in the art as a Web crawler. Without regularly crawling the Web to update the information there available, a search engine will rapidly become outdated and irrelevant. Further the Web crawling subsystems are needed to be efficient and to operate on a relatively large scale. Ideally such search engines should operate without disrupting the Web itself or the sites (pages) that are crawled. Many innovations in this area are sought, including methods for checking pages for updates including soliciting involvement from content owners in notifying the search engine enterprises of relevant changes, methods for caching data and parallelizing the process of crawling, and more. Typically the result of the Web crawling is a database of Web content that may span more than 10 billion Web pages, all or part of the content of which may be collected and archived by the search engine.
Pages collected by a crawler subsystem are analyzed in a variety of ways well known in the art to create an index of page identifiers and links to the pages. Such a search index serves much the same purpose as the index of a book; for any term or terms entered as search criteria, a list of pages, with links to those pages, is returned. More broadly, a goal of the Web search index is to return a list of pages when a user enters a search query such as, for example, “dramatic innovations”. Typically pages returned are pages in which the terms are simply present, although it might be preferable to also return pages that may not contain the search terms, but may nevertheless be relevant to the needs of the person who enters the search query. For instance, in response to a search query stated as “dramatic innovations”, the search engine might return links to the history of the Wright Brothers' airplane innovation, even though the history may not comprise the specific term. Relevance is of great importance. A Web crawler is a means to an end in search. An index built from information garnered by a crawler is one of the core elements of a search system.
An index, however, is of little use unless users can use it to search the Web, so a user interface is needed. In such an interface, typically operated from an application known in the art as a browser, the user enters a search query and typically presses Enter. The query is sent, via the Internet network, to the enterprise hosting the search service, of which several major enterprises are well-known. The search engine then uses the present index (the index may change over time as Web crawling progresses) to make a list of Web pages that match the search query. Again, a key challenge is to provide that the most relevant results for this particular user are displayed at or near the top of the list.
The known need for relevance has been a very important motivator in developing a page ranking algorithm. A page ranking algorithm (or node ranking algorithm) is a ranking subsystem, which determines the order of display of the search results. The criticality of this function is that a person searching is going to look at the top-listed pages, rather than digging down to buried information, especially if it is clear that there is a ranking system meant to present more relevant pages nearer the top. Additionally, if the relevance determinations are considered authoritative by many users, the tendency to only look at highly-ranked search results becomes more pronounced, making the impact of the relevance scores very large.
One of the most effective page ranking algorithms in the art at the time of filing the present application is the PageRank algorithm of Google™, Incorporated. The effectiveness of the PageRank algorithm is related in the current art, at least in part, to a structural graph and a matrix computation. The structural graph is a representation of the structure of linkages between pages in the form of a “graph”, as is well known in the art of graph theory. It is well known that, although there are additions and variations, the PageRank system basically works by giving indexed pages a score that is calculated by adding up the number of links that point to the page to be ranked from other pages, and weighting this score based on similar scores calculated for the linking pages. That is, if there are five pages that link to a page to be ranked, but no other page links to the five pages, then the PageRank for that page will be much lower than for a page that has five in-links that each come from highly ranked linking pages (these in turn are highly ranked because many pages link to them, and so on). It is clear that the calculation for page ranking involves relatively complex mathematics, since the score of one page is determined by the scores of linking pages, whose scores are in turn determined by the scores of their linking pages, whose scores are determined by the scores of their linking pages, and so on at least to some pre-determined depth.
From this description it becomes clear why a graph is needed—in current art it is necessary to understand the structure of linkages that connect Web pages in order to perform the calculation, which is based on these links.
In a somewhat abstract sense one may visualize the WWW as a vast array of dots (points, or nodes), each of which represents a Web page connected in the Internet network. To represent nearly all of the existing pages at any one point in time would need perhaps 10 10 points. Each of the pages is, of course, a collection of code, typically in HTML format (or one of its well-known extensions such as DHTML, Cascading Style Sheets, etc.), that defines page content, which may be presented by the page through a user's computer typically using a web browser, which may include text, graphics, audible music and voice, video, and more. Another component of almost any page in the Web is at least one link for initiating a transfer to a different page, or in some cases more recently, initiating a transfer of code and data to a user's computer for some purpose, without requiring transition to a different page.
FIG. 1 is a very simple illustration of the one-dot-for-a-page illustration or view of the WWW introduced above. Only five page-representative dots are shown, as sufficient for the purpose, these being pages 101 through 105 . A link for the present purpose may be considered the well-known navigational element in the display of a web page for which the cursor typically turns into a hand with a mouseover, and for which clicking-on asserts an address (such as a Universal resource locator URL), which takes the user to another Web page. The link area in a display can be an icon, text, or even an animated figure.
In FIG. 1 the links are shown as arrows. Note that page 105 has links to all of pages 101 through 104 , none of which link back to page 105 . Links 101 through 104 each have one link to another one of the pages. It is helpful to consider that, although a link is a link, there is a difference in links from the view of the page itself. From the viewpoint of the page, a link may be an out-link (an outgoing link to another page) or an in-link to the instant page from another page. Consider, for example, page 103 , which has two in-links, one each from pages 102 and 105 , and one out-link to page 104 . Consider also that not all links to or from these five pages may be shown, because a very limited subset of pages is illustrated. Page 105 , for example, may have several in-links from pages not shown. For the purpose of a state-of-the-art page ranking system, it is the in-links that are typically most important.
In the current art, according to all of the information known to the inventor, the PageRank algorithm and all other search ranking systems are based on the static link structure of the World Wide Web, as briefly described above. The random page graph shown, with the links shown, however, is not a good mathematical model for the purpose. For better computation efficiency a better model (graph) is shown in FIG. 2 . The inventor terms this graph a Structural Web Graph (SWG). It should be understood as well, at the outset, that a SWG may only ever show a subset of the WWW structure, and the size and structure of the WWW is in constant flux. In this SWG concept each Web page in the WWW (or a subset) is still a point, but the pages are not illustrated in random space, but in rows and columns. So in the SWG of FIG. 2 there are five rows, each identified by the page association, and also five columns, each also identified by the same page association. By using the same five pages as in FIG. 1 , a six-by-six matrix results, considering the five pages and the necessity of having an origin to the matrix. If the matrix were defined for essentially all Web pages, it would be as big as 10 10 rows and 10 10 columns.
In FIG. 2 the rows and columns are shown with identifiers for the pages associated with each row and column. In a workable, mathematical definition to be machine-manipulated, the rows and columns would simply be identified in a data convention; the matrix might never be displayed.
The matrix as shown in FIG. 2 creates a row-column intersection for each page represented with every other page represented in the matrix. This is a basis of its utility. There is also an intersection for each page with itself, which has no utility for the present purpose, and these intersections have been marked in FIG. 2 by an X.
Now consider, as an example of the utility of the SWG, which is well-known in the art, the following illustration. The intersection of the row for page 104 with the column for page 102 , which is labeled in FIG. 2 as element 201 , presents an opportunity to represent a particular relationship between pages 104 and 102 , which may be shown in a number of ways, one of which is simply a value placed at the intersection. In this case the value, by convention, is to represent whether there is an in-link from 102 to 104 . Since there is not, the value is zero.
It should be recognized that at an intersection the convention of labeling the intersection with a value based on the existence of a link from the page represented by the column to the page represented by the row is arbitrary; one could as easily have chosen a convention of in which the element 201 would represent a link from page 104 to page 102 , and would thus still be set to zero (since the path from 102 to page 104 is indirect; there is no link from 102 to 104 in FIG. 1 ). A primary function of the SWG utilized in most search engines in the art is to capture the plurality of link relationships between pages in a computationally useful way. In-links are the most useful, since they represent the choices of web page designers to link from the pages they are designing to other web pages. It will be appreciated that pages that are heavily linked to are likely to be more relevant, whereas pages with many out-links may or may not be relevant (the designers of these pages being free to add more out-links, since they control the content of their own pages, they would be able to easily inflate the relevance scores of their pages). A web crawler may garner this information by crawling each web page and noting the links from that page to other pages; in the case of element 201 of FIG. 2 , the crawler when reaching page 104 would have noted no link to page 102 and thus marked a zero in element 201 , as shown in FIG. 2 .
Crawling FIG. 1 provides information that page 104 is linked (has in in-link) from page 103 , but not from page 102 . Therefore the value at 201 is zero, but the value at the intersection of the row for 104 and the column for page 103 is 1. By the same process, crawling FIG. 1 the values at all of the other intersections are determined, and have been indicated in FIG. 2 .
In this particular example, the values are one or zero, which may be convenient for computer simulation and manipulation. Of course other values may be assigned, and in the real world values may be weighted by a number of other considerations, not just whether there is an in-link from the secondary to the primary page. For example, it is common in the art to normalize the values of the Structural Web Graph so that the sum of all of the values in the Structural Web Graph is equal to one, making each value equal to a probability that a random web surfer might make a particular transition from one page to the next (and, continuing this convention, the sum of the values of a column represent the probability that a random web surfer will, after a long session, find herself on the page represented by the column).
A page ranking algorithm, which may take many forms, might, in a primitive form, just consider the SWG once to rank a page. The value at each intersection may be one or zero, but there is a possibility of a 1 for a primary page at each intersection for another page. For page 104 the sum of values at intersections across the row is two. So page 104 may be given a rank value of two, since two pages ( 103 and 105 ) link into page 104 . The rank value for page 105 would be the sum for the row for page 105 , or zero, since no pages link in to page 105 . In FIG. 2 the sum for every row but 105 is two, so the pages other than 105 may have equal rank, or there may be a tie-breaker in the algorithm. In a real-world case there are many, many more intersections to consider, and one page may be seen to be linked to from dozens or hundreds of other pages.
In a more sophisticated situation, the page ranking algorithm may first consider the row sum for a page, and then look at the in-links for each of the secondary pages at the positive intersections; that is, an answer to the question: How many pages link in to each page that links directly to the page being ranked, which may be extended to how many (and which ones) link to each page that links to the instant page. Now the value for ranking becomes more realistic and granular, but is still limited to the structural links designed into the pages of the Web. This approach is the basis of the well-known PageRank algorithm pioneered by Google™; the heuristic that drove this step was that links represented authorities, and the relative in-link density of a given authority provides a good indication of the importance of that authority. So at least a nominal relevancy was indicated.
In summary, a search engine in the present art comprises a few key elements, such as a Web crawler to discover and gather information about Web pages, an index of Web pages composed of information garnered by the crawler, a search function that determines which of the pages in the index to present to a viewer, based at least in part on the search query entered by the browsing person, a Structural Web Graph based also on the information retrieved by the crawler, and a PageRank algorithm that uses the Structural Web Graph and values assigned in the graph to give each page a unique PageRank score, for ordering the displayed return of the pages. U.S. Pat. No. 6,285,999 issued to Lawrence Page describes and claims such a PageRank system. U.S. Pat. No. 6,285,999 is incorporated by reference in the present application.
Bearing in mind many of the difficulties attendant to search technology, many of which are described above, it is clear that provision of correct and expedient search criteria by individuals seeking information from networked collections is a serious difficulty, and returning information ranked for relevancy is also a distinct challenge for conventional search systems, such as those provided by Mozilla™, Google™ and Yahoo™. Having considered all of these difficulties the inventor believes that what is clearly needed is an intermediary system and methods that will provide greatly enhanced search capability for individuals in dealing with more conventional search services.
BRIEF SUMMARY OF THE INVENTION
The inventors in the present case, having determined that there are serious problems in conventional search systems and practice, have developed a unique compound system to produce far better results. In one embodiment a search service is provided, comprising a network-connected server, a data repository coupled to the first server, and software resident in the data repository and executing on the first server. The service, through the software, presents an interactive interface to a user, determines, through iterative interaction with the user a purpose for a search, develops search criteria for the search, enters the criteria to one or more standard search engines accessible through the network, and collects results of the search on behalf of the user.
In another aspect of the invention a method for searching is provided, comprising steps of (a) presenting, by an interactive search service executing on a network-connected server executing software from a coupled data repository, an interactive interface to a user; (b) determining by the service, through iterative interaction with the user a purpose for a search; (c) developing search criteria; (d) entering the developed criteria to one or more standard search engines connected to the network; and (e) collecting results of the search on behalf of the user.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a simple representation of page nodes in an Internet network.
FIG. 2 is an illustration of a Structural Web Graph.
FIG. 3 is a diagram depicting a compound searching system in an embodiment of the present invention.
FIG. 4 is a process flow diagram depicting a process in an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In yet another aspect of the present invention methods and systems are provided for enhancing search capabilities for individuals seeking information from networked collections like the WWW.
FIG. 3 is a diagram depicting architecture pertinent to an overall searching system in an embodiment of the present invention. Mobile appliance 301 represents mobile appliances of all sorts, such as many cellular telephones, the Apple™ iPhone™, the Blackberry™ device, other personal digital assistants, and the like that have ability to access a wide-area network (WAN) 303 like the well-known Internet network, and from which searches might be initiated through commercially available search systems. In this specification the Internet network is used in description of embodiments, but is not necessarily the only network useful in embodiments of the invention. As is common in the art, appliances 301 are wirelessly enabled, and communicate wirelessly via base stations, such as station 302 . In some cases in the art stations are arranged in a hierarchical manner, and there are a variety of architectures through which signals from and to the mobile appliances may be transmitted. The simple diagram shown is meant to represent all such architectures.
A laptop computer 314 is illustrated as connecting also wirelessly through base station 102 , using what is termed in the art an air card, which accomplishes Internet activity through a cellular telephone network. The laptop might connect also via WiFi networks, such as those offered by Starbucks™ and many others. The laptop might also connect directly by modem, such as by DSL through a landline telephone system.
A desktop computer 315 is illustrated connecting by landline through an Internet Service Provider 316 . The desktop might connect in other ways as well.
The illustration of mobile appliance 301 , laptop computer 314 and desktop computer 315 , all connecting in one manner or another to line 304 , which is meant to represent all of the interconnections in the Internet network, is to represent all of the ways that computing devices might connect to the Internet and other wide-area networks.
Internet-connected server 305 executing software 306 from an associated data repository 309 in an embodiment of the invention provides a first stage in a two (or more) stage search process in an embodiment of the invention. Internet-connected servers 307 executing software 308 from an associated data repository 310 , and 311 executing software 312 from a data repository 313 represent commercially available, and publically available search services, such as Mozilla™, Google™ and Yahoo™. In various embodiments of the invention, persons operating devices 301 , 314 or 315 connect to server 305 , which provides a unique service in search, as is described in enabling detail below.
FIG. 4 is a flow chart illustrating a search procedure for retrieving information from the Internet network, accomplished by a person operating one of devices 301 , 314 or 315 . At a first step 401 the user connects to a web page of the service of the invention provided by server 305 executing software 306 . Typically the service will present a “welcome” page to the user, who, in a preferred embodiment, will be a client of the service. The service will thus have a profile for the client stored in data repository 309 , and will recognize the client and address the client by name (or alias).
A purpose of the service is to provide a substantially richer and more detailed service for the client to address the many problems of the standard search services. One of the problems described above is the problem of the nature of search criteria, and the difficulty, for most people, of immediately coming up with useful words or phrases to enter as a search criteria in a standard search engine. Typically, in a standard search engine interactive page, there is a single entry window where a user may enter a word, a phrase, or a combination of words and phrases with logical operators.
In an embodiment of the present invention a user is directed to describe to the service the nature of the information desired, in more detail than in conventional search services, and in context, indicated as step 402 in FIG. 4 . In one embodiment the user is prompted with specific questions to elicit and refine the user's intent. The interface will typically be a text entry window, but may be voice enabled in some embodiments, and there may be multiple choice questions to be answered. In this phase, the service determines the exact nature of the search to be conducted.
As an example of the process of the service in determining and refining the nature of the search the user may first enter a paragraph (step 403 ), perhaps as follows: “I want information about Abraham Lincoln, and particularly details of the assassination of Lincoln, and what became of the assassins.” Such an entry would never suit a standard search engine for criteria. After the user's entry, the service will analyze, standardize and summarize the input, and in some instances provide a feedback to the user in one or more steps. The service might post to the user: “We determine the main focus is Abraham Lincoln” Yes/No. “A secondary focus is his assassination” Yes/No. “You want to know who were the assassins” Yes/No. The Yes/No combinations are interactive, and the user is prompted to select for each level. In this case the user would select Yes, Yes, No. The service then makes a more determined effort for the last portion, and returns “You want to know the further history of the assassins” Yes/No. The user may be satisfied with this, and indicate yes.
Now the service, at step 404 , using the determined nature of the search, together with knowledge of standard search services and how they work, and together also with other knowledge about the user, develops specific search criteria to be entered to one or more standard search services. The service may, for example, determine that the search is a simple matter, and will require only a simple search on Google™, and will postulate search criteria for Google™. It may be that only one standard search engine may be used, but it will generally be the case that more than one search will be made. The service may postulate, for example, three sets of search criteria.
At step 405 the service opens three Google™ searches, one for each of the criteria sets determined to be best for the nature of the search determined, causes the three searches to be initiated, resulting in three “page-ranked” sets of results being returned to the service at step 406 . At step 407 the service processes the results. The processing may simply be a selection and re-ranking of pages returned to the service, which may be based on client transaction history and other criteria, such as keywords in titles of the pages returned, and in most cases the listing will be truncated to a manageable number of pages. In a more robust embodiment, content of pages will be selected and “lifted” by the service to become a part of a composite report to the client. In this embodiment the client may get, at step 408 , both ranked or re-ranked page titles (of course interactive, as in a standard search engine), but may also get a composite report, prepared by context analysis and summarization techniques, which, hopefully, will go a long way to present exactly what the client asked for: The story of the assassination, and what happened afterward.
As a further service to the user/client the service may provide for each client a specific portion of data repository 309 where a history of the client's searches may be recorded, and may be searchable in future by the client. The service would provide periodically to the client a chronological outline, and also an interactive search interface where the client may search his/her own past searches, and may reorganize and present the data in and from different searches in different ways.
In some embodiments of the invention the service use several standard search engines, and may develop in an interactive process with the client a range of search criteria for each, and may narrow and refine searches interactively with the client until the client is satisfied. So the service in some embodiments is a service that acts between a client and standard search engines, aiding the client in doing the best possible and most thorough searches for what the client really wants to find out, and that also interacts with the client as the searches develop, so the client can further refine a guide the search. The service in some embodiments also analyzes, standardizes and summarizes information in returned pages, and prepares in many embodiments a comprehensive search report based on the nature of the original search. For example, the unique service of the invention may summarize all of the discovered information for the person who wants the information about Abraham Lincoln as described above, in a normalized and standardized report, rather than only returning web links for ranked pages, as in commercial, conventional search facilities. In one embodiment the unique service of the invention may also provide a mapping of where the information was found; that is, a summary as well as the pages from which the info for the summary was taken, and indication of where in the pages the info was found.
In the case of mobile appliances 301 , another piece of information involved in the overall interactive search will be the location of the mobile appliance, determined in many instances by a global positioning system (GPS) integrated into the mobile appliance. This information may be valuable in the step of determining the nature of the search, and also in what material might be returned and stored for the client.
It will be apparent to the skilled artisan that the embodiments and examples described above are not the only embodiments of the invention, and that many alterations and amendments may be made without departing from the spirit and scope of the invention. The invention is therefore limited only by the claims that follow.
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A search service includes a network-connected server, a data repository coupled to the first server, and software resident in the data repository and executing on the first server. The service, through the software, presents an interactive interface to a user, determines, through iterative interaction with the user a purpose for a search, develops search criteria for the search, enters the criteria to one or more standard search engines accessible through the network, and collects results of the search on behalf of the user.
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FIELD OF THE INVENTION
This invention relates generally to devices for contacting particulate materials with fluids. More specifically, the invention relates to the design of the internals of reactors for fluid-particle contact.
GENERAL BACKGROUND AND RELATED ART
Numerous processes use radial flow reactors to effect the contacting of particulate matter with a gaseous stream. These processes include hydrocarbon conversion, adsorption, and exhaust gas treatment. These reactors contain a vertically extending annular bed of particles through which the gases flow radially in an inward or outward direction. The annular bed is formed by an outer screen element located along the outer diameter of the particle bed and an inner screen element located along the inner diameter of the particle bed. The outer screen element alternatively may comprise a series of closed conduits having an oblong cross-section that circles the outside of the particle bed and borders the inside of the particle containing vessel, such that the backs of the conduits will fit closely against the wall of the vessel and thereby minimize the volume between the back of the conduit and the vessel. An alternative design uses a section of profile wire or screen to form conduits positioned against the inner wall of a vessel. Such conduits have an inner wall joined to a pair of side wall portions, generally in a trapezoidal configuration.
However, the known art has failed to address issues of flow distribution and axial and radial stresses in a cost-effective way
SUMMARY OF THE INVENTION
A broad embodiment of the present invention provides an improved device for distributing fluid in a radial-flow direction through particles within a vertically extended vessel having a curved vessel wall, a fluid inlet and a fluid outlet, comprising a plurality of vertically extended cylinders arranged circumferentially about the interior of the vessel wall, each cylinder having a hollow interior and a multiplicity of cylinder perforations, and at least one end of each cylinder communicating with one of the fluid inlet and the fluid outlet; a particle-retaining outer conduit substantially parallel to the vessel wall and adjacent to the cylinders in the direction of the center of the reactor and having a multiplicity of conduit perforations; and a perforated central conduit located in the center of said vessel and communicating with the other of said fluid inlet and said fluid outlet that is not communicating with the cylinders.
In a more specific embodiment, the invention comprises an improved device for distributing fluid in a radial-flow direction through particles within a vertically extended vessel having a curved vessel wall, a fluid inlet and a fluid outlet, comprising a plurality of vertically extended cylinders arranged circumferentially about the interior of the vessel wall, each cylinder having a hollow interior and a multiplicity of cylinder perforations; and at least one end of each cylinder communicating with one of the fluid inlet and the fluid outlet; a plurality of panels, each defined by an arcuate section of a particle-retaining outer conduit having a multiplicity of conduit perforations and connected to a plurality portion of cylinders, which portion is fewer than the number of cylinders in the device, in the direction of the center of the reactor and substantially parallel to the vessel wall; and a perforated central conduit located in the center of said vessel and communicating with the other of said fluid inlet and said fluid outlet that is not communicating with the cylinders.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view of a single vertically extended cylinder.
FIG. 2 is a view of a panel of cylinders.
FIG. 3 is a cross-sectional view of a vessel, showing the placement of two panels of cylinders.
FIG. 4 is a view of a connector linking two panels of cylinders.
FIG. 5 shows alternative configurations for the end section of a panel
FIG. 6 is a schematic view of a stacked-reactor system.
FIG. 7 is a partial sectional view of the reactor of FIG. 6 .
DETAILED DESCRIPTION OF THE INVENTION
This invention is especially suitable to facilitate radial flow or cross flow through a bed of particles within a vessel, and can be applied to any fluid-particle contacting apparatus or process. The invention is particularly beneficial in processes where transient temperature gradients or temperature fluctuations are imposed on vessel internals, causing stresses on these internals and any catalyst particles used to effect a particular reaction. These stresses can impart both axial and radial forces on internal structures and catalyst and result from differences in thermal expansion and even steady-state operating temperatures among the materials within the reactor vessel.
The plurality of cylinders of the invention may be arranged in any configuration which is useful to distribute or collect fluids in order to effect the desired fluid-particle contact. Typically, the plurality of cylinders is arranged circumferentially inside the wall of a vessel to distribute fluids through a perforated outer conduit, across a catalyst retention space in a radial direction, and into a perforated central conduit located in the center of the vessel. In this arrangement, the cylinders communicate with the reactor inlet and the central conduit communicates with the reactor outlet. The number of cylinders in the plurality is defined by the circumference of the inner wall of the vessel, cross-sectional area for fluid flow, and size of the cylinders.
FIG. 1 shows a single vertically extended cylinder 10 . The cylinder of the present invention can have any curved bounding surface which is useful to effect the desired distribution or collection of fluids. For example, the cylinder may have an oblong cross-section. However, it is preferred that the cylinder has a substantially circular cross-section. The cylinder can be fabricated from any suitable material which can be perforated in a manner to effect the transfer of fluids. Preferably the cylinder comprises a perforated extended section of standard pipe. Alternatively, the cylinder can be fabricated from a single sheet of steel which is rolled into the desired shape and welded along a vertical joint. Either the pipe or the sheet comprises a multiplicity of perforations as is known in the art to enable egress or ingress of fluids; when perforated, this material is referred to as a “perforated-plate” or “punched-plate” cylinder. The perforations 12 can be of any size or orientation for effective distribution or collection of fluids while maintaining the structural integrity of the cylinder and also being small enough to contain the catalyst particles in the event that the primary catalyst containment of outer conduit 22 is breached, and preferably are oblong or slotted in shape.
FIG. 2 illustrates a panel 20 of cylinders, each of which is represented as 10 in FIG. 1 . The panel comprises a plurality 24 of cylinders enclosed in an arcuate section of outer conduit 22 which has been cut away partially in the drawing to show the location and orientation of the cylinders. The size of the arc of the panel is determined by the diameter of contained cylinders required for flow distribution as well as fabrication and maintenance considerations; although fabrication of the panel in situ (within the vessel) is within the scope of the invention, it is preferred that the panel would be fabricated outside the vessel and brought in via a vessel opening. The plurality of cylinders may be partially enclosed by the outer conduit 22 or may be totally enclosed in a panel comprising an enclosure conduit 26 , and optionally are attached to the conduit by, for example, welding. The outer conduit and optional enclosure conduit 26 in a panel are arcuate sections of conduits within the vessel which parallel the inner vessel wall at a distance sufficient to accommodate the cylinders and conduits. The outer conduit 22 comprises a multiplicity of perforations as is known in the art to enable passage of fluids and retain particles within a particle-retaining space, preferably as perforated-plate or punched-plate steel as described above; alternatively, profile wire as described in U.S. Pat. No. 5,366,704 may be used. The enclosure conduit 26 preferably is solid, but may be partially or totally perforated sheet to prevent dead spaces of fluid between the panel and the vessel. Preferably the perforations in the cylinder and in the conduit are oriented in opposite directions to avoid complete blockage of one layer (cylinder and/or conduit) of perforations by solid portions of the other layer. When the orientation is opposite for each layer it is not possible for one layer to completely block off the other, and the total open area can be calculated reliably without using some elaborate alignment scheme
FIG. 3 is a cross-sectional view of a vessel 30 , showing the placement of two panels 32 of cylinders as described in FIG. 2 around the inner wall of the vessel. The panels are shown without the optional enclosure conduit shown as 26 in FIG. 2 . The optional connector 34 linking the panels is further described in FIG. 4 . Of course, such panels would extend all around the inner periphery of the vessel and the optional connector would extend substantially along the entire length of each panel.
FIG. 4 is an expanded view of a connector linking two panels of cylinders. Vessel wall 30 and panel 32 relate to corresponding views in FIG. 3 ; in this illustration, the panel comprises the optional back shown as 26 in FIG. 2 . Connector 34 is a T-bar extending the length of the panels, and preferably is fabricated from the same steel as the panels. Coverplate 36 presses against the T-bar via notches 38 and may be welded in place; the coverplate prevents particles from entering the space between the panels. This system of connectors permits the panels to expand and contract with changes in temperature inside the vessel while maintaining the integrity of the device.
FIG. 5 shows alternative configurations for the end section of a panel of cylinders. For orientation of the end section with respect to the previous figures, the inner section adjacent to the catalyst bed of each alternative is designated as 22 to correspond to the same designation in FIG. 2 . The section paralleling the vessel wall is designated as 26 to correspond to the designation in FIG. 2 . Only options ( 1 ) and ( 2 ) represent an actual panel outer enclosure as shown in FIG. 2 , but the designation nevertheless orients the panel with respect to its placement in a reactor. Options ( 1 ) and ( 2 ) require the largest spacing between panels because the enclosed ends require space in order to be able to insert and remove an individual panel. Options ( 3 ) and ( 4 ) provide more maneuverability through partially rounded ends. Option ( 5 ), in which the outer cylinder forms a portion of the panel wall, affords the most maneuverability and thus the closest potential spacing.
The device and the resulting advantages in the collection or distribution of fluids can be readily appreciated from in the context of an apparatus and process for reforming hydrocarbons. The description of this invention in the limited context of a specific apparatus and process, is not meant to restrict the broad application of this invention to any specific apparatus or process for fluid solid contacting.
The catalytic reforming process is well known in the art. A hydrocarbon feedstock and a hydrogen-rich gas are preheated and charged to a reforming zone containing typically two to five reactors in series. The hydrocarbon feed stream that is charged to a reforming system comprises naphthenes and paraffins boiling within the gasoline range. The preferred class of feed streams includes straight-run naphthas, thermally or catalytically cracked naphthas, partially reformed naphthas, raffinates from aromatics extraction and the like. Usually such feedstocks have been hydrotreated to remove contaminants, especially sulfur and nitrogen. A gasoline-range charge stock may be a full-range naphtha having an initial boiling point from about 40° to about 70° C. and an end boiling point within the range from about 160° to about 220° C., or may be a selected fraction thereof.
Operating conditions used for reforming processes usually include an absolute pressure selected within the range from about 100 to about 7000 kPa, with the preferred absolute pressure being from about 350 to about 4250 kPa. Particularly good results are obtained at low pressure, namely an absolute pressure from about 350 to about 2500 kPa. Reforming conditions include a temperature in the range from about 315° to about 600° C. and preferably from about 425° to about 565° C. As is well known to those skilled in the reforming art, the initial selection of the temperature within this broad range is made primarily as a function of the desired octane of the product reformate, considering the characteristics of the charge stock and of the catalyst.
The reforming conditions in the present invention also typically include sufficient hydrogen to provide an amount from about 1 to about 20 moles of hydrogen per mole of hydrocarbon feed entering the reforming zone, with excellent results being obtained when about 2 to about 10 moles of hydrogen are used per mole of hydrocarbon feed likewise, the liquid hourly space velocity (LHSV) used in reforming is selected from the range from about 0.1 to about 10 hr −1 , with a value in the range from about 1 to about 5 hr −1 being preferred.
A multi-functional catalyst composite, which contains a metallic hydrogenation-dehydrogenation component on a porous inorganic oxide support providing acid sites for cracking and isomerization, is usually employed in catalytic reforming. Most reforming catalyst is in the form of spheres or cylinders having an average particle diameter or average cross-sectional diameter from about 1/16″ to about 3/16″. Catalyst composites comprising platinum on highly purified alumina or on zeolitic supports are particularly well known in the art. Metallic modifiers that improve product yields or catalyst life, such as rhenium, iridium, tin, and germanium, also may be incorporated into the catalyst.
The principal reactions that take place are the dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins, isomerization of paraffins and naphthenes, hydrocracking of paraffins to light hydrocarbons, and formation of coke which is deposited on the catalyst. Coke formation causing the catalyst to lose activity gradually over time requires regeneration and/or replacement of the catalyst, and transfer of catalyst from and to the reactor on a continuous basis is highly desirable.
A reforming reaction section operating with the continuous addition and withdrawal of catalyst particles through a series of radial flow reactors, as illustrated in FIG. 6 , thus provides a good example of a fluid/solid contacting apparatus that can benefit from the present invention. The reaction section contains a series of four reactors arranged vertically in a stacked-reactor vessel 40 . The individual reactors or reaction zones are identified by numerals I-IV. Catalyst particles enter the top of the stacked-reactor arrangement through catalyst transfer line 42 and pass through the series of four reactors under gravity flow. After passage through each reactor section, the catalyst particles are withdrawn from the bottom of reactor IV by one or more catalyst withdrawal lines 44 . Catalyst withdrawn through lines 44 is regenerated by the oxidation and removal of coke deposits in a regeneration zone not shown in this illustration. After regeneration, catalyst particles are again returned to the process by line 42 .
The combined hydrocarbon and hydrogen feeds enter the process through a line 50 and pass through a heater 52 to raise its temperature before entering reaction zone I. Partially converted feed is collected from the top of reaction zone I in line 54 and passes through an interstage heater 56 into reaction zone II. Intermediate reactor lines 58 and 60 carry the partially converted feed through reaction zones III and IV, with interstage heaters 62 and 64 respectively bringing the partially converted feed to reaction temperature. A reformate product is recovered from reaction zone IV by a product line 66 .
As the catalyst passes through the adjacent stacked reactors of FIG. 6 , it is retained in a bed in each reactor. The arrangement of the internals for forming is the catalyst bed and effecting fluid-particle contacting in FIG. 7 shows a sectional view of reaction zone III, but is representative of intermediate reaction zone II as well. Catalyst particles (not shown) are transferred from a particle-retaining space 72 in zone II by a series of transfer conduits 74 into reaction zone III. A bed of catalyst particles is formed below the transfer conduits in a particle-retaining space defined by vessel partition or head 76 , outer conduit 88 and inner conduit 92 . The catalyst particles eventually are withdrawn from zone III through another series of transfer conduits 78 into reaction zone IV for ultimate removal from the stacked reactor.
The partially converted feed enters reaction zone III through a nozzle 80 and flows into a distribution chamber 82 . A cover plate 84 extends across the bottom of chamber 82 to separate it from the particle-retaining space. Chamber 82 communicates the feed through a series of risers 85 that extend through the cover plate into the interior of a plurality of vertically-extended cylinders 86 ; there preferably is provision for a sliding fit between the cover plate 84 and risers 85 . Cylinders 86 and outer conduit 88 are as described in FIG. 2 for cylinders 24 and outer conduit 22 . Coverplate 90 for the panels defined by cylinders 86 and outer conduit 88 is as described in FIG. 4 for coverplate 36 .
The foregoing description is presented only to illustrate certain specific embodiments of the invention, and should not be construed to limit the scope of the invention as set forth in the claims. There are many possible other variations, as those of ordinary skill in the art will recognize, which are within the spirit of the invention.
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The distribution of fluids within a radial-flow reactor is improved using vertically extended cylinders distributed around the circumference of the vessel. Cylinders with a circular cross-section provide substantial vertical strength, and the configuration minimizes low-flow areas which could cause undesirable reactions. The cylinders are isolated from particles in the reactor by a particle-retaining outer conduit. The cylinders may be fabricated in panels for ease of installation and servicing.
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BACKGROUND OF THE INVENTION
I. Field of the Invention
The present invention relates to an apparatus for reproducing signals from a disc; and more particularly, relates to an apparatus for simultaneously reproducing audio signals for multiple channels or multiple languages from a DVD (Digital Versatile Disc or Digital Video Disc) and a method therefor.
II. Description of the Related Art
FIG. 1 illustrates a block diagram of a conventional apparatus for reproducing audio signals from a DVD. As shown in FIG. 1, the conventional reproducing apparatus includes a pickup 102 detecting audio signals recorded on a disc 101 such as a DVD, a high frequency (HF) processor 103 processing the signals detected by the pickup 102 and outputting the processed HF signals; an audio decoder 104 decoding the processed HF signals and outputting the decoded audio signals; and a controller 105 controlling the operation of the audio decoder 104 and the HF processor 103.
The operation of the conventional reproducing apparatus is as follows. The pickup 102 detects data recorded in the DVD. The HF processor 103 processes the detected signals of the pickup 102 under the control of the controller 105, and outputs the processed HF signals. At this point, the audio decoder 104 receives the processed HF signals, decodes the processed HF signals under the control of the controller 105, and outputs the decoded audio signals. The output of the audio decoder 104 can then be heard through speakers or headphones.
A problem with the conventional apparatus is that it reproduces and outputs audio signals for only one channel or language from among multiple channels or languages recorded in the DVD.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an apparatus and method for reproducing audio signals for a plurality of channels or languages from a disc which simultaneously outputs audio signals for a plurality of selected channels or languages recorded on the disc.
Another object of the present invention is to provide an apparatus for reproducing audio signals for a plurality of channels or languages from a disc which simultaneously decodes audio signals for a plurality of channels or languages recorded on the disc.
A further object of the present invention is to provide an apparatus and method for reproducing audio signals for a plurality of channels or languages from a disc which simultaneously decodes audio signals for a plurality of selected channels or languages recorded on the disc, mixes the selectively decoded audio signals, selects audio signals for desired channels or languages from among the mixed audio signals and outputs the selected audio signals.
These and other objects are achieved by providing an audio signal processor receiving digital audio signals for more than one channel reproduced from a disc, and processing said received digital audio signals; a controller setting at least a first channel for reproduction, and generating a first control signal indicative thereof; at least a first decoder receiving said processed audio signals and said first control signal, and extracting and decoding audio signals for said first channel included in said processed audio signals based on said first control signal.
These and other objects are also achieved by providing (a) receiving digital audio signals for more than one channel reproduced from a disc; (b) processing said received digital audio signals; (c) setting at least one channel for reproduction; (d) extracting audio signals for said channel set in said step (c) from said processed audio signals; and (e) decoding said extracted audio signals.
Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus, are not limitative of the present invention, and wherein:
FIG. 1 is a block diagram of a conventional apparatus for reproducing audio signals from a DVD;
FIG. 2 is a block diagram illustrating an apparatus for reproducing audio signals from a DVD according to a first embodiment of the present invention;
FIG. 3 shows an example of an audio channel selection menu used in the reproducing apparatus of FIG. 2;
FIG. 4 is a flow chart of the operation of the reproducing apparatus of FIG. 2;
FIG. 5 is a block diagram illustrating an apparatus for reproducing audio signals from a DVD according to a second embodiment of the present invention;
FIG. 6 is a block diagram illustrating an apparatus for reproducing audio signals from a DVD according to a third embodiment of the present invention and an apparatus for outputting the reproduced audio signals;
FIG. 7 is an example of an audio channel selection menu used in the reproducing apparatus of FIG. 6; and
FIG. 8 is a flow chart of the operation of the reproducing apparatus of FIG. 6.
DESCRIPTION OF THE INVENTION
FIG. 2 is a block diagram of an apparatus for reproducing audio signals for a plurality of channels or languages from a DVD according to a first embodiment of the present invention. As shown, the reproducing apparatus includes a pickup 202 detecting multiple audio signals recorded on a disc 201, such as a DVD; a high frequency (HF) processor 203 processing the audio signals detected by the pickup 202 and outputting the processed HF signals; first and second audio decoders 204-1 and 204-2 which decode the processed HF signals and output respective first and second decoded audio signals; and a controller 205 controlling the HF processor 203 and the first and second audio decoders 204-1 and 204-2 based on key or user input.
The operation of the reproducing apparatus shown in FIG. 2 will be described with reference to FIG. 4. FIG. 4 illustrates a flow chart of the operation of the reproducing apparatus shown in FIG. 2. First, if the disc 201 is loaded, the pickup 202 detects guide information recorded in the header of the disc. Then the HF processor 203 processes the guide information, and transfers the processed information to the controller 205. The controller 205 determines in Step S10 whether or not the transferred information is related to audio data for multiple channels or languages.
If the transferred information relates to audio data for multiple channels or languages, the controller 205 causes this information to be displayed on display devices (not shown), such as digitrons and on-screen displayers, as a selection menu of audio channels. An example display of such a selection menu is shown in FIG. 3. For example, the selections include Audio 1 (English), Audio 2 (German), Audio 3 (Japanese), etc. If the disc 201 does include audio data related to multiple channels or languages, processing ends.
Next, users push selection keys to select one of the channels or languages from among the multiple audio channels or languages displayed. The number of channels or languages selected is limited to the number of decoders in the reproducing apparatus. The users then push the set key to set the selections made. For example, a first user enters Audio 1 (English) or channel CH1 and a second user enters Audio 3 (Japanese) or channel CH3.
At step S11, the controller 205 receives the user input (not shown) and judges whether two or more channels or languages have been selected. If two or more channels have been selected, the controller 205 determines if the reproduction process is under way in step S12.
When the reproduction process starts, the pickup 202 detects the audio signals recorded on the disc 201. The HF processor 203 then processes the detected audio signals, and outputs the processed HF signals to the first and second audio decoders 204-1 and 204-2. The controller 205 determines if the reproduction process is under way by judging whether the first and second audio decoders 204-1 and 204-2 are receiving processed audio signals from the HF processor 203 in step S12.
Based on the selections made by the users, the controller 205 instructs the first audio decoder 204-1 to extract and decode the audio signals for one of the selected channels or languages, and instructs the second audio decoder 204-2 to extract and decode the audio signals for another one of the selected channels or languages (steps S13 and S14). For example, the first audio decoder 204-1 extracts and decodes Audio 1 (English) or channel CH1, while the second audio decoder 204-2 extracts and decodes Audio 3 (Japanese) or channel CH3. If two or more channels (e.g., languages) are not being reproduced in step S11, if the reproduction process is not under way in step S12 or if the selected audio streams are not being extracted in step S13, processing ends.
Each of the first and second audio decoders 204-1 and 204-2 outputs audio signals for one of the channels or languages according to the selection made by a user. Therefore, multiple users can listen to audio output in the language of their choice.
While this embodiment has been described as including two audio decoders, this should not be taken as limiting the number of audio decoders to two. The number of audio decoders may be more than two. Further, although the above embodiment describes users selecting the desired channels or languages after the disc 201 is loaded, the embodiment can be easily modified so that the channels or languages for reproduction are preset before the reproduction process begins.
Each of the plurality of audio decoders in the above embodiment should preferably include a plurality of decoding function sections. Also, the reproducing apparatus can be easily applied to an apparatus for selecting and simultaneously outputting a plurality of desired sound channels such as discussed with respect to FIG. 6.
Referring to FIG. 5, a reproducing apparatus reproducing audio signals for a plurality of channels or languages according to a second embodiment of the present invention will now be described. As shown in FIG. 5, the reproducing apparatus according to the second embodiment of the present invention includes a pickup 202 detecting audio signals for multiple audio channels or languages recorded on a disc 201, such as a DVD; a high frequency (HF) processor 203 processing the signals detected by the pickup and outputting the processed HF signals; an audio decoder 222 including first and second input terminals 223 and 224, which each receiving the output of the HF processor 203; a delayer 211 delaying the processed HF signals received by the second input 224; and a controller 205' setting channels or languages to be processed by the audio decoder 222 based on key or user inputs (not shown) and controlling the above operations of the HF processor 203 and the audio decoder 222.
The audio decoder 222 includes a first and second buffer 244-1 and 244-2. The first and second buffers 244-1 and 244-2 temporarily store the signals received at the first and second input terminals 223 and 224, respectively. The audio decoder 222 uses (1) the time difference between the audio signals received at the first and second input terminals 223 and 224 and (2) the first and second buffers 244-1 and 244-2 to extract, in time-division mode, audio signals for the corresponding channel or language selected by a user from the output signals of the HF processor 203. The audio decoder 222 decodes the extracted audio signals and outputs the decoded signals to corresponding audio outputs.
The reproducing apparatus according to the second embodiment shown in FIG. 5 operates in the same manner as the reproducing apparatus according to the first embodiment shown in FIG. 2, with the exception that the former uses the delayer 211 and an audio decoder 222 with first and second buffers 244-1 and 244-2 to extract and decode selected audio signals. Therefore, only the operation of elements which are different from the first embodiment will be explained with reference to FIG. 5 to avoid repetition.
Referring again to FIG. 5, the output signals of the HF processor 203 are input to the first and second input terminals 223 and 224 with a time difference caused by the delayer 211. The audio decoder 222 stores the signals received at the first and second input terminals 223 and 224 in the first and second buffers 244-1 and 244-2, respectively. Using a single internal decoder, the audio decoder 222, under the control of the controller 205', selectively decodes portions of the signals stored in the first and second buffers 244-1 and 244-2, and routes the decoded signals to a respective one of the audio outputs such that each audio output supplies a decoded audio signal for a selected one of the channels or languages. Thus, the second embodiment of the present invention shown in FIG. 5 can use the internal buffers of only one audio decoder, instead of a plurality of audio decoders to process, in a time-division mode to extract and decode the audio signals of the selected two or more channels or languages.
FIG. 6 illustrates a reproducing apparatus 300 according to a third embodiment of the present invention and an audio output apparatus 310 connected thereto.
As shown in FIG. 6, the reproducing apparatus 300 includes a pickup 302 detecting audio signals for multiple channels or languages recorded on a disc 301, such as a DVD; a high frequency (HF) processor 303 processing the audio signals detected by the pickup 302 and outputting the processed HF signals; first and second audio decoders 304-1 and 304-2 decoding the output signals of the HF processor 303; an audio encoder 306 mixing and encoding the output signals from the first and second audio decoders 304-1 and 304-2; and a controller 305 setting which channels or languages are to be processed by the first and second audio decoders 304-1 and 304-2 and controlling the operation of the HF processor 303, the first and second audio decoders 304-1 and 304-2, and the audio encoder 306.
The audio output apparatus 310 includes an audio selector 311 selectively outputting audio signals for a desired channel or language from among the mixed audio signals output by the audio encoder 306 based on input from a switch 315; and a third audio decoder 312 decoding the output signals of the audio selector 311, and outputting the decoded audio signals to speakers 313 and 314.
The operation of the reproducing apparatus according to the third embodiment will now be explained with respect to FIGS. 7 and 8. FIG. 8 illustrates a flow chart of the operation of the reproducing apparatus shown in FIG. 6. First, when the disc 301 is loaded, the pickup 302 detects guide information recorded in the header of the disc. Then the HF processor 303 processes the guide information, and transfers the processed information to the controller 305. The controller 305 determines in step S101 whether or not the transferred information relates to audio signals for multiple channels or languages.
If so, the controller 305 causes this information to be displayed on display devices (not shown), such as digitrons and on-screen displayers, as a selection menu of audio channels (e.g., Audio 1, Audio 2, Audio 3, . . . , Audio n). An example display of such a selection menu is shown in FIG. 7.
Next, users push selection keys to select one of the channels or languages from among the recorded multiple audio channels or languages shown in the selection menu of FIG. 7. The number of channels or languages which can be selected is limited to the number of audio decoders in the reproducing apparatus 300. The users then push the set key to set the selections made. Since two audio decoders, first and second audio decoders 304-1 and 304-2, are exemplified in the reproducing apparatus 300 of FIG. 6 according to the third embodiment, two reproduction routes for two channels or languages can be selected.
At step S111, the controller 305 receives the user input (not shown) and judges whether two or more channels or languages have been selected. If two or more channels (e.g., languages) have been selected, the controller 305 determines if the reproduction process is under way in step S121.
When the reproduction process starts, the pickup 302 detects the audio signals recorded on the disc 301. Then the HF processor 303 processes the detected audio signals, and outputs the processed HF signals to the first and second audio decoders 304-1 and 304-2.
The controller 305 determines if the reproduction process is under way by judging whether the first and second audio decoders 304-1 and 304-2 are receiving processed audio signals from the HF processor 303 in step S121.
Based on the selections made by the users, the controller 305 instructs the first audio decoder 304-1 to extract and decode the audio signals for one of the selected channels or languages, and instructs the second audio decoder 304-2 to extract and decode the audio signals for another one of the selected channels or languages (steps S131 and S141). For example, the first audio decoder 304-1 extracts and decodes Audio 1 or channel CH1, while the second audio decoder 304-2 extracts and decodes Audio 3 or channel CH3. If two or more languages are not being reproduced in step S111, if the reproduction process is not under way in step S121 or if the selected audio streams are not being extracted in step S131, processing ends.
Next, in step S151 the audio encoder 306 multiplexes the audio signals output by the first and second audio decoders 304-1 and 304-2, and outputs the multiplexed audio signals to the audio output apparatus 310. At the audio output apparatus 310, a user selects a channel or language he wants to hear via switch 315, and the audio selector 311 outputs the audio signals for the selected channel or language from the multiplexed audio signals. The third audio decoder 312 then decodes the selected audio signals, and outputs the decoded audio signals to the speakers 313 and 314. Accordingly, the user can hear the audio signals for a desired channel or language from among multiple channels or languages recorded on the disc.
In the above embodiment, if multiple audio output apparatuses 310 are connected to the reproducing apparatus 300, multiple users can simultaneously enjoy audio signals for multiple channels or languages recorded on the disc.
Except for the addition of the audio encoder 306, the reproducing apparatus 300 of FIG. 6 is the same as the reproducing apparatus of FIG. 2, and like modifications can be made. As a further modification of the third embodiment of the present invention. The structure corresponding to the reproducing apparatus of FIG. 2 can be replaced by the structure of the reproducing apparatus shown in FIG. 5. In this instance, the audio encoder 306 is connected to the audio outputs of the audio decoder 222. The number of channels or languages which can be decoded is then limited to the number of buffers in the audio decoder 222.
As described above, the present invention reproduces audio signals for multiple channels or languages recorded on a disc, such as a DVD, selects audio signals for desired channels or languages, and simultaneously outputs the selected audio signals; thereby giving a user or multiple users greater satisfaction and convenience.
As will be evident to those skilled in the art, various modifications of this invention can be made or followed in light of the foregoing disclosure without departing from the spirit of the disclosure or from the scope of the claims.
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A reproducing method and apparatus include an audio signal processor, a controller, and at least one decoder. The audio signal processor receives digital audio signals for more than one channel reproduced from a disc, and processes the received digital audio signals. The controller sets at least a first channel for reproduction, and generates a first control signal indicative thereof. The first decoder receives the processed audio signals and the first control signal, and extracts and decodes audio signals for the first channel included in the processed audio signals based on the first control signal.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. 11/910,987 filed Nov. 27, 2007, now pending, which is a 35 U.S.C. 371 national application of PCT/US2005/015577 filed May 4, 2005, which claims priority or the benefit under 35 U.S.C. 119 of U.S. provisional application No. 60/567,488 filed May 3, 2004, the contents of which are fully incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to methods and compositions for improving chlorine dioxide treatment processes, such as, pulp delignification and bleaching processes.
BACKGROUND
[0003] Chlorine dioxide is one of the most widely used delignification/bleaching agents in the pulp and paper industry, providing a high-quality, low-cost delignification and bleaching process. Chlorine dioxide treatment is superior to chlorine bleaching processes in that it virtually eliminates all dioxin discharges into the environment, and has accordingly, helped pulp and paper manufactures to employ environmentally friendly processes and to meet environmental requirements. Accordingly, the use of chlorine dioxide treatment is increasing and most pulp and paper mills now have at least one chlorine dioxide delignification or bleaching stage. Chlorine dioxide treatment has also been used to treat wastewater, sludge and other process streams.
[0004] During the chlorine dioxide treatment processes some of the chlorine dioxide is converted to chlorate and chlorite, which decreases the efficiency of the chlorine dioxide treatment. Methods have been proposed to improve the efficiency of the chlorine dioxide treatment process by reducing chlorate and chlorite formation. Seger et al., Chiang, Tappi J., 1992, 75(7):174-180, for example, discloses a two step high-pH and low-pH process, which is believed to reduce the formation of chlorate at the higher pH and chlorite becomes reactive in the low-pH step. Joncourt et al., International Symp. Wood Pulping Chemistry, Montreal, Jun. 9-12, 1997, discloses the use of iron to regenerate chlorine dioxide from chlorite. Jiang et al, U.S. Pat. No. 6,235,154, discloses process for improving chlorine dioxide delignification or bleaching by regenerate chlorine dioxide from the chlorite using formaldehyde.
[0005] New compositions and methods are needed to improve the efficiency and effectiveness of chlorine dioxide treatment, including, chlorine dioxide delignification and bleaching processes.
SUMMARY OF THE INVENTION
[0006] The present invention relates to methods and compositions for chlorine dioxide delignification and/or bleaching processes by reacting pulp with chlorine dioxide and a peroxidase and/or a laccase. In accordance with the present invention, a peroxidase and/or a laccase is/are added to a chlorine dioxide delignification and/or bleaching step. Although not limited to any one theory of operation, the addition of a peroxidase and/or a laccase to a chlorine dioxide treating composition is believed to result in the regeneration of chlorine dioxide from chlorite, resulting in improved delignification and/or brightening during bleaching of pulp.
[0007] The present invention relates to methods and compositions for chlorine dioxide treatment of wastewater, sludge or any other process stream. In accordance with the present invention, a peroxidase and/or a laccase is added to a chlorine dioxide treatment step to improve the chlorine dioxide treatment process.
DETAILED DESCRIPTION
[0008] A “peroxidase” means a peroxidase (E.C.1.11.1.7) and/or a haloperoxidase, such, as, preferably, a chloride peroxidase (E.C.1.11.1.10). Preferably, the peroxidase is an acid stable peroxidase.
[0009] Peroxidases may be obtained from any suitable source, such as, e.g., from plants (e.g., a soy bean or horseradish peroxidase) and from microorganisms (fungi and bacteria, such as, e.g., the peroxidase may be obtained from a strain of Coprinus, e.g., C. cinerius or C. macrorhizus, or of Bacillus, e.g. B. pumilu ). Some preferred fungal sources include strains belonging to the subdivision Deuteromycotina, class Hyphomycetes, e.g., Fusarium, Humicola, Tricoderma, Myrothecium, Verticillum, Arthromyces, Caldariomyces, Ulocladium, Embellisia, Cladosporium or Dreschlera, in particular, Fusarium oxysporum (DSM 2672), Humicola insolens, Trichoderma resii, Myrothecium verrucana (IFO 6113), Verticillum alboatrum, Verticillum dahlie, Arthromyces ramosus (FERM P-7754), Caldariomyces fumago, Ulocladium chartarum, Embellisia alli or Dreschlera halodes. Other preferred fungal sources include strains belonging to the subdivision Basidiomycotina, class Basidiomycetes, e.g., Coprinus, Phanerochaete, Coriolus or Trametes, in particular Coprinus cinereus f. microsporus (IFO 8371), Coprinus macrorhizus, Phanerochaete chrysosporium (e.g., NA-12) or Coriolus versicolor (e.g., PR4 28-A). Further preferred fungal sources include strains belonging to the subdivision Zygomycotina, class Mycoraceae, e.g., Rhizopus or Mucor, in particular, Mucor hiemalis.
[0010] Some preferred bacterial peroxidase sources include strains of the order Actinomycetales, e.g., Streptomyces spheroides (ATTC 23965), Streptomyces thermoviolaceus (IFO 12382) or Streptoverticillum verticillium ssp. verticillium. Other preferred bacterial sources include Bacillus pumillus (ATCC 12905), Bacillus stearothermophilus, Rhodobacter sphaeroides, Rhodomonas palustri, Streptococcus lactis, Pseudomonas purrocinia (ATCC 15958) or Pseudomonas fluorescens (NRRL B-11).
[0011] Haloperoxidases may be obtained form any suitable source. Haloperoxidases, for example, have been isolated from various organisms, including mammals, marine animals, plants, algae, a lichen, fungi and bacteria (for reference see Biochimica et Biophysica Acta 1161, 1993, pp. 249-256). Suitable choloroperoxidases include the chloroperoxidase obtained from the fungus Curvularia inaequalis (see SWISS-PROT:P49053), the chloroperoxidase obtained from the fungus Curvularia verruculosa (see WO 97/04102) and the chloroperoxidases disclosed in Svendsen et al, U.S. Pat. No. 6,372,465.
[0012] Laccases (EC 1.10.3.2) may be obtained from any suitable sources, such as, from a genus selected from the group consisting of Aspergillus, Botrytis, Collybia, Fomes, Lentinus, Myceliophthora, Neurospora, Pleurotus, Podospora, Polyporus, Scytalidium, Trametes, and Rhizoctonia. In a more preferred embodiment, the laccase is obtained from a species selected from the group consisting of Humicola brevis var. thermoidea, Humicola brevispora, Humicola grisea var. thermoidea, Humicola insolens, and Humicola lanuginosa (also known as Thermomyces lanuginosus ), Myceliophthora thermophila, Myceliophthora vellerea, Polyporus pinsitus, Scytalidium thermophila, Scytalidium indonesiacum, and Torula thermophila. The laccase may be obtained from other species of Scytalidium, such as Scytalidium acidophilum, Scytalidium album, Scytalidium aurantiacum, Scytalidium circinatum, Scytalidium flaveobrunneum, Scytalidium hyalinum, Scytalidium lignicola, and Scytalidium uredinicolum. Rhizoctonia solani and Coprinus cinereus. The laccase may be obtained from other species of Polyporus, such as Polyporus zonatus, Polyporus alveolaris, Polyporus arcularius, Polyporus australiensis, Polyporus badius, Polyporus biformis, Polyporus brumalis, Polyporus ciliatus, Polyporus colensoi, Polyporus eucalyptorum, Polyporus meridionalis, Polyporus varius, Polyporus palustris, Polyporus rhizophilus, Polyporus rugulosus, Polyporus squamosus, Polyporus tuberaster, and Polyporus tumulosus.
[0013] A “chlorine dioxide treatment” means any chloride dioxide treatment process, such as, for example, chlorine dioxide treatment stages used in pulp and paper mills and chlorine dioxide treatment of wastewater and/or sludge, for example, plant wastewater or ordinary household sewage or wastewater.
[0014] Typically chlorine dioxide treatment is applied in a pulp and paper mills in delignification and pulp bleaching processes. Any suitable pulp may be treated, although preferably, the pulp is a lingocellulosic pulp. The pulp may be treated with other delignification and/or bleaching agents prior to, during or following the chlorine dioxide treatment, such as, e.g., oxygen delignification, peroxide treatment, and enzyme treatment processes.
[0015] The chlorine dioxide used in the treatment process may be generated by any suitable method. However, because chlorine dioxide is unstable as a gas and can only stored as a solution, it is usually generated on-site, e.g., at the pulp mill. Once in solution, however, chlorine dioxide is fairly stable.
[0016] Chlorine dioxide is generally added in amounts effective to treat the pulp or process waters (e.g., waste water), as are known in the art.
[0017] Typically, chlorine dioxide treatment of pulp is carried out at a temperature from about 40 to 80° C. for a period of about 15 to 120 min. The effectiveness of the chlorine dioxide depends in part on pH, and is maximized at a pH of about 2 to 4. Because the pH of pulp streams and other process waters are typically more basic, acid may be added to the treatment water to reduce the pH. In some processes, the pH of the process water may be controlled by applying excess amounts of chlorine dioxide.
[0018] The peroxidase and/or laccase is/are applied directly to the chlorine dioxide process stream in an amount effective to improve the chlorine dioxide treatment process, as exemplified below. The peroxidase and/or laccase may be applied as part of the chlorine dioxide solution, a part of a filtrate used to prepare the process water (e.g. delignification or bleaching liquour), in the recycled process water, and/or by a separate addition.
[0019] The peroxidase and/or laccase are applied in an amount effective to improve the chlorine dioxide treatment process, such as, as measured by improved pulp delignification and/or improved pulp bleaching. An example of an effective amount of a peroxidase is 0.005 mg-10 g/L of process water, more preferably 0.01-1000 mg/L of process water, and most preferably 0.05-500 mg/L of process water. In regard to pulp applications, such effective amount of a peroxidase will include 0.01 g-20 kg/ton of pulp, more preferably 0.1 g-5 kg/ton of pulp, and most preferably 1 g-2 kg/ton of pulp. An example of an effective amount of a laccase is 0.005 mg-10 g/L of process water, more preferably 0.01-1000 mg/L of process water, and most preferably 0.05-500 mg/L of process water. In regard to pulp applications, such effective amount of a laccase will include 0.01 g-20 kg/ton, more preferably 0.1 g-5 kg/ton, and most preferably 1g-2 kg/ton. The peroxidases and laccases are preferably selected based their compatibility with the process conditions for the pulp treatment or waste water/sludge treatment, e.g., pH optimum, temperature optimum, acid stability.
[0020] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims.
EXAMPLES
Example 1
[0021] 160 mg of NaClO 2 was dissolved in 100 mL of DI water. 10 mL aliquots of the NaClO 2 solution were added to different test tubes. 20 uL of acetic acid were added to each tube and the pH was adjusted to about 3.5. Then 100 uL of enzyme was added to the solution. After 30 min of incubation at ambient temperature, the solution was diluted 3 times by DI water. ClO 2 formation was detected by UV absorbency at 360 nm. It is evident that all of the enzymes can generate ClO 2 to some extent under the conditions used in this experiment.
[0000]
TABLE 1
Enzymatic Chlorine Dioxide Generation
Absorbency
No.
Sample
at 360 nm
1
Control
0.155
2
Peroxidase from Coprinus cinereus
0.764
(Novozymes)
3
Haloperoxidase from Curvularia verruculosa
0.168
(Novozymes)
4
Laccase from Trametes villosa
0.802
(Novozymes)
5
Laccase from Coprinus cinereus
0.190
(Novozymes)
6
Laccase from Myceliophthora thermophila
0.197
(Novozymes)
7
Chloroperoxidase from Caldariomyces fumago
0.393
(Sigma, C-0278)
Example 2
[0022] 5 g (o.d. dry) of unbleached kraft pulp was added to each beaker and diluted to about 5% consistency. The pulp was adjusted to various pH by 2N H 2 SO 4 . 10 mL of 11.3/L of NaClO 2 was added to each beaker. 500 ul of peroxidase ( Coprinus cinereus peroxidase, Novozymes) was added to the solution and the beaker was incubated at 60° C. for 1 hr. After bleaching, the pulp was rinsed with DI water and handsheets were made and tested for brightness. Brightness was tested according to Tappi standard (T452). It is clear the peroxidase improved pulp brightness in all the pH range.
[0000]
pH
Sample
Brightness
3
Control
50.4
3
Peroxidase
51.4
4
Control
46.8
4
Peroxidase
47.3
5
Control
43.3
5
Peroxidase
44.2
6
Control
42.8
6
Peroxidase
45.0
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The present invention relates to methods and compositions for chlorine dioxide delignification and/or bleaching processes by reacting pulp with chlorine dioxide and a peroxidase and/or a laccase.
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FIELD OF THE INVENTION
[0001] The present invention relates to improvements to exhaust extractor manifolds.
DESCRIPTION OF THE PRIOR ART
[0002] Excess exhaust backpressure is detrimental to vehicle engine performance. It is known that reducing restrictions to the flow of the combustion by-products (exhaust) from the combustion chamber of an internal combustion engine yields considerable improvements in the torque and power outputs, and the fuel, volumetric and thermal efficiencies of the engine.
[0003] The removal of the exhaust gases from the combustion chamber using the momentum of the exhaust gases in a long exhaust pipe, or by taking advantage of the pressure waves set up in the exhaust pipe by the discharge of the previously expelled gases, is known as scavenging. In addition to improving the exhausting of the combustion chamber, this scavenging effect also works in conjunction with the vacuum created by the piston during the inlet stroke, to assist in drawing in a fresh fuel charge.
[0004] Exhaust manifolds adapted to maximise scavenging effects are often known as ‘extractors’ or ‘headers’.
[0005] A well-designed extractor manifold comprises a plurality of bent steel pipes (one per cylinder), physically arranged so as to promote this scavenging effect. The pipes are also arranged in a fashion that consolidates them, so that there is only the one pipe channeling exhaust from that manifold to the rear of the car for release. These branches of pipes must therefore be consolidated at pipe connections or Junctions. For example, extractors for a six cylinder engine may incorporate three 2 into 1 junctions, and a further 3 into 1 junction further downstream.
[0006] It is an object of this invention therefore to provide an exhaust extractor manifold that provides improved scavenging, or at the least provides the public with a useful alternative to the exhaust manifolds of the prior art.
[0007] Other objects and advantages of the present invention will become apparent from the following description, taken in connection with the accompanying drawings, wherein, by way of illustration and example, an embodiment of the present invention is disclosed.
SUMMARY OF THE INVENTION
[0008] In one form of this invention, there is proposed a venturi pipe for insertion in a pipe of an extractor manifold so that exhaust gas will pass there through, the venturi pipe including a portion having a locally reduced internal diameter and a portion that is adapted to promote the swirling of exhaust gas passing there through.
[0009] Preferably, the portion having a locally reduced internal diameter is at or toward an upstream end of the venturi pipe, and the portion adapted to promote swirling of exhaust gas passing there through is at or toward the downstream end of the venturi pipe.
[0010] In a further form, the invention may be said to lie in a portion of a pipe of an extractor manifold including a portion having a locally reduced internal diameter, and a portion that is adapted to promote swirling of exhaust gas passing there through.
[0011] Preferably, the portion adapted to promote swirling of exhaust gas passing there through is downstream of the portion having a locally reduced internal diameter.
[0012] In a further form, the invention may be said to lie in a connector portion for an extractor manifold having an upstream end adapted to accept at least two converging upstream supply pipes, where said connector pipe defines a substantially helical path in a downstream direction.
[0013] Preferably, the connector portion has an upstream end with an outer perimeter shape which substantially matches the outer perimeter shape of the converging supply pipes, there being a bulbous portion for each supply pipe, where each bulbous portion is progressively less outwardly protruding in a downstream direction, but also veering in a curved path which is for each and all of the bulbous portions in a same handed direction.
[0014] Preferably, the respective bulbous portions define together a helical path in a downstream direction of the single pipe.
[0015] In a further form, the invention may be said to lie in an exhaust extractor manifold assembly including at least two upstream pipes converging at a pipe having a connector portion, the connector portion having an upstream end that is adapted so as to accept the upstream pipes and define a substantially helical path in a downstream direction, the assembly further including a venturi pipe having a portion of locally reduced internal diameter and a portion that is adapted to promote swirling of exhaust gas passing there through, wherein the venturi pipe is inserted in a pipe of the assembly in a position located downstream of the connector portion, so that the connector portion and the venturi pipe are adapted to co-operatively define a substantially helical path for exhaust gasses in a downstream direction of the connector portion.
[0016] Preferably, the helical path defined by the venturi pipe and the bulbous portions are adapted to generate a vortex in exhaust gases passing through the assembly, which will augment the scavenging affect provided by the extractor manifold.
[0017] In a further form, the invention may be said to lie in an exhaust extractor manifold including at least two upstream pipes converging at a connector portion, the connector portion having an upstream end that is adapted so as to accept the upstream pipes and define a substantially helical path in a downstream direction, the assembly further including portion of pipe having a portion of locally reduced internal diameter and a portion that is adapted to promote swirling of exhaust gas passing there through, wherein said portion of pipe is in a position located downstream of the collector pipe so that the connector portion and said portion are adapted to co-operatively define a substantially helical path for exhaust gasses in a downstream direction of the connector portion.
[0018] In a further form, the invention may be said to lie in an installation in which there is an internal combustion engine, with an extractor assembly having one or more of the above-mentioned features.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] For a better understanding of this invention it will now be described with respect to the preferred embodiment which shall be described herein with the assistance of drawings wherein;
[0020] FIG. 1 is a perspective view of the connector portion of an exhaust extractor manifold;
[0021] FIGS. 2 and 3 are perspective views of the venturi pipe from the exhaust extractor manifold in FIG. 1 ;
[0022] FIG. 4 is a cross-sectional view through the venturi pipe in FIGS. 2 and 3 ;
[0023] FIG. 5 is a perspective view of the connector portion of an exhaust extractor manifold according to a further embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Now referring to the illustrations, and in particular to FIG. 1 , where there is illustrated the connector portion 1 of an exhaust extractor manifold, which is made from tubular steel.
[0025] This connector portion 1 connects the upstream supply pipes 2 , 4 , 6 , and 8 , to a single pipe 12 . An exhaust manifold assembly of this type would typically be adapted for use on a four cylinder engine, or a bank of 4 cylinders on a V8 engine, where each of the upstream pipes 2 , 4 , 6 , and 8 is receiving combustion by-products from a combustion chamber of a cylinder, and the four pipes are converged into one pipe 12 via the connector portion 1 , for the transfer of combustion by-products to the rear of the vehicle, where they are released to atmosphere.
[0026] Each of the upstream pipes 2 , 4 , 6 and 8 has a downstream end, each of a substantially circular shape, which are arranged in a converging and mutually adjoining alignment. The connector 1 has an upstream end with an outer perimeter shape that will accept within in it the outer perimeter shape of the mutually adjoining supply pipe ends. The result is an upstream defined by 4 bulbous forms 20 , 22 , 24 and 26 . Each bulbous form is progressively less outwardly protruding at it extends in the downstream direction, and each also veers in an identical curved path in the downstream direction.
[0027] Positioned in the single pipe 12 at a position just downstream of the connector 10 is a steel venturi pipe 30 , which provides an exhaust gas passageway 32 for the exhaust gasses to pass there through. All of the exhaust gas leaving the connector 1 passes through this venturi pipe 30 .
[0028] The passageway 32 through the venturi pipe 30 has an inlet at A; just downstream of inlet A the pipe 30 tapers down, thereby reducing the internal diameter of the pipe at B. The exhaust gasses speed up as they pass through the restriction created by this reduced diameter, reducing their pressure and creating a partial vacuum, all of which are a result of the Bernoulli affect. After the restriction at B, the venturi pipe gradually opens out again along the remainder of the pipes length at C.
[0029] A pair of swirled grooves 40 and 42 are formed into the wall of the venturi pipe 30 so that they project inwardly of the wall of the pipe in the region C where the venturi pipe gradually opens out again. As exhaust gasses pass through the venturi pipe downstream of the constriction at B, they are swirled into a vortex by these swirled grooves 40 and 42 .
[0030] In use then, the combined effect of the helical path defined by the shape of the connector 10 and the swirled grooves 40 and 42 in the venturi pipe 30 , is intended to generate a vortex (clockwise in this case), which will create a suction that augments the scavenging affect provided by providing the correct arrangement of supply pipes 2 , 4 , 6 , and 8 entering the connector; that arrangement being one which cooperates with the firing order of the engine to maximise the scavenging effect provided by the exhaust gas pulses.
[0031] It would be understood by a person skilled in the art that it is possible to use either of the shaped collector 10 or the venturi pipe 30 independently in an extractor manifold to obtain a performance gain. The best results however are obtained when these are used in combination as described.
[0032] Referring now to FIG. 5 , where there is illustrated an exhaust manifold assembly 100 wherein the venturi B and swirled portions 42 are formed in the outer pipe 12 .
[0033] It is considered therefore that an exhaust extractor assembly such as that described herein would prove to be of considerable benefit to those seeking an exhaust extractor manifold that will improve the torque and power outputs, and the fuel, volumetric and thermal efficiency of their car engine.
[0034] Although the invention has been herein shown and described in what is conceived to be the most practical and preferred embodiment, it is recognised that departures can be made within the scope of the invention, which is not to be limited to the details described herein but is to be accorded the full scope of the appended claims so as to embrace any and all equivalent devices and apparatus.
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The invention relates to an extractor manifold for an internal combustion engine including a pipe having a portion with a locally reduced internal diameter so as to thereby form a venturi, and a portion that is adapted to promote swirling of exhaust gas passing there through.
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BACKGROUND OF THE INVENTION
This invention relates to that field of building construction which utilizes a lattice-like three-dimensional frame structure covered by a flexible sheet canopy or skin to form an enclosure. The canopy is fabric-like in nature, but is very often a plastic film. The bottom edge of the canopy is secured to a base, and in some cases the interior of the enclosure which is formed is subjected to air at slightly greater than atmospheric pressure. In most cases, the canopy is not fastened to discrete portions of the frame, but merely engages the frame. This engagement of the canopy with the frame, particularly at the points of juncture of frame elements, causes wear and stress in the sheet material of the canopy, often resulting in rupture.
It is the general object of the present invention to provide means for supporting the canopy on the frame, particularly at frame juncture points, which will minimize the wear and stress in the sheet.
SUMMARY OF THE INVENTION
In accordance with the present invention, the frame structure comprises a lattice-like network of support elements connected together at points of juncture, and a resilient ball-like buffer is supported by the frame at each juncture point to engage the canopy and thus to prevent its direct engagement with the frame at such points. The preferred ball-like buffer is gas filled, and the preferred frame elements comprise pipes or tubes which are connected to a source of gas, such as nitrogen or air, under pressure. The frame elements, or at least one of them at each juncture point has an outlet connected to the buffer so that all of the buffers in the building construction are maintained at substantially the same pressure. A still further feature of the concept involves a safety valve arrangement whereby if a rupture occurs at one of the buffers or in a structural element pipe, there will not be a loss of pressure in all of the canopy sustaining buffers. This will permit repair or replacement as is needed at a minimal expense and without disrupting the general use of the building construction and enclosure.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a parti-elevational view of a building construction incorporating the features of the present invention and showing the canopy or skin in section;
FIG. 2 is a cross-sectional view taken through a juncture point of the frame construction as indicated by the line 2--2 in FIG. 1; and
FIG. 3 is a schematic illustration of the gas pressure supply system utilized with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIG. 1, a building construction provided in keeping with the present invention comprises a lattice-like frame structure 2 made up of a plurality of elongated frame elements 6 which are arranged with respect to each other as shown in the drawing to be connected together at a plurality of juncture points 1. At each such juncture point a buffer 4 (which will be described in more detail) is connected to the frame structure to support a fabric-like sheet 5, which may be a gas impervious plastic material, which is draped over the frame 2.
It will be observed in FIG. 1 that the frame elements 6 are connected together at juncture points 1 to form the latticelike frame network 2 in three-dimensional configuration extending from a base B. The fabric-like sheet material 5 is thus draped over the frame 2 as a canopy to form an enclosure and is secured along its bottom edge to the base B in any well known and acceptable manner. In many such building constructions, a source of air is provided at slightly more than atmospheric pressure to keep the sheet or canopy 5 slightly expanded and out of general contact with the frame structure 2. However, there will be inevitably some engagement between the canopy or skin and the frame, and heretofore this has been the source of a problem causing great wear and stress to the canopy 5, whether it be inflated or not, at the juncture points 1.
In keeping with the present invention such wear and stress on the canopy or skin is greatly reduced by the provision of a buffer 4 at each juncture point, the preferred form of such buffer being a gas inflated balloon or ball-like element. As better shown at FIG. 2, the gas-filled ball-like buffer 4 is mounted at any juncture point 1 at a plate 3 which is preferably metal but which can be made of any easily deformable material so that it can be bent to embrace and grip a substantial portion of the buffer 4 and thus to hold it. The plate 3 is in turn held as by welding or the like to juncture point plates 7 which form an envelope sealed at its edges and provided with openings along its edges adapted to receive the ends of frame elements 6, 6 as by threading or the like in a gas-tight manner.
As shown in FIG. 1, there are at least two and there may be as many as six or conceivably more frame elements 6 connected together at a junction point 1. In keeping with the invention, each frame element 6 comprises a hollow tube or pipe connected with a source of gas, such as nitrogen or air, under pressure as will be described in more detail hereinafter. The pipes 6, 6 thus supply the gas under pressure to the various buffers 4. As shown in FIG. 2, at each juncture point 1, one of the frame element pipes 6 is provided with a hose or tube connecting outlet 8 receiving a tube extension 9 from the associated buffer 4, thus to inflate the buffer with the air or nitrogen under the pressure in the frame system.
As also shown in FIG. 2, one or more of the gas carrying frame elements 6 may have its end closed as indicated at 6a within the juncture point envelope defined by the plates 7, and still other elements connected at the same juncture point may have open ends such as indicated at 6b within the envelope. This permits a plurality of the frame elements 6 to be connected together in series at different juncture points 1 whereby to define a branch supplying air or nitrogen under pressure to a plurality of buffers. For example, and as shown in FIG. 1, those conduit or pipe frame elements 6 identified as a, a, a may be series connected to form a frame branch 2a, those identified as b, b, b being series connected to form frame branch 2b, the elements c, c, c being series connected to form branch 2c and the elements d, d, d being series connected to form branch 2d. Obviously, there can be a plurality of such branches connected in parallel with each other to a single source or supply of the air or nitrogen under pressure.
This is shown in FIG. 3 wherein the reference number 10 designates a pressurized tank or supply of air or nitrogen or other gas under pressure, and the number 11 designates a pressure reducing valve connected to the outlet of the said tank. The controlled pressure outlet of the valve 11 is connected to the parallel branches of the supporting structure framework 2, four of these branches being shown and indicated as 2a, 2b, 2c and 2d in FIG. 3. Preferably, each such parallel branch includes a valve 12 which will automatically close and prevent flow into the branch in the event of rupture of one of the elements 6 or a buffer 4 in such branch. Thus, in the event of rupture somewhere in the network, only one branch outlet network suffers the loss of pressure and the remaining branches including all of their buffers are maintained at the same pressure set at the valve 11.
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A building structure comprising a lattice-like network of support elements connected together at junctures to form a three-dimensional frame supporting a fabric-like canopy or skin laid thereover as an enclosure and wherein a resilient ball-like buffer is supported by the frame at each juncture point to engage the canopy and thus to prevent its direct engagement with the frame at the juncture points to reduce its wear and stress.
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INCORPORATION BY REFERENCE
[0001] This is a divisional of application of U.S. Ser. No. 10/843,035, filed May 12, 2004, entitled “Method of Pulse Welding and Contact Tip Therefor”, by William T. Matthews, et al., the disclosure of which is hereby incorporated by reference in its entirety.
[0002] The present invention relates to a welding gun or torch especially designed for use in pulse welding aluminum wherein an aluminum wire passes through a contact tip positioned at the exit end of a gun. Such contact tips are well known and used consistently in welding guns of the type where a welding wire is passed through the gun, melted and used for the welding process. An example of such a contact tip for a welding gun is described in Parmelee U.S. Pat. No. 4,731,518. This patent is incorporated by reference herein to show the technology involved in the present invention. One aspect of the present invention involves a ceramic sleeve in the central passage of the contact tip to guide the wire through the tip without engaging the electrically conductive portion of the tip. An example of the use of ceramic to guide a moving welding wire through a contact tip is illustrated in Kinney U.S. Pat. No. 3,025,387, also incorporated by reference herein as background information.
BACKGROUND
[0003] In a pulse welding process where a welding wire is directed through the commonly used contact tip of a welding gun as the tip is subjected to a pulsed current signal, it is advantageous to tailor the background current and peak current to create a ball and to propel the ball at a specific time toward the workpiece. It has been found that the creation of the molten metal ball on the end of the advancing electrode depends on the spacing between the workpiece and the actual contact point of the wire with the contact tip. This distance between the contact point and the workpiece should remain coordinated with the profile of the pulse current. In this manner, the melting of the ball and the propelling of the ball are timed with the actual pulses of the electric current. Such coordination maintains the stability of the arc and assures the quality of the welding process. In other welding processes such as short arc or spray MIG welding, the coordination of the ball and propelling force with the waveform profile is not critical. In these processes, conventional tips are used satisfactorily with both iron and aluminum. In some instances, this standard short tip when not used for MIG welding included a ceramic block spring biased into the passageway to engage the wire and force the wire against the passage. Such spring biased ceramic block in a short tip was only for the purpose of ensuring contact. Thus, its expense was not justified and it was not accepted practice. The present invention relates to a contact tip specially designed for use in pulse welding aluminum wire. The aluminum wire passing through the passage of the tip engages the surface of the passage somewhere in the length. This uncertainty as to the contact point of the aluminum wire as it passes through the long contact tip reduces the stability of the arc and affects the quality of the pulsed welding with aluminum wire. In view of this background, there is a need for creating a contact tip specially designed for pulse welding with aluminum wire. A contact tip specially designed for aluminum pulse welding should also overcome the requirement for a special contact tip for each diameter and type of aluminum wire. In the past, this diameter of the passage in the contact tip had to be especially sized for each aluminum wire. Indeed, the passage was sized for the heat expansion of the specific aluminum wire. The diameter of the passage was about 0.010 inches larger than the diameter of the aluminum wire being welded. This required a special tip for each aluminum wire diameter. It has also been found that the contact tip and aluminum wire expand differently according to the process being performed and the alloy of the aluminum. Thus, the tip had to be specially designed not only for the diameter of the aluminum wire, but also for the expansion caused by heating associated to the welding process. When using aluminum wire, the welding tip had to be specially and accurately controlled as to the diameter of the passage for both pulse welding by aluminum wire and regular MIG welding by aluminum wire. Consequently, there is a need for a tip to be used in aluminum, especially for aluminum pulse welding which need not be accurately dimensioned and still present a specific, fixed contact point. This feature increases the arc stability. Prior contact tip disadvantages for the pulse welding process have been overcome by the present invention.
BRIEF DESCRIPTION
[0004] The present invention relates to a new method of pulse welding with aluminum wire and also a novel contact tip especially for aluminum wire, primarily for pulse spray welding of aluminum but also for conventional MIG welding of aluminum.
[0005] By implementing the inventive method of aluminum pulse welding, the melting of the aluminum and the propelling of the aluminum toward the workpiece is consistently synchronized with the pulsed current used in the process. This consistency is accomplished in a long contact tip where the aluminum wire is positively pushed against the contact tip at a fixed location spaced from the exit end of the contact tip. The distance between the contact point and the workpiece remains constant during the pulse welding process. By using this method, arc stability is maintained and the melting of the ball on the end of the aluminum wire is coordinated and synchronized with the actual current pulses of the welding process. In accordance with another aspect of the invention, the novel contact tip for use with aluminum allows the diameter of the passage in the contact tip to be enlarged so that the tip will accommodate aluminum wire having a variety of diameters. In the past, the diameter of the control passage was very close to the diameter of the wire and also was adjusted to compensate for expansion by heat during the welding process. Using the present invention, the diameter of the passage is such that aluminum wire between 0.035 inches and 0.062 inches can be processed by a single contact tip. Indeed, one embodiment of the present tip has a diameter of about 0.080 inches and can still be used for aluminum welding wire as small as 0.035 inches. This specially designed contact tip is oversized and accommodates the normal range of wire diameters used in aluminum welding, as well as, being especially advantageous for aluminum pulsed spray welding. The novel contact tip has a length greater than 1.5 inches and has a spring biased pressure block carried by the tip and forced inwardly against the wire at a position adjacent the upper portion of the contact tip. To isolate the contact point between the moving wire and the contact tip at the pressure block or pressure element, one embodiment of the invention utilizes a raised pressure pad located opposite the element or block that is forced against the wire. This causes a pinching action at a specific location in the long contact tip to assure that the welding process using aluminum wire has a consistent distance between the contact point in the tip and the workpiece. Another aspect of the invention is the shape of the pressure block, which block is spring biased against the wire passing through an opening in the contact tip. This shape includes two spaced, parallel edges, each of which has a tapered upper end and a tapered lower end. Consequently, the pressure block forced against the wire has no special orientation. Irrespective of the position of the block in the opening into the passage, there is still a lead-in tapered portion, so that the aluminum wire can be pushed past the spring biased pressure block when first stringing the aluminum wire in the welding gun.
[0006] In accordance with the present invention, there is provided a method of pulse welding with an aluminum welding wire comprising moving the welding wire toward a workpiece and through a central passage of a contact tip, where the contact tip has an innermost end, an outermost wire exit end and a length of over 1.5 inches. The method involves positively urging the wire against the contact tip at a fixed position closer to the innermost end of the tip than to the exit end of the tip and passing a pulse weld signal between the contact tip and thus the welding wire and the workpiece to melt the wire by the electrical signal and deposit the molten metal wire onto the workpiece. This is a standard pulsed spray welding process using a fixed contact point instead of a movable contact point.
[0007] In accordance with an aspect of the invention, the urging of the wire is by a spring biased insulator element or block forced through an opening in the contact tip and against the wire in a manner to force the wire against the surface of the passage at a fixed location in the contact tip. The contact tip has a length in the general range of 2-3 inches. In accordance with an aspect of the invention, a shielding gas is passed toward the workpiece and around the aluminum wire as it is being melted and deposited onto the workpiece.
[0008] Still a further aspect of the present invention is the provision of a novel contact tip for a welding gun. The tip is especially applicable to aluminum and is primarily for pulse welding. The tip has a central passage for welding wire moving in a given direction toward the workpiece and receives a welding signal by the contact of the wire with the tip. The passage has an innermost end, an outermost exit end and a length of at least 1.5 inches. An opening in the side of the contact tip intersects the passage and is generally perpendicular to the given direction of movement of the wire. A pressure element or block slidably mounted in the opening moves toward and against the wire so that a spring around the contact tip can engage the element or block to urge the element against the wire moving through the passage of the tip. In the preferred embodiment, the spring is a circular sheet spring surrounding the tip and fitting in an annular groove machined in the contact tip and intersecting the opening for the movable pressure element. The groove includes a key extending between the distal ends of the spring surrounding the contact tip to orient the spring on the tip and prevent its rotation. The pressure element is a block of insulating material which, in the preferred embodiment, has a special shape with two opposite, parallel edges, each of which has tapered ends so that orientation of the pressure block is not important.
[0009] In accordance with another aspect of the present invention, the passage has a raised pressure pad located opposite the opening for the pressure block, so the pressure block and pad pinches the wire at a fixed location adjacent the upper portion of the contact tip for uniform pulsed welding by aluminum wire. The diameter of the passage is generally about 0.068 inches in diameter to accommodate all commonly used sizes of aluminum wire. In the broadest sense, the diameter of the passage is about 0.080 so that there is a clearance which can be filled with a ceramic sleeve to guide the aluminum wire through the contact tip. In one embodiment using a ceramic sleeve, there is no pressure mechanism for the wire, the wire merely engages the contact tip at a lower portion of the passage so that the ceramic sleeve prevents contact at any place, except at the outlet of the contact tip. The contact point is at the end of the passage since there is no spring that can be affected by excessive heat. This particular type of contact tip is an alternative of the present invention and is preferred from an economic perspective but not from a wide range of application perspectives. This tip uses the broadest aspect of the invention to fix the contact point of aluminum wire moving through a long tip.
[0010] The primary object of the present invention is the provision of a method for pulse welding with aluminum wire, which method provides arc stability and consistently coordinates the melting of the aluminum wire and the deposition of the molten metal with the actual profile of the current pulses used in the pulse welding process.
[0011] Another object of the present invention is the provision of a novel contact tip designed for use in the method defined above.
[0012] Yet another object of the present invention is the provision of a contact tip, as defined above, which contact tip has a spring biased pressure block forcing the wire against the surface of the passage at a fixed location adjacent the upper portion of the contact tip. This tip is used in a process where the fixed location is essential to the operation of the process. This is not the case when using the steel wire.
[0013] Yet a further object of the present invention is the provision of a novel contact tip, as defined above, which contact tip has an oversized passage to accommodate a majority of the wire sizes used in aluminum pulse welding. This novel tip need not be closely coordinated with a given wire and designed for a certain wire diameter.
[0014] These and other objects and advantages will become apparent from the following description taken together with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a graph of a pulse welding process coordinated with the characteristics of the electrode at different times in the welding process;
[0016] FIG. 2 is a partially cross-sectioned view of the welding gun of the type used in performing the novel welding method and using the novel contact tip of the invention;
[0017] FIG. 3 is a partially cross-sectioned view of the welding gun illustrating the preferred embodiment of the present invention;
[0018] FIG. 4 is an enlarged cross-sectional view of the preferred embodiment of the invention shown in more detail in FIG. 3 ;
[0019] FIG. 5 is a cross-sectional view of the contact tip used for aluminum welding in the prior art;
[0020] FIG. 6 is a cross-sectional view showing characteristics of a tip constructed in accordance with the preferred embodiment of the present invention;
[0021] FIG. 7 is a cross-sectional view similar to FIG. 6 illustrating a modification of the preferred embodiment of the present invention;
[0022] FIG. 8 is a cross-sectional view similar to FIG. 7 illustrating still a further addition to the modified embodiment of the present invention;
[0023] FIG. 9 is a cross-sectional view of contact tip used for aluminum having a broad feature of the preferred embodiment of the invention;
[0024] FIG. 10 is a perspective view of the symmetrical ceramic pressure block used in accordance with the preferred embodiment of the present invention; and,
[0025] FIG. 11 is an enlarged cross-sectional view taken generally along line 11 - 11 of FIG. 4 .
DETAILED DESCRIPTION
[0026] FIG. 1 represents a pulse weld process for aluminum wire W using a standard signal 10 having peak current portions 12 and background current portions 14 . Each of these portions is formed by a plurality of current pulses 16 in accordance with standard waveform technology pioneered by The Lincoln Electric Company of Cleveland, Ohio. At time or point 20 , the end of wire W is liquefied to form ball B. At time or point 22 , ball B is released from the advancing wire by the increasing current and propelled toward workpiece WP. From point 20 to 22 , a new ball is formed. This process is repeated in a pulse welding process. For uniformity and synchronization with the pulses, the contact point of wire W as it passes through a contact tip or sleeve in the welding gun must be maintained somewhat constant. This is very difficult. It is not pushed against either side of the contact tip passage as it moves through the passage. A prior art contact tip is shown in FIG. 5 . Tip 30 is long to accommodate aluminum wire and has a threaded top 32 and central passage 34 , with a conical lead-in 36 . The length of passage 34 is greater than 1.5 inches and preferably in the general range of 2-3 inches. Passage 34 has a diameter that is about 0.005-0.010 inches greater than the diameter of wire W. Thus, each contact tip 30 is designed for a specific aluminum wire. Wire W and contact tip 30 have a different expansion coefficient, according to the welding process; therefore, the diameter of passage 34 becomes quite critical matching specific wire diameters and expansion tolerances. When using long tip 30 , the wire can contact the inner surface of passage 34 at various locations illustrated as a 1 , a 2 , a 3 , a 4 and a 5 . Thus, when welding with aluminum wire W, especially in the very critical pulse welding process, the welding process changes drastically according to the spacing of the contact point from the workpiece W. The distance between the actual contact point and the workpiece constitutes the heated portion of wire W plus the length of arc A which should be held generally constant. A long length for passage 34 is required to assure that there is at least a point of good contact between the moving wire and contact tip 30 . Contact tip 30 is used in pulse welding of aluminum together with other types of welding processes using a wire W formed of aluminum. The present invention is designed specifically for aluminum wire W and overcomes the disadvantages of contact tip 30 now used for welding processes involving aluminum wire.
[0027] FIG. 2 illustrates a welding gun G for use of the present invention. Flexible conduit 40 is joined by connector 42 to the wire feeding mechanism illustrated as having feed rolls 50 , 52 with an inlet guide 54 and an outlet guide 56 in a supporting fixed housing 58 . This housing could be assembled onto a robot, automatic or semiautomatic hand held torch. Gun G includes an outer housing 60 with an inwardly tapered portion 62 and an insulating sleeve 64 as shown in FIG. 3 . Mounting head 70 is a standard component and includes a center gas and wire passage 72 and a threaded receiver 74 . An outer cylindrical surface 76 defines an annular shielding gas passage 80 so that openings 82 direct pressurized shielding gas S through the openings and through annular passage 80 to shield arc A during the welding process. The electric signal for the pulse welding process or other welding process is introduced through an outer power sleeve or coupling 84 to mounting head 70 for use in the welding process.
[0028] In accordance with the present invention, a novel contact tip is designed especially for pulse welding of aluminum wire W. Novel tip 100 is best shown in FIGS. 3 and 4 as including a central passage 102 having an outer surface 104 surrounding wire W as the wire passes through gun G and through contact tip 100 . Tip 100 includes an uppermost end 106 and a lowermost wire exit end 108 with an upper conical inlet 110 on threaded top 112 . As so far described, contact tip 100 is a standard long tip of the type used for aluminum wire W. In accordance with the invention, a perpendicular rectangular opening 120 receives a matching rectangular pressure block 130 formed from an insulating material, such as ceramic and having an innermost pressure friction edge 132 and an outer pressure edge 134 . Block 130 is generally symmetrical with two parallel edges that are identical so block 130 can fit into opening 120 with either edge facing inwardly toward passage 102 . A circular groove 140 is machined in the outer surface of contact tip 100 to receive C-shaped sheet metal spring 150 mounted in groove 140 to force rectangular pressure block 130 inwardly against wire W. In this manner, the ductile wire is forced against surface 104 at a specific point opposite block 130 and closer to the uppermost end 106 and to the lowermost end 108 . This spacing is to isolate springs 150 from the heat of arc A. As wire W moves through passage 102 , it is forced against surface 104 by the inwardly urged block 130 so edge 132 forces the wire against the surface of the passage. Thus, there is a fixed distance between (a) the contact point of wire W with tip 100 and (b) workpiece WP. This provides arc stability and coordinates the molten metal shown in FIG. 1 with the pulses of signal 10 to optimize the welding process and prevent variations as explained in the discussion of FIG. 5 . The advantage of the present invention is illustrated schematically in FIG. 6 wherein the length z of the contact tip is generally in the range of 1.5 inches and preferably in the range of 2-3 inches. By using the present invention, diameter x of passage 102 can be substantially greater than diameter y of wire W. In practice, x is preferably 0.068 inches so that the diameter is oversized and not determined by the diameter of wire W, which diameter can be as small as about 0.035 inches. By making passage 102 oversized, contact tip 100 need not be specifically dimensioned for use with a single wire, but can be used with a number of different sized aluminum wires. Irrespective of the size of the wire, the wire connects tip 100 at point a F which is fixed to give a consistent pulse welding operation or MIG welding operation for aluminum. The diameter of wire W can vary noticeably. This is a great advantage in the welding of aluminum. The inventory of tips for different wires is drastically reduced at a substantial saving.
[0029] Symmetrical ceramic pressure block 130 is best shown in FIG. 10 as including a rectangular member formed of ceramic with a width m, height n and length o. As illustrated, the height and length are the same and the width is about 25% of the height. Consequently, opening 120 is rectangular with a width of substantially dimension m and a height of substantially dimension n. According to the orientation of block 130 in opening 120 either edge 132 or edge 134 engages wire W and forces it against surface 104 at a positive contact position opposite the pressure edge. Each edge has a tapered end 160 , 162 , 164 or 166 . In this manner, irrespective of the orientation of block 130 in opening 120 , wire W first engages a tapered end to cam block 130 outwardly against spring 150 as the wire is threaded through gun G. An advantage of the present invention is the interchangeable shape of generally symmetrical block 130 .
[0030] FIGS. 7 and 8 show a modified contact tip 100 ′ generally the same as tip 110 , except for a raised pressure pad 200 generally opposite to and matching the profile of edge 132 . The pad is elongated with a width m. An upper tapered end 102 allows threading of wire W through tip 100 ′ at the start of the welding process. Again, the diameter of opening 102 is oversized for wire W so that one tip fits generally all aluminum wires. If the wire is overly flexible and moveable in passage 102 below pressure block 130 , a thin ceramic sleeve 210 can be inserted into the passage to abut against the lower end of pad 200 , as shown in FIG. 8 . This ceramic sleeve has an inner opening 212 generally matching the diameter of wire W. The gap is in the range of 0.005-0.010 inches. When using this insulation sleeve, a different sleeve is inserted into the same contact tip 100 ′ to match the diameter of the wire. The only change in the tip is the selection of the ceramic guide sleeve 210 to accommodate a given wire. Thus, all the screw machine operations and boring of opening 120 is the same for all the aluminum wire diameters. A special sleeve is used for taking up the slack and preventing movement of wire W below block 130 , especially for smaller diameter aluminum wires. The features of FIGS. 7 and 8 are improvements of the general invention as previously described in connection with FIGS. 2-4 and FIG. 10 . Another improvement in the invention is illustrated in FIG. 11 which is a cross-sectioned view of FIG. 4 . Spring 150 in groove 140 surrounds the tip and pushes pressure block 130 inwardly against wire W. The C-shaped spring has distal ends 150 a, 150 b defining a gap 220 . By providing an elongated key boss 222 in groove 140 at a position opposite to opening 120 , gap 220 is oriented with respect to boss 222 . Spring 150 is held in the proper position around tip 100 or rip 100 ′ in groove 140 . This improvement in the invention is illustrated in FIGS. 4 and 11 .
[0031] An alternative contact tip 300 for aluminum wire W is illustrated in FIG. 9 as including an uppermost threaded end 302 and a lowermost exit end 304 with a large diameter passage 310 terminating in a lower rim 312 defining a smaller opening 314 generally matching the diameter of wire W. To assure that the contact point is only in the relatively short area p, passage 310 is provided with a ceramic insulator sleeve 320 with a tapered upper end 322 . Tip 300 provides a relatively precise contact point for wire W to allow a consistent aluminum welding process. This contact can be adjacent exit end 304 since it does not involve a metal spring 150 as used in the basic implementation of the present invention. This tip is a broad embodiment of the invention and does not involve the use of a pressure block; however, it provides a fixed point for electrical contact in the tip. This aspect of the invention uses a long contact tip with an element at a given location of passage 310 to assure a specific, fixed point of electrical contact. Rim 312 defines the fixed point. In the preferred embodiment, block 130 defines the specific point. Other modifications of this broad concept for aluminum pulse welding come within the invention.
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A contact tip for a welding gun having a central passage for a welding wire moving in a given direction toward a workpiece and receiving a welding signal by contact of the wire with the tip. The passage has an innermost end, an outermost exit end and a length of at least 1.5 inches and an opening in the contact tip intersects the passage so a pressure block slidably mounted in the opening is biased toward the wire by a spring around the contact tip urging the block against the wire. This tip is dimensioned and constructed to perform pulse welding by a relatively ductile aluminum wire.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention is related to touch-screens, and more particularly, to a novel method of interacting with the touch-screen through the use and recognition of circular gestures.
[0003] 2. Description of the Related Art
[0004] The hardware associated with touch-screens and the corresponding conventional method of operation are well known in the art. However, new modes of operation for interacting with a touch-screen are continually desired. For the ever-increasing demand for touch input devices, such as a touch-screen, there is a need to have a least strain and most intuitive gesture to detect sustained continuous adjustments. Circular gesturing on touch sensitive surface is the best way to indicate prolonged continual adjustments.
[0005] What is desired, therefore, is a method to parameterize and recognize circular gestures on touch sensitive surfaces such as a touch-screen.
SUMMARY OF THE INVENTION
[0006] The method of the invention, therefore, parameterizes circular gestures made anywhere on a touch sensitive surface. The method of the present invention includes extracting parameters to indicate clockwise or counter-clockwise motion of circular gestures made anywhere on a touch sensitive surface. The method of the present invention also includes extracting parameters to indicate the speed of the clockwise or counter-clockwise motion of circular gestures made anywhere on a touch sensitive surface.
[0007] The method to parameterize and recognize circular gestures on touch sensitive surfaces according to the present invention includes dividing the touch sensitive surface into four quadrants, detecting a transition from a first quadrant into a second quadrant, time-stamping and tracking each detected quadrant transition, and computing the time between quadrant transitions so that the circular speed and direction of the circular gestures on the touch sensitive surface can be detected. The detected direction can be either a clockwise or a counter-clockwise direction. Each of the four quadrants of the touch-screen is classified. Each touch point (X, Y) on the touch-screen across time is grouped in a respective quadrant depending on the changes in the current X and Y positions in a current touch frame with respect to a previous frame. A tracking touch point is classified in Quadrant 1 (Q 1 ) when a current Y coordinate is less than a previous Y coordinate and a current X coordinate is greater than a previous X coordinate. A tracking touch point is classified in Quadrant 2 (Q 2 ) when a current Y coordinate is greater than a previous Y coordinate and a current X coordinate is greater than a previous X coordinate. A tracking touch point is classified in Quadrant 3 (Q 3 ) when a current Y coordinate is greater than a previous Y coordinate and a current X coordinate is less than a previous X coordinate. A tracking touch point is classified in Quadrant 4 (Q 4 ) when a current Y coordinate is less than a previous Y coordinate and a current X coordinate is less than a previous X coordinate. Each tracked touch point is monitored for quadrant transitions, and a clockwise touch point movement is recognized by a sequence of increasing quadrant numbers. Each tracked touch point is monitored for quadrant transitions, and a counter-clockwise touch point movement is recognized by a sequence of decreasing quadrant numbers. The method of the present invention further provides a quadrant transition value. A quadrant transition value of 00 comprises a no quadrant transition value. A quadrant transition value of 01 comprises a clockwise quadrant transition value. A quadrant transition value of 10 comprises a counter-clockwise quadrant transition value. The method of the present invention further provides a timestamp value when there is a quadrant transition. The timestamp value measures the time lapsed between a current and a previous quadrant transition.
[0008] A first method for circular gesture recognition associated with a touch-screen according to the present invention includes providing a timer loaded with a chosen number of ticks to count down to zero, and the timer is reloaded whenever it reaches zero or when there is a change in direction of a quadrant transition, providing a transition counter that increments on every quadrant transition, and the counter is cleared on timer load or reload, and if the number of quadrant transitions in the same direction is equal to or above the criteria threshold when the timer reaches zero, a circular gesture is recognized.
[0009] A second method for circular gesture recognition associated with a touch-screen according to the present invention includes providing a transition counter that increments on every quadrant transition, and the counter is cleared when a chosen fixed number of same direction quadrant transitions is reached or when there is a direction change before the chosen number of transitions is reached, and providing a timestamp that is accumulated for every quadrant transition, and the timestamp accumulation is cleared when the transition counter is cleared, and if the accumulated time is less than the threshold time when the transition counter reaches the chosen number of quadrant transitions, a circular gesture is recognized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Other objects and advantages of the present invention will become apparent from the following description of the preferred embodiment with reference to the drawings, in which:
[0011] FIG. 1A is a block diagram of the quadrant processing flow for a touch-screen system according to the present invention;
[0012] FIG. 1B is a flow chart associated with the block diagram of FIG. 1A ;
[0013] FIG. 2 is a diagram of touch movements on a touch-screen classified into four quadrants according to the present invention;
[0014] FIG. 3 is a diagram of a touch-screen illustrating the definition of clockwise movement according to the quadrant touch-screen convention used in FIG. 2 ;
[0015] FIG. 4 is a diagram of a touch-screen illustrating the definition of counter-clockwise movement according to the quadrant touch-screen convention used in FIG. 2 ;
[0016] FIG. 5 is a flow diagram illustrating a first method of circular gesture and speed recognition according to the present invention; and
[0017] FIG. 6 is a flow diagram illustrating a second method of circular gesture and speed recognition according to the present invention.
DETAILED DESCRIPTION
[0018] Referring now to FIG. 1A , a touch-screen system 100 is shown in FIG. 1A for driving a touch-screen (not actually shown in FIG. 1A ). The touch-screen system 100 includes drive/sense circuitry 102 for communicating with the X-lines and Y-lines in the touch-screen. The drive/sense circuitry 102 is in communication with a capacitance-to-voltage conversion block 104 to produce an output voltage. The output voltage of the capacitance-to-voltage conversion block 104 is sensed by an analog-to-digital (ADC) quantization block 106 to provide a sixteen bit digital output. The output of the ADC block 106 is coupled to a frame buffer 108 . The digital output of the frame buffer 108 is coupled to a touch X, Y coordinate determination block 110 to provide an (X, Y) output. The output of the coordinate determination block 110 is coupled to a touch ID (TID) assignment block 112 . The TID assignment block has an output that provides X, Y, and TID information for normal touch-screen information processing. The X, Y, and TID information is received by the quadrant processing block 114 including a quadrant classification block 116 and a quadrant transition tracking block 118 . The quadrant classification block 116 receives the X, Y, and TID information and provides X, Y, TID, and QN (Quadrant Number) information at a first output. A second output of the quadrant classification block 116 provides new TID information including X, Y, TID, and QN information. The quadrant transition tracking block 118 receives the X, Y, TID, and QN information, as well as system time information to provide the X, Y, TID, QT (Quadrant Transition, clockwise or counter-clockwise) and TS (Time Stamp or time between transitions) information. The outputs of the quadrant processing block 114 is further used for recognition of circular gestures as is described in further detail below.
[0019] A flow chart 120 of the quadrant processing method according to the present invention is shown in FIG. 1B . FIG. 1B illustrates the quadrant processing method for a typical touch-screen frame data processing flow according to the present invention. Flow chart 120 starts with a sampled touch frame at step 122 . The touch X, Y coordinates of the touch frame are determined at step 124 . The point coordinates are then tracked at step 126 . The tracked points are then processed at the quadrant processing block 128 . The quadrant processing task 128 is divided into two parts: quadrant classification 130 and quadrant tracking 132 .
[0020] Quadrant classification is further described with respect to FIG. 2 . It should be noted that classification is based on relative touch movement on a TID and not on absolute position of TID on the screen. Point movement history is classified into FOUR quadrants Quadrant 1 (Q 1 ), Quadrant 2 (Q 2 ), Quadrant 3 (Q 3 ), and Quadrant 4 (Q 4 ) shown in FIG. 2 . In FIG. 2 , X and Y are the Cartesian coordinates of a touch array surface. Each touch point (X,Y) across time is grouped in the respective quadrant depending on the changes in the current X and Y positions in current touch frame from previous frame. A tracking touch point is classified in Quadrant 1 (Q 1 ) when the current Y coordinate is less than the previous Y coordinate and the current X coordinate is greater than the previous X coordinate. A tracking touch point is classified in Quadrant 2 (Q 2 ) when the current Y coordinate is greater than the previous Y coordinate and the current X coordinate is greater than the previous X coordinate. A tracking touch point is classified in Quadrant 3 (Q 3 ) when the current Y coordinate is greater than the previous Y coordinate and the current X coordinate is less than the previous X coordinate. A tracking touch point is classified in Quadrant 4 (Q 4 ) when the current Y coordinate is less than the previous Y coordinate and the current X coordinate is less than the previous X coordinate.
[0021] Clockwise quadrant tracking is shown in FIG. 3 . After quadrant classification, each tracked touch point can be monitored for quadrant transitions. FIG. 3 explains the clockwise quadrant definition. Clockwise touch point movement can be recognized by a sequence of increasing quadrant numbers with Q 4 returning to Q 1 as shown in FIG. 3 . A tracked touch point can start from any quadrant number.
[0022] Counter-Clockwise quadrant tracking is shown in FIG. 4 . After quadrant classification, each tracked point can be monitored for quadrant transitions. FIG. 4 explains the counter-clockwise quadrant definition. Counter-clockwise touch point movement can be recognized by a sequence of decreasing quadrant numbers with Q 1 returning to Q 4 as shown in FIG. 4 . A tracked touch point can start from any quadrant number.
[0023] According to the method of the present invention, it is important that quadrant transition speed be measured. Each quadrant transition can be time-stamped and tracked. The time between quadrant transitions can be computed to indicate circular speed of gestures. The two additions to the information of a tracked TID (QT,TS), referred to in FIG. 1A , are used to recognize circular gestures and the corresponding speed thereof as follows:
[0024] Quadrant Transition (QT) has three values:
For an example of QT encoding:
‘00’—no quadrant transition ‘01’—clockwise quadrant transition ‘10’—anticlockwise quadrant transition
[0029] A timestamp (TS) is provided when there is a quadrant transition. TS measures the time lapsed between a current and a previous quadrant transition. This time information is useful to compensate for latency in processing the QT data. Some systems may choose to ignore TS for simplicity or if latency is not an issue.
[0030] A first method for gesture and speed recognition according to the present invention uses a transition threshold criteria. A minimum number of quadrant transitions in the same direction in a chosen period of time is used in this method. A timer is loaded with a chosen number of ticks to count down to zero. This timer is reloaded whenever it reaches zero or when there is a change in direction of quadrant transition. A transition counter increments on every quadrant transition. This counter is cleared on timer load or reload. If the number of quadrant transitions in the same direction is equal to or above the criteria threshold when the timer reaches zero, circular gesture is recognized. The higher the number of same direction quadrant transitions is above the criteria threshold, the faster is its circular speed. Timestamp (TS) information is not used in this method.
[0031] The first method is shown in the flow diagram 500 of FIG. 5 . The method starts at a first step 502 . A timer is loaded and the transition count is reset at step 504 . At step 506 the timer is decremented. At decision block 508 the method detects whether a directional change has been made. If yes, the timer is again loaded and the transition count is reset at step 504 . In no, the method continues to decision block 510 . At decision block 510 the method detects whether the timer value is equal to zero. If no, the timer is again decremented at step 506 . If yes, the method continues to decision block 512 . At decision block 512 , the method detects whether or not the transition count is greater or equal to a predetermined threshold. If no, the timer is again loaded and the transition count is reset at step 504 . If yes, then a circular gesture is recognized at step 514 , and the timer is again loaded and the transition count reset at step 504 .
[0032] A second method for gesture and speed recognition according to the present invention uses a time threshold criteria. A maximum time taken for a chosen number of quadrant transitions in the same direction is used in this method. A transition counter increments on every transition. This counter is cleared when the chosen fixed number of same direction transitions is reached or when there is a direction change before the chosen number of transitions is reached. The timestamp is accumulated for every quadrant transition. The timestamp accumulation is cleared when the transition counter is cleared. If the accumulated time is less than the threshold time when the transition counter reaches the chosen number of quadrant transitions, a circular gesture is recognized. The lower the accumulated time is below the threshold time, the faster is its circular speed.
[0033] The second method is shown in the flow diagram 600 of FIG. 6 . The method starts at a first step 602 . A timestamp accumulator and the transition count is reset at step 604 . At decision block 606 the method detects whether a quadrant transition has been made. If no, the method continues to periodically check whether or not a quadrant transition has been. In yes, the method increments the transition count at step 608 . At decision block 610 detects whether or not a directional change has been made. If yes, the time accumulator and the transition count is reset at step 604 . If no, the timestamp is accumulated at step 612 . At decision block 614 , the method detects whether or not the transition count has been met. If no, the method detects whether or not a quadrant transition has been made at decision block 606 . If yes, then the method checks whether or not the time accumulator value is less than a predetermined threshold at decision block 618 . If no, then the time accumulator and transition count is again reset at step 604 . If yes, then a circular gesture is recognized at step 616 , and the time accumulator and transition count is reset at step 604 .
[0034] Since the quadrant classification and quadrant transition tracking are based on a single tracked touch ID (TID), the method of the present invention can be expanded to recognize circular gestures of other TIDS present on the same touch-screen
[0035] While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not as a limitation. Thus, the breadth and scope of the present invention 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.
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A method to parameterize and recognize circular gestures on touch sensitive surfaces includes dividing the touch sensitive surface into four quadrants, detecting a transition from a first quadrant into a second quadrant, time-stamping and tracking each detected quadrant transition, and computing the time between quadrant transitions so that the circular speed and direction of the circular gestures on the touch sensitive surface can be detected. The detected direction can be either a clockwise or a counter-clockwise direction.
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SPONSORED RESEARCH AND DEVELOPMENT
Research and development of the present invention and application have not been Federally-sponsored, and no rights are given under any Federal program.
CROSS REFERENCE TO RELATED APPLICATIONS
This is a division of application Ser. No. 10,464, filed Feb. 3, 1987, now U.S. Pat. No. 4,754,899.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to hand-held dispensers, and more particularly to dispensers of the type having a base cap part that is applied to a container, and an overcap or twist cap applied to the base cap, and wherein discharge of the container contents is controlled by manually turning the twist cap between an open, discharging position and a closed, sealing position.
2. Description of the Related Art Including Information Discussed Under 37 CFR SS1.97-1.99
One prior twist cap construction is illustrated and described in my U.S. Pat. No. 4,424,918, and relates to a non-resealable dispenser construction. A twist or cover cap is turnably carried on a base cap in such a manner that when the cover cap is initially unscrewed, a shoulder on the latter is received in a groove on the base cap and the resulting interference therebetween prevents the twist cap from being pushed down and re-seated on the base cap. Inadvertent build-up of pressure in the dispenser is thus prevented, following initial use.
This patented dispenser incorporated no means for controlling the flow of product being discharged. The rate of discharge was determined by the size of the openings on opposite sides of the stopper peg, and the viscosity of the liquid.
U.S. Pat. No. 4,438,870 shows a different construction wherein a twist cap is raised by cam lugs carried on its underside and which engage cam tracks on a base cap, and is retracted by cooperable threads on both the twist and base caps. While this construction was capable of providing an adjustable flow, control was difficult to set or calibrate, since it depended for the most part on the relatively sudden removal of the stopper peg from the orifice in the twist cap. In actuality, the control was more in the nature of a simple "on-off" type of control, rather than one providing continuous adjustment over a reasonably well defined range.
Thus, the capability of providing a simple and foolproof high precision adjustable discharge function in a twist cap was not provided in any of the devices disclosed in the patents listed above.
A number of other twist cap constructions have been proposed and produced. It is believed that the above identified two patents constitute the closest prior art of which applicant is aware.
SUMMARY OF THE INVENTION
The above disadvantages and drawbacks of prior dispensing cap constructions are obviated by the present invention which has for one object the provision of a novel and improved dispensing cap which is both extremely simple in operation, and which provides a calibrated, adjustable-rate discharge of the contents so as to enable the consumer to dispense, with a high degree of accuracy, the precise amount of product desired.
A related object of the invention is to provide an improved dispensing cap construction as above set forth, wherein a flow rate can be pre-set by the consumer, prior to the occurrence of any discharge of the product.
Still another object of the invention is to provide an improved dispensing cap construction as above characterized, wherein a predetermined discharge flow rate can be "dialed" or set, and following use of the dispenser and closing of the same, the exact same flow rate re-set at a later time.
Yet another object of the invention is to provide an improved dispensing cap construction of the kind indicated, wherein a plurality of different, calibrated flow rates can be set by the consumer, either prior to or during use of the dispenser.
A still further object of the invention is to provide an improved dispensing cap construction as outlined above, wherein the flow rate mechanism, once set, resists subsequent inadvertent movement which might otherwise disturb the initially selected, desired setting.
Still another object of the invention is to provide an improved dispensing cap construction wherein the components can be readily fabricated as molded parts in simple mold cavities, thus maintaining the manufacturing costs as low as possible.
Yet another object of the invention is to provide an improved dispensing cap construction in accordance with the foregoing wherein two separate and distinct closed, sealing positions can be utilized, one adapted for a temporary sealing of the dispenser, and a second, more permanent sealing position intended for use when the dispenser is initially filled at the factory, and shipped to a distributor, warehouse, store, etc.
The above objects are accomplished by a dispensing cap construction comprising a base cap attachable to a container, the base cap having a spout formation provided with a side wall and with a flow passage in the side wall, and a cover cap which is both turnably mounted on the base cap and axially movable thereon between a lowered sealing position and a raised dispensing position. The cover cap has a discharge orifice, and a valving wall and discharge passage in the valving wall, both of which move circumferentially around the side wall of the spout formation. The valving wall moves into and out of a sealing position wherein it covers or uncovers the flow passage in the side wall of the base cap when the cover cap is turned. The valving wall has positions intermediate its full cover and full uncover positions wherein it only partially closes the flow passage. The discharge orifice of the cover cap is sealed at a point downstream of the flow passage of the base cap when the cover cap is in its lowered position thereon.
Other features and advantages will hereinafter appear.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, illustrating a preferred embodiment of the invention:
FIG. 1 is a view, partly in side elevation and partly in axial section, of the adjustable flow rate dispenser cap construction made in accordance with the present invention. The device is shown in a fully closed, sealing position.
FIG. 2 is an axial section of the adjustable flow rate dispenser cap construction on FIG. 1, shown with the cover or twist cap in a raised position on the base cap, and with a valving wall of the cover cap closing off flow passages in a spout formation of the base cap.
FIG. 3 is a top plan view of the adjustable flow rate dispenser cap construction of FIGS. 1 and 2, shown with the cover cap in a fully closed sealing position on the base cap.
FIG. 4 is a view, partly in side elevation and partly in axial section, of the base cap of the construction of FIGS. 1-3. The base cap is shown rotated 90° from the view of FIG. 2.
FIG. 5 is a top plan view, partly broken away, of the base cap of the construction of FIGS. 1-4.
FIG. 6 is a horizontal section taken on the line 6--6 of FIG. 2. The twist cap is illustrated as having been turned to a position wherein valving walls thereof completely close off flow passages in the spout formation of the base cap.
FIG. 7 is a view like that of FIG. 6, except showing the cover cap turned to a position wherein the valving walls of the cover cap fully uncover or expose flow passages in the spout formation of the base cap, thereby permitting a high rate of discharge of the dispenser contents to occur.
FIG. 8 is a view like FIGS. 6 and 7, except showing the cover cap turned to an intermediate position, wherein the valving walls of the cover cap only partially cover the flow passages in the spout formation of the base cap, thereby permitting a precisely calibrated discharge of the dispenser contents to occur.
FIG. 9 is a bottom plan view of the cover or twist cap of the construction of FIGS. 1-3 and 6-8, and
FIG. 10 is a fragmentary axial section of the twist cap, particularly showing the discharge passage therein, such passage having an upper tubular portion, and a lower portion constituted as a semi-cylindrical recess in the valving wall of the twist cap.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIGS. 1-3 there is illustrated a dispensing cap construction designated generally by the numeral 10, comprising a base cap 12 and a cover cap or twist cap 14 carried thereby. The base cap 12 has a depending skirt 16 with internal screw threads 18 intended to mate with cooperable external threads on the neck of a container (not shown). An inner skirt 20 is provided, and is received in the container opening so as to form a seal therewith, all in the usual manner.
The base cap 12 is particularly illustrated in FIGS. 4 and 5. It has a transverse top wall 22, FIG. 2, and an annular peripheral recess 24, FIGS. 2 and 4, formed therein. Disposed within the recess 24 is a pair of arcuate cam tracks 26 and 28, each extending through an angle on the order of 135 degrees, although other track lengths could be substituted for those shown.
The twist cap 14 is particularly illustrated in FIGS. 9 and 10. It has a depending skirt 30 which is received in the annular recess 24 of the base cap 12 when the two are assembled and the twist cap 14 is disposed in the fully seated, closed, sealing position as in FIG. 1. Disposed on the underside of the twist cap, and extending radially inwardly from the skirt is a lug 32 constituting a cam follower, FIG. 9, which is intended to ride up one of the cam tracks 26, 28 of the base cap 12 as the twist cap 14 is turned in an unscrewing direction. As can be readily seen, the twist cap 14 is moveable axially on the base cap 12, and as the cam lug 32 rides up the cam track 26, it carries with it the twist cap 14.
In FIG. 4, the base cap 12 is provided with an upstanding spout portion 34 having a bore that communicates with the area adjacent the threads 18 of the base cap. The spout portion 34 has an annular side wall containing diametrically opposed arcuate cut-out portions constituting flow passages 36, 38 for liquid to pass through. The passages are illustrated particularly in FIGS. 6-8. At the top of the spout portion 34 is a transverse wall 40 carrying an upstanding stopper pin or sealing peg 42 that is receivable in an upper discharge passage 44 in the twist cap, this upper passage 44 constituting a discharge orifice. The sealing relationship of the peg 42 and the walls of the orifice 44 is shown in FIG. 1. The outer surface of the annular wall of the spout has a pair of spaced annular external beads 46 and 48. The lower bead 46 is intended to be by-passed by a cooperable inwardly extending retainer and ratchet tooth 50, of the twist cap 14, FIGS. 2 and 9, as the twist cap arrives at a raised position wherein the lug 32 thereof is nearing the upper end of the cam track 26, during initial unscrewing of the twist cap 14.
The twist cap 14 has an annular side wall, the exterior surface of which is generally conical, and the inner surface of which is stepped.
In accordance with the present invention, a central portion of the stepped wall is cooperable with the flow passages 36, 38 of the spout portion 34, and constitutes a valving wall 52 that controls movement of product through the flow passages 36 and 38 by forming two oppositely disposed arcuate surfaces or shutters 54 and 56 capable of moving across and blocking the passages. As best seen in FIGS. 6-8, the shutters 54, 56 are carried by, and thus turn with the twist cap 14. Arcuate recesses 58, 60 in the valving wall 52, constituting lower discharge passages of the twist cap 14, are defined by the opposite shoulders of the shutters 54 and 56. These recesses or grooves are shallow and wide, being also illustrated in FIGS. 6-8. In the appended claims the peg 42 and lower end of the passage 44 are referred to as a cooperable sealing means closing off the remainder of the dispensing orifice 44. Also, the valving wall 52, comprising shutters 54 and 56, and the flow passages 36, 38 are referred to as cooperable valving means separate and distinct from the sealing means, and responsive to turning of the cover cap when it is in its raised position on the base cap, for selectively establishing and interrupting communication between the bore of the spout formation and the dispensing orifice of the cover cap.
By the invention there is provided a plurality of axially aligned, longitudinal ribs 62 extending between the annular beads 46, 48, as in FIG. 4. The ribs 62 define a plurality of vertical grooves and thus constitute, with the tooth 50, a ratchet mechanism. The ribs are shown in the broken away portion of FIG. 5. During unscrewing of the twist cap 14, this tooth 50 snaps past the lower bead 46, arriving at the space between the beads 46, 48, and becomes seated in one of the vertical grooves defined by the ribs 62. The ratchet action of the tooth 50 and ribs 62 restrains the twist cap against inadvertent turning movement in the absence of a manually applied turning force thereto. It thus constitutes a yieldable detent.
FIG. 6 illustrates the relative positions of the valving wall shutters 54, 56 and flow passages 36, 38 corresponding to a complete seal of the dispenser. That is, portions 54, 56 of the valving wall 52 completely cover the flow passages 36, 38 of the spout portion 34.
In FIG. 7, the shutters 54, 56 have been shifted 90° to positions wherein the flow passages 36, 38 lie radially within the recesses 60, 58 between the shutters 54, 56, this corresponding to a fully open, discharging position of the twist cap. FIG. 8 illustrates a condition wherein the valving wall portions or shutters 54, 56 of the twist cap close off just under one-half of each flow passage 36, 38, giving rise to a partial restriction of product flow.
Also, by the invention, there are provided cooperable marker means comprising indicia 64 on an annular flat surface 66 of the base cap 12 and an index mark on the lower portion of the twist cap, for indicating the relative positions of the valving wall shutters 54, 56 and flow passages 36, 38. For example, the index mark can take the form of an external nib 68 on the twist cap 14, and can be aligned with an arrow designated "FULL OPEN" on the base cap 12, which would correspond to the showing of FIG. 7. Similarly, the twist cap 14 can be turned such that the nib 68 will align with the designations "3", "2", or "1", indicating successive reduction in flow through the flow passages 36, 38. With the nib 68 aligned with the arrow "CLOSE-PUSH DOWN", the shutters 54, 56 completely cover the flow passages 36, 38, as in FIG. 6; in addition, the cam lug 32 overlies the region adjacent the end or shoulder of the cam track 28, the lug being shown in dotted outline in FIG. 5. In this position, the dispenser is in a sealing condition; it can be opened by merely turning the twist cap 14 in either a clockwise or counterclockwise direction. Alternately, the twist cap 14 can be pushed down such that the tooth 50 by-passes the lower bead 46, and the skirt 30 of the twist cap again occupies the recess 24 of the base cap, as in FIG. 1. This position of the twist cap 14 as shown in FIG. 1 provides a more secure seal than that where the twist cap 14 is raised, since from the position of FIG. 1, turning of the twist cap in a clockwise direction is effectively prevented by the engagement of the lug 32 with the shoulder at the upper end of the cam track 28. Even though turning of the twist cap 14 in a counterclockwise direction is possible, the dispenser would not arrive at an open condition until the cam lug 32 had ridden completely up the cam track 26, and had passed the end thereof. In the position of FIG. 1, the sealing peg 42 occupies the discharge passage 44, thereby providing an additional seal downstream from the flow passages 36, 38. Accordingly, the dispensing cap is always initially assembled with the twist cap positioned as shown in FIG. 1, to minimize the possibility of inadvertent leakage during shipping and storage, distribution to warehouses, or display in merchandising outlets or department stores, etc.
Also, by the invention the lower portion 70 of the valving wall 52 is always disposed completely below the flow passages 36, 38, even when the twist cap 14 is raised as in FIG. 2. This construction prevents any liquid from flowing downwardly in this figure, toward the upper bead 48 on the spout portion 34. Since this lower portion 70 of the valving wall 52 is cylindrical, and the cooperable outer surface 72 of the spout portion 34 engaged by this valving wall portion 70 is also cylindrical, an effective seal is realized at all times, irrespective of the relative turning which occurs between the two parts. It is considered that the seal is important from the standpoint of eliminating any build up of solidified product in the area above the bead 48, which might eventually interfere with smooth operation of the dispenser. The wall of the spout portion 34 adjacent to the surface 72 and to the flow passages is tapered, as shown in FIGS. 1 and 2, with the thin portion of the taper being just beneath the respective flow passage opening 36 or 38.
The disclosed construction has a number of distinct advantages. Since the flow rate of the product being dispensed is controlled by a pair of shutters or valving wall portions that open or close by the same angular extent and at the same angular velocity as that at which the twist cap is turned, a very precise positioning of the shutters is made possible, resulting in a high degree of control, regardless of the viscosity of the substance being dispensed. A transition from a fully closed to a fully open position occurs with somewhat less than a 90° turning of the twist cap, which is convenient for the user, since multiple turns are not required, as in previous cap designs. Stated differently, turning the twist cap from the position shown in FIG. 7 to that of FIG. 6 closes off the dispenser from its fully open position, and the degree of control or resolution is seen to be high. The number of increments or steps provided is limited only by the spacing of the ribs 62 on the spout portion 34. The number of such ribs 62 can be increased if necessary, to increase the resolution or degree of control as might be required with substances of different viscosities.
The disclosed construction consists essentially of two one-piece molded parts which can be readily fabricated in relatively inexpensive mold cavities and assembled by automatic assembly equipment.
The device is thus seen to represent a distinct advance and improvement in the field of hand-held dispensers.
Variations and modifications are possible without departing from the spirit of the invention.
Each and every one of the appended claims defines an aspect of the invention which is separate and distinct from all others, and accordingly it is intended that each claim be treated as such when examined in light of the prior art devices in any determination of novelty or validity.
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A dispensing cap construction including a base cap attachable to a container, the base cap having a spout formation provided with a side wall and with a flow passage in the side wall, and a cover cap which is both turnably mounted on the base cap and axially movable theron between a lowered sealing position and a raised dispensing position. The cover cap has a discharge orifice, and a valving wall and dischage passage in the valving wall, both of which move circumferentially around the side wall of the spout formation. The valving wall moves into and out of a sealing position wherein it covers or uncovers the flow passage in the side wall of the base cap when the cover cap is turned. The valving wall has positions intermediate its full cover and full uncover positions wherein it only partially closes the flow passage. The discharge orifice of the cover cap is sealed at a point downstream of the flow passage of the base cap when the cover cap is in its lowered position thereon.
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FIELD OF THE INVENTION
[0001] The invention relates to a differential current output unit for supplying an output current to a load in accordance with an input differential voltage inputted to the unit.
BACKGROUND OF THE INVENTION
[0002] It is often the case that a load such as an electric motor is driven by an output current in accord with the polarity and the magnitude of a differential input voltage. An example of such motor is a single-phase electric motor for driving a fan, a voice coil electric motor (VCM) of a hard disk drive (HDD), and a dc motor for driving a VTR, a CD-ROM, and a DVD drive.
[0003] Some of them are controlled by a signal or signals controlling on-off operation of the output transistors of the drive circuit of the motor based on the comparison of the input voltage with a reference voltage. This type of drive circuit, however, has a drawback in that the output current sharply changes across the point where the polarity of the output current changes (or zero-crossing point), and generates big noise. Furthermore, an inflow transistor circuit and an outflow transistor circuit of the drive circuit can be simultaneously turned on to allow a so-called huge penetration current to flow, and hence requires a delay circuit to circumvent the penetration current.
[0004] In order to circumvent such sharp change in the output current by smoothly switching the polarity of the output current across the zero-crossing point, an operational amplifier may be used to control the output current of the power amplifier circuit of a drive circuit. (See, for example literature 1; Masaomi Suzuki, “Standard Textbook: Designing Transistor Circuits”, 13th edition, CQ Publishing Co., Jul. 1, 1998, p. 315, FIG. 27.)
[0005] However, a drive circuit utilizing an operational amplifier not only has a complicated circuit configuration but also requires extra phase compensation capacitors. Since the drive circuit is usually built in on an IC chip, the chip must have a large area for the phase compensation capacitors. This raises the production cost of the drive circuit.
SUMMARY OF THE INVENTION
[0006] It is, therefore, an object of the invention to provide a differential current output unit having a simplified circuit structure involving a minimum number of capacitors and a minimum chip area, yet capable of smoothly changing its output current in accordance with the change in an inputted differential input voltage.
[0007] It is another object of the invention to provide a differential current output unit for providing an output current in a stable manner, affected only negligibly by changes in current amplification factors of transistors due to, for example, a change in temperature.
[0008] A differential current output unit of the invention comprises:
[0009] a difference input circuit 10 that includes
a first constant current source Q 17 for providing a first constant current I 0 , a first and a second differential amplification transistors Q 15 and Q 16 , respectively, for amplifying an inputted differential input voltage Vin so as to distribute the first constant current I 0 among the differential amplification transistors, a first current mirror source transistor Q 11 for generating a first voltage (referred to as first mirror source voltage) i proportional to a first current I 1 flowing through the first differential amplification transistor Q 15 , and a second current mirror source transistor Q 13 for generating a second voltage (referred to as second mirror source voltage) ii proportional to a second current I 2 flowing through the second differential amplification transistor Q 16 ;
[0014] a current subtraction circuit 20 that includes
a first mirror transistor (referred to as first mirror target transistor) Q 22 for flowing therethrough a first mirror current M*I 1 that is M times the first current I 1 in response to the first mirror source voltage i, with M being a first predetermined mirror ratio, and a second mirror transistor (referred to as second mirror target transistor) Q 21 for flowing therethrough a second mirror current M*I 2 that is M times the second current I 2 in response to the second mirror source voltage ii,
[0017] wherein the subtraction circuit is adapted to output a difference current M*I 1 -M*I 2 that is the difference between the first mirror current M*I 1 and second mirror current M*I 2 ;
a delivery circuit 30 for generating current output instruction signals vi-ix in accord with the magnitude of the difference current M*I 1 -M*I 2 and for delivering the current output instruction signals in accord with the polarity of the difference current M*I 1 -M*I 2 ; and
[0019] a current output circuit 40 having a multiplicity of output transistor circuits 40 - 1 - 40 - 4 each including a third mirror source transistor that is enabled by one of the current output instruction signals and a third mirror target transistor for flowing therethrough an output current that is N times the current flowing through the third mirror source transistor, with N being a second predetermined mirror ratio, wherein the current output circuit 40 is adapted to supply an output current Iout to a load 70 in a positive or a negative direction in accord with the polarity and the magnitude of the current output instruction signals.
[0020] The differential current output unit may have a current level setting circuit 60 for controlling the current level I 0 of the first constant current source Q 17 .
[0021] In the current subtraction circuit 20 , the first mirror target transistor Q 22 may be serially connected at a node to a second constant current source Q 24 supplying a second constant current M*I 0 /2 so as to output a first difference current from the node in accord with the difference current M*I 1 -M*I 2 , and the second mirror target transistor Q 21 may be serially connected at a node to a third current source Q 23 supplying the second constant current M*I 0 /2 so as to output from the node a second difference current M*I 2 -M*I 1 having opposite polarity with respect to the first difference current M*I 1 -M* 12 .
[0022] The differential current output unit may be provided with a current level setting circuit 60 for simultaneously controlling the current levels of the first, second, and third constant current sources Q 17 , Q 24 , and Q 23 , respectively, by the same ratio.
[0023] The current subtraction circuit 20 A may be modified to include
[0024] a first mirror target transistor Q 21 a for flowing therethrough the first mirror current M*I 1 connected in series with a first subtraction transistor Q 24 a for flowing therethrough a current M*I 2 that is M times the second current I 2 in accord with the second mirror source voltage ii to thereby output from the node a first difference current in accord with the difference current M*I 1 -M*I 2 , and
[0025] a second mirror target transistor Q 26 a for flowing therethrough the second mirror current M*I 2 connected in series with a second subtraction transistor Q 29 a for flowing therethrough a current M*I 1 that is M times the first current I 1 in accord with the first mirror source voltage i to thereby output from the node of these transistors a second difference current M*I 2 -M*I 1 of opposite polarity with respect to the first difference current M*I 1 -M*I 2 , wherein M is the second mirror ratio.
[0026] The delivery circuit 30 may include:
[0027] a first delivery transistor circuit Q 32 and a second delivery transistor circuit Q 33 for respectively outputting a current output instruction signal that is controlled in accordance with the difference current M*I 1 -M*I 2 when the difference current has negative polarity; and
[0028] a third delivery transistor circuit Q 31 and a fourth delivery transistor circuit Q 34 for respectively outputting a current output instruction signal that is controlled in accordance with the difference current M*I 1 -M*I 2 when the difference current has positive polarity.
[0029] The current output circuit 40 may include:
[0030] a first output transistor circuit 40 - 1 for flowing therethrough an output current in response to a current output instruction signal vii received from the first delivery transistor circuit Q 32 ;
[0031] a second output transistor circuit 40 - 2 for flowing therethrough an output current in response to a current output instruction signal viii received from the second delivery transistor circuit Q 33 ;
[0032] a third output transistor circuit 40 - 3 for flowing therethrough an output current in response to a current output instruction signal vi received from the third delivery transistor circuit Q 31 ; and
[0033] a fourth output transistor circuit 40 - 4 for flowing therethrough an output current in response to a current output instruction signal ix received from the fourth delivery transistor circuit Q 34 , wherein the current output circuit 40 is adapted to establish
[0034] a first load current path for flowing the output current of the first output transistor circuit 40 - 1 to an external load and flowing the output current of the second transistor circuit 40 - 2 from the external load, and
[0035] a second load current path, opposite in direction with respect to the first current path, for flowing out the output current of the third output transistor circuit 40 - 3 to the external load and flowing in the output current of the fourth output transistor circuit 40 - 4 from the external load.
[0036] Each of the first through fourth output transistor circuits 40 - 1 - 40 - 4 , respectively, may include a mirror source transistor controlled by respective current output instruction signals received from the delivery circuit 30 , and a mirror target transistor for flowing therethrough a current that is N times the current flowing through the mirror source transistor, where N is the second predetermined mirror ratio.
[0037] The first and third output transistor circuits 40 - 1 and 40 - 3 , respectively, may include a mirror source transistor controlled by respective one of current output instruction signals vii and vi received from the delivery circuit 30 and a mirror target transistor for flowing therethrough a current that is N times the current flowing through the mirror source transistor, wherein N is the second mirror ratio. The second and fourth output transistor circuits 40 - 2 and 40 - 4 , respectively, may include a mirror source transistor controlled by a respective one of current output instruction signals viii and ix received from the delivery circuit 30 and a mirror target transistor for flowing therethrough a current that is N×α times the current flowing through. this mirror source transistor, wherein N is the second mirror ratio and α is an arbitrary number other than 1.
[0038] Each of the first through fourth output transistor circuits 40 - 1 - 40 - 4 , respectively, may have a first current mirror circuit having a fourth predetermined mirror ratio Q and being controlled by a respective current output instruction signal received from the delivery circuit 30 , and a second current mirror circuit having a fifth predetermined mirror ratio P and being controlled by the output current of the first current mirror circuit.
[0039] Since a differential current output unit of the invention uses no operational amplifier and fewer capacitors, the unit has a simplified circuit structure that can be formed on a smaller chip area.
[0040] Moreover, smooth zero-point crossing of the output current is secured, since the output current changes to accurately follow the input voltage, thereby resulting in reduced noise.
[0041] Moreover, since a delivery circuit is used to separate the inflow- and outflow-transistor circuits, no penetration current will flow through the inflow- and outflow-output transistor circuits, thereby advantageously preventing destruction of the output transistors due to penetration current and reducing the power loss.
[0042] Still further, since the current level of the output transistor circuits can be controlled by controlling the common emitter current level (i.e. constant current level) of the difference input circuit, the level of the output current can be easily adjusted.
[0043] In addition, since the differential current output unit of the invention is entirely formed of differential circuits and current mirror circuits having predetermined mirror ratios, current output characteristics of the unit are little affected by a change in, for example, current gain hfe of a transistor involved.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] FIG. 1 is a schematic circuit diagram of a differential current output unit in accordance with a first embodiment of the invention.
[0045] FIG. 2 is a circuit diagram illustrating the operation of the differential current output unit of FIG. 1 .
[0046] FIG. 3 is schematic circuit diagram of a subtraction circuit for use in the differential current output unit in accordance with a second embodiment of the invention.
[0047] FIG. 4 is a schematic circuit diagram of a current output circuit for use in a differential current output unit in accordance with a third embodiment of the invention.
[0048] FIG. 5 is a schematic circuit diagram of another current output circuit for use in a differential current output unit in accordance with a fourth embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0049] Referring to the accompanying drawings, embodiments of the invention will now be described in detail with reference to a differential current output unit. FIG. 1 shows a circuit structure of a differential current output unit in accordance with a first embodiment of the invention. FIG. 2 shows a diagram describing the operation of the differential current output unit of FIG. 1 .
[0050] As shown in FIG. 1 , a difference input circuit 10 of the differential current output unit is supplied with an input voltage Vin. A series connection of an NPN type bipolar transistor (hereinafter referred to as NPN transistor) Q 17 and a resistor R 15 forms a first constant current source. This first constant current source provides a first constant current 10 in response to a current level setting signal iii. The emitters of a first NPN transistor Q 15 and a second NPN transistor Q 16 for differential amplification of the input are connected together with this first constant current source. The input voltage Vin is applied between the bases of these transistors Q 15 and Q 16 . The transistors Q 15 and Q 16 together differentially amplify the input voltage Vin so as to distribute the first constant current I 0 among the transistors Q 15 and Q 16 . As a consequence, a first current I 1 flows through the NPN transistor Q 15 , and a second current I 2 flows through the NPN transistor Q 16 .
[0051] Connected between the collector of the NPN transistor Q 15 and a power supply voltage Vcc is a series connection of a resistor R 11 and a PNP type bipolar transistor (hereinafter referred to as PNP transistor) Q 11 serving as a first mirror source transistor. There are provided a PNP transistor Q 12 having an emitter connected to the base of the PNP transistor Q 11 and a base connected to the collector of the PNP transistor Q 11 and a collector connected to the ground, and a resistor R 12 connected between the base of the PNP transistor Q 11 and the power supply voltage Vcc.
[0052] In this arrangement, the first current I 1 flows via the series connection of the PNP transistor Q 11 and resistor R 11 , and a first mirror source voltage i proportional to the first current I 1 is generated at the base of the PNP transistor Q 11 . In what follows, voltages will be referenced to the ground potential unless otherwise stated.
[0053] Connected between the collector of the NPN transistor Q 16 and the power supply voltage Vcc is a series connection of a resistor R 13 and a PNP transistor Q 13 serving as a second mirror source transistor. Further, there is provided a PNP transistor Q 14 having an emitter connected to the base of the PNP transistor Q 13 , a base connected to the collector of the PNP transistor Q 13 , and a grounded collector and a resistor R 14 connected between the power supply voltage Vcc and the base of the PNP transistor Q 13 . In this arrangement, the second current I 2 flows via the series connection circuit of the PNP transistor Q 13 and the resistor R 13 , and a second mirror source voltage ii proportional to The second current I 2 is generated at the base of the PNP transistor Q 13 .
[0054] A current subtraction circuit 20 includes a series connection of a resistor R 22 , a first mirror transistor (referred to as first mirror target transistor) in the form of a PNP transistor Q 22 for flowing therethrough a first mirror current M*I 1 that is M times the first current I 1 in response to the first mirror source voltage i with M being a first predetermined mirror ratio, a second constant current source in the form of an NPN transistor Q 24 for flowing therethrough a second constant current M*I 0 /2, and a resistor R 24 . From the node of the PNP transistor Q 22 and the NPN transistor Q 24 , a current v is outputted in accord with a first difference current M*I 1 -M*I 2 . The first predetermined mirror ratio M can be set to an arbitrary magnitude.
[0055] The current subtraction circuit 20 also includes a series connection of a resistor R 21 , a second mirror transistor (referred to as second mirror target transistor) in the form of a PNP transistor Q 21 for flowing therethrough a second mirror current M*I 2 that is M times the second current I 2 in response to the second mirror source voltage ii with M being the first predetermined mirror ratio, a third current source in the form of an NPN transistor Q 23 for flowing therethrough the second constant current M*I 0 /2, and a resistor R 23 . From the node of the PNP transistor Q 21 and the NPN transistor Q 23 , a second current iv is outputted in accord with a second difference current M*I 2 -M*I 1 having a polarity opposite to that of the first difference current.
[0056] The NPN transistors Q 23 and Q 24 have a current ratio of M/2 that of the NPN transistor Q 17 . By varying the voltage iii supplied to the respective bases of the NPN transistors Q 23 , Q 24 and Q 17 using a current level setting circuit 60 , levels of the constant current I 0 and M*I 0 /2 can be simultaneously controlled by the same ratio.
[0057] The current level setting circuit 60 comprises a variable current source I 61 connected between the power supply voltage Vcc and the ground, an NPN transistor Q 61 , and an NPN transistor Q 62 having an emitter connected to the base of the NPN transistor Q 61 , a base connected to the collector of the NPN transistor 61 , and a collector connected to the power supply voltage Vcc. The base of the NPN transistor Q 61 is connected to the respective bases of the NPN transistors Q 23 , Q 24 , and Q 17 . By varying the current level of the variable current source I 61 , the base voltage of the NPN transistor Q 61 can be controlled. The constant currents through the respective NPN transistors Q 23 , Q 24 , and Q 17 forming a current mirror configuration can be controlled by controlling the base voltage iii of these NPN transistors.
[0058] A delivery circuit 30 includes: an NPN transistor Q 32 serving as a first delivery transistor; an PNP transistor Q 33 serving as a second delivery transistor; an NPN transistor Q 31 serving as a third delivery transistor; a PNP transistor Q 34 serving as a fourth delivery transistor; and voltage dividing resistors R 31 and R 32 for dividing the power supply voltage Vcc to generate at the voltage division node thereof a predetermined divided voltage.
[0059] The divided voltage is preferably equal to the output voltage of the current subtraction circuit 20 when-the first difference current M*I 1 -M*I 2 (and the second difference current M*I 2 -M*I 1 as well) is zero.
[0060] The bases of the first through fourth delivery transistors Q 32 , Q 33 , Q 31 , and Q 34 , respectively, are connected to the voltage division node. A current v in accord with the first difference current M*I 1 -M*I 2 is supplied to the emitters of the first and the fourth delivery transistors Q 32 and Q 34 , respectively.
[0061] A current iv in accord with the second difference current M*I 2 -M*I 1 is supplied to the emitters of the second and the third delivery transistors Q 33 and Q 31 , respectively.
[0062] First through fourth current output instruction signals (that is, first through fourth current levels) vi-ix are outputted from the respective first through fourth delivery transistors Q 32 , Q 33 , Q 31 , and Q 34 , respectively, in accord with the polarities and magnitudes of the currents v and iv.
[0063] A current output circuit 40 includes: a first output transistor circuit 40 - 1 for flowing therethrough an output current in accord with the current output instruction signal vii received from the NPN transistor Q 32 ; a second output transistor circuit 40 - 2 for flowing therethrough an output current in accord with the current output instruction signal viii received from the PNP transistor Q 33 ; a third. output transistor circuit 40 - 3 for flowing therethrough an output current in accord with the current output instruction signal vi received from the NPN transistor Q 31 a ; and fourth output transistor circuit 40 - 4 for flowing therethrough an output current in accord with-the current output instruction signal ix received from the PNP transistor Q 34 .
[0064] The first output transistor circuit 40 - 1 has a PNP transistor Q 44 serving as a third mirror source transistor connected between the collector of the NPN transistor Q 32 and the power supply voltage Vdd. The-first output transistor circuit 40 - 1 also has a PNP transistor Q 45 having an emitter connected to the base of the PNP transistor Q 44 and a base connected to the collector of the PNP transistor Q 44 , and a collector connected to the ground, and a resistor R 42 connected between the base of the PNP transistor Q 44 and power supply voltage Vdd.
[0065] In this arrangement, the current output instruction signal vii flows via the PNP transistor Q 44 , resulting in a third mirror source voltage proportional to the current output instruction signal vii at the base of the PNP transistor Q 44 . In response to the third mirror source voltage, a third mirror current N*vii that is N time the second current output instruction signal vii flows through a PNP transistor Q 46 serving as a third mirror target transistor, with N being the second predetermined mirror ratio. The third mirror current is outputted as a differential output load current Iout to a load 70 . The second predetermined mirror ratio N can be set to an arbitrary magnitude. N is preferably not less than 1.
[0066] The second output transistor circuit 40 - 2 has an NPN transistor Q 51 serving as a third mirror source transistor connected between the collector of the PNP transistor Q 33 and the ground. The second output transistor circuit 40 - 2 also has an NPN transistor Q 52 having an emitter connected to the base of the NPN transistor Q 51 , a base connected to the collector of the NPN transistor Q 51 , and a collector connected to the power supply voltage Vdd, and a resistor R 51 connected between the base of the NPN transistor Q 51 and the ground.
[0067] In this arrangement, the current output instruction signal viii flows via the NPN transistor Q 51 , resulting in a third mirror source voltage proportional to the current output instruction signal viii at the base of the NPN transistor Q 51 . The second output transistor circuit 40 - 2 has a further NPN transistor Q 53 serving as a third mirror target transistor, through which a third-mirror current N*viii that is N times the current output instruction signal viii flows in response to the third mirror source voltage, where N is the second predetermined mirror ratio. This current flows-into a load 70 as a load current Iout.
[0068] The third output transistor circuit 40 - 3 includes PNP transistors Q 41 , Q 42 , and Q 43 and a resistor R 41 in a configuration similar to that of the first output transistor circuit 40 - 1 . In this arrangement, a third mirror current N*vi that is N times the current output instruction signal vi flows through the PNP transistor Q 43 , with N being the second predetermined mirror ratio. This current flows into the load 70 as a load current Iout.
[0069] The fourth output transistor circuit 40 - 4 is formed of NPN transistors Q 54 , Q 55 , and Q 56 and a resistor R 52 in a configuration similar to that of the second output transistor circuit 40 - 2 . Because of this arrangement, the third mirror current N*ix that is N times the current output instruction signal ix flows through the NPN transistor Q 56 , with N being the second predetermined mirror ratio N. This current flows into the load 70 as the load current Iout.
[0070] Thus, a first load current path is formed to flow the output current N*vii from the first output transistor circuit 40 - 1 to the load 70 and flow the output current N*viii from the load 70 to the second output transistor circuit 40 - 2 . A second load current path, opposite in direction to the first, is also formed to flow an output current N*vi from the third output transistor circuit 40 - 3 to the load 70 , and flow an output current ix from the load 70 to the fourth output transistor circuit 40 - 4 .
[0071] Referring further to FIG. 2 , operation of the differential current output unit of FIG. 1 will now be described.
[0072] The first constant current I 0 is set to a predetermined level by the current level setting circuit 60 . As a consequence, the second constant current becomes M*I 0 /2, in accord with the current ratio of M/2.
[0073] When the input voltage Vin is zero at time t 1 as shown in FIG. 2 , the first current I 1 and the second current I 2 are equal in magnitude, so that both the first mirror current M*I 1 and the second mirror current M*I 2 are equal to M*I 0 /2. As a consequence, since the difference currents iv and v are zero, all the current output instruction signals vi-ix are zero, resulting in no load current Iout.
[0074] When the input voltage Vin is positive at the (+) input terminal of the difference input circuit 10 and negative at the (−) input terminal thereof during a period T 1 as shown in FIG. 2 , the first current I 1 is larger than the second current 12 in accord with the magnitude of Vin. The first and the second current I 1 and I 2 , respectively, are correctly converted by the first mirror ratio M. Thus, the first mirror current M*I 1 is larger than the second mirror current M*I 2 (i.e. M*I 1 -M*I 2 >0) In this case, since the difference current v equals M*I 1 -M*I 0 /2 which is negative, a current of (M*I 1 -M*I 2 )/2 flows out. Since the difference current iv equals M*I 2 -M*I 0 /2 which is positive, a current of (M*I 2 -M*I 1 )/2 flows in. That is, the inflow current and outflow current has the same magnitude and opposite directions.
[0075] The difference current iv controls on-off operation of the third delivery transistor Q 31 , supplying the current output instruction signal vi to the third output transistor circuit 40 - 3 . On the other hand, the difference current v controls on-off operation of the fourth delivery transistor Q 34 , supplying the current output instruction signal ix to the fourth output transistor circuit 40 - 4 .
[0076] Accordingly, a current N*vi flows from the PNP transistor Q 43 of the third output transistor circuit 40 - 3 to the load 70 as the positively polarized load current Iout. A current N*ix flows from the load 70 to the NPN transistor Q 56 of the fourth output transistor circuit 40 - 4 as a load current Iout. These outflow and inflow currents are the same in magnitude.
[0077] When the input voltage Vin is positive at the (−) input terminal of the difference input circuit 10 and negative at the (+) input terminal thereof during a period T 2 as shown in FIG. 2 , the second current I 2 is larger than the first current I 1 both in accord with the magnitude of Vin. In this case, the first mirror current M*I 1 is smaller than the second mirror current M*I 2 , that is, M*I 1 -M*I 2 <0. Since the difference current v equals M*I 1 -M*I 0 /2<0, a current of (M*I 1 -M*I 2 )/2 flows in. Since the difference current iv equals M*I 2 -M*I 0 /2>0, a current of (M*I 2 -M*I 1 )/2 flows out. That is, the inflow and outflow of currents have the same magnitude and opposite directions.
[0078] The difference current v controls on-off operation of the first delivery transistor Q 32 , supplying the current output instruction signal vii to the first output transistor circuit 40 - 1 . On the other hand, the difference current iv controls on-off operation of the second delivery transistor Q 33 , supplying the current output instruction signal viii to the second output transistor circuit 40 - 2 .
[0079] Accordingly, a current N*vii flows from the PNP transistor Q 46 of the output transistor circuit 40 - 1 to the load 70 as a load current Iout of the negative polarity. Moreover, a current N*viii through the NPN transistor Q 53 of the output transistor circuit 40 - 2 is fed from the load 70 as a load current Iout. These outflow and inflow currents have the same magnitude. The load current Iout is presently assumed to saturate at a predetermined level as shown in FIG. 2 . It should be understood, however, that the load current Iout need not to saturate.
[0080] Thus, depending on the directions of the difference currents v and iv, either the first delivery transistor Q 32 in the outflow section and the second delivery transistor Q 33 in the inflow section, or the third delivery transistor Q 31 in the outflow section and the fourth delivery transistor Q 34 in the inflow section of the delivery circuit 30 , are controlled for delivery of current output instruction signals. That is, two separate sets of an inflow and an outflow transistor circuits of the current output circuit are automatically changed over from one to the other by current output instruction signals.
[0081] Next, operation of the unit will now be described for a period in which the input voltage Vin changes from positive to negative polarity across zero volt. This is a case where the voltage passes zero point at time t 2 between the periods T 1 and T 2 as shown in FIG. 2 .
[0082] During the period T 1 , the third delivery transistor Q 31 is controlled by-the difference current iv to supply the current output instruction signal vi to the third output transistor circuit 40 - 3 . At the same time, the fourth delivery transistor Q 34 is controlled by the difference current v to supply the current output instruction signal ix to the fourth output transistor circuit 40 - 4 .
[0083] The difference currents iv and v have the same polarity as the input voltage Vin and magnitudes exactly proportional to Vin due to the actions of the difference input circuit 10 and the current subtraction circuit 20 . As a consequence, as the (positive) input voltage Vin decreases towards zero, the magnitudes and the polarities of the difference currents iv and v also decrease in the same manner. Accordingly, when the input voltage Vin becomes zero, the difference currents iv and v also become zero.
[0084] Entering the period T 2 , the input voltage Vin changes from zero to a negative level, the difference currents iv and v to increase in magnitude with the opposite polarity as compared with the change in the period T 1 .
[0085] Thus, in accordance with the directions and the magnitudes of the difference currents iv and v, separation of the upper and lower (inflow- and outflow-) transistor circuits of the delivery circuit 30 are automatically controlled. Based on the controlled delivery of the current output instruction signals from the delivery circuit 30 , smooth inflow and outflow of the output current of the output transistor circuits 40 - 1 - 40 - 4 are provided. This can be done by supplying a load current Iout in accord with the differential input voltage Vin so as to smoothly change the output current Iout across a zero crossing point of the load current Iout. It will be appreciated that destruction of, the output transistors by a large (penetration) current is prevented by the delivery circuit 30 changing over the upper and lower sections of the current output circuit 40 (i.e. changing over the two sets of outflow and inflow transistor circuits) to prevent simultaneous flow of currents through the inflow and outflow output transistors.
[0086] It should be also appreciated that the degree of amplification in terms of the ratio of the load current Iout to the input voltage Vin, that is, amplification factor of the difference current output unit, can be arbitrarily altered by changing the output level of the variable current source I 61 of the current level setting circuit 60 . The ratio can be easily regulated by simultaneously altering the constant current I 0 of the difference input circuit 10 and the constant current M*I 0 /2 of the current subtraction circuit 20 by the same ratio.
[0087] Referring to FIG. 3 , there is shown another subtraction circuit of the differential current output unit according to a second embodiment of the invention.
[0088] As shown in FIG. 3 , this current subtraction circuit 20 A has a series connection of: a resistor R 22 a , a PNP transistor Q 21 a serving as a first mirror source transistor for flowing therethrough a first mirror current M*I 1 that is M times the first mirror current I 1 in response to the first mirror source voltage, where M is a first predetermined mirror ratio; and an NPN transistor Q 24 a serving as a first subtraction transistor for flowing therethrough a second mirror current M*I 2 that is M times the second current 12 with M being the first predetermined mirror ratio.
[0089] In order to obtain the second mirror current M* 12 of the NPN transistor Q 24 a , the current subtraction circuit is formed to include a resistor R 21 a , an PNP transistor Q 20 a for flowing therethrough the second mirror current M*I 2 in response to the second mirror source voltage ii; and a current mirror transistor circuit formed of NPN current transistors Q 22 a and Q 23 a for flowing the current M*I 2 of the PNP transistor Q 20 a through an NPN transistor Q 24 a.
[0090] The first difference current v of M*I 1 -M*I 2 is outputted from the node of the PNP transistor Q 21 a and the NPN transistor Q 24 a.
[0091] The differential current output unit 20 A also includes a series connection of: a resistor R 24 a ; a PNP transistor Q 26 a serving as a second mirror target transistor for flowing therethrough the second mirror current M* 12 that is M times the second current I 2 in response to the second mirror source voltage ii, with M being the first predetermined mirror ratio; and an NPN transistor Q 29 a serving as a second subtraction transistor for flowing therethrough the first mirror current M*I 1 that is M time the first current I 1 , with M being the first predetermined mirror ratio.
[0092] In order to obtain the first mirror current M*I 1 of the NPN-transistor Q 29 a , the differential current output unit 20 A includes a resistor R 23 a , an PNP transistor Q 25 a for flowing therethrough the first mirror current M*I 1 in response to the first mirror source voltage i; and a current mirror transistor circuit formed of NPN transistors Q 27 a and Q 28 a for flowing the current M*I 1 of the PNP transistor Q 25 a through an NPN transistor Q 29 a.
[0093] The second difference current iv of M*I 2 -M*I 1 is outputted from the node of the PNP transistor Q 26 a and the NPN transistor Q 29 a.
[0094] The current subtraction circuit 20 A of FIG. 3 functions in the same way as the current subtraction circuit 20 of FIG. 1 .
[0095] It is noted that in the current subtraction circuit 20 A the first difference current v of M*I 1 -M*I 2 and the second difference current iv of M* 12 -M*I 1 are respectively formed by the same current mirror circuits as the current mirror circuit forming the first and the second mirror source voltages i and ii respectively. Thus, the current subtraction circuit 20 A is free of the error that can be otherwise contained in the second constant current of FIG. 1 . Hence, the circuit 20 A results in more accurate first and second difference currents.
[0096] Referring to FIG. 4 , there is shown another a current output circuit 40 A of the differential current-output unit in accordance with a third embodiment of the invention.
[0097] As shown in FIG. 4 , current output transistor circuits 40 - 1 - 40 - 4 of the current output circuit 40 A has the same circuit arrangement as the current output circuit 40 of FIG. 1 . However, current output circuit 40 A differs from the circuit 40 in that both the NPN transistor Q 53 a provided in the inflow section for flowing therethrough the output current of the second output transistor circuit 40 - 2 and the NPN transistor Q 56 a provided in the inflow section for flowing therethrough the output current of the fourth output transistor circuit 40 - 4 have a current mirror ratio of M*α. The factor alpha can be basically any number other than 1.
[0098] As an example, we consider a case where α is 1.5. In this case, in the first load current path, the output current N*vii of the first output transistor circuit 40 - 1 is fed to the load 70 , and the output current N* a *viii of the second output transistor circuit 40 - 2 is fed from the load 70 . In this first load current path, the load current Iout becomes equal to the smaller output current N*vii.
[0099] On the other hand, in the second output transistor circuit 40 - 2 , the NPN transistor Q 53 a is controlled to flow a larger output current N*α*viii. As a consequence, the degree of electric conduction becomes higher in the NPN transistor Q 53 a than in the PNP transistor Q 46 of the first output transistor circuit 40 - 1 . Thus, the collector voltage of the NPN transistor Q 53 a reduces to a mere potential drop across the on-state resistance of the transistor Q 53 a , which is extremely small. When this is the case, the collector can be regarded as substantially at the ground potential.
[0100] The same is true for the load current that is obtained in the second load current path formed by the third output transistor circuit 40 - 3 and the fourth output transistor circuit 40 - 4 . That is, the collector voltage of the NPN transistor Q 56 a becomes equal to the negligibly small potential drop across the on-state resistance of the NPN transistor Q 56 .
[0101] Consequently, the load voltage impressed on the load 70 is a ground-based voltage. In this arrangement, even if the impedance balance between the first output transistor circuit 40 - 1 and the second output transistor circuit 40 - 2 has collapsed, the load 70 is impressed with the ground based voltage, thereby stabilizing the output voltage. In the same way, the waveform of the output voltage can be stabilized even when the impedance balance between the third output-transistor circuit 40 - 3 and the fourth output transistor circuit 40 - 4 has collapsed.
[0102] Incidentally, the magnitude of the factor a, can be smaller than 1. In this case, the load 70 is impressed with a voltage based on the power supply voltage Vdd (Vdd-based voltage). Yet, the waveform of the output voltage can be stabilized. In actuality, however, it is appropriate to set the value of α in the range from 1.1 to 1.5 (1.1<α<1.5) (or in the range from 1/1.5<α<1/1.1), taking account of characteristics of the circuit.
[0103] FIG. 5 shows an arrangement of current output circuit of the differential current output unit in accordance with a fourth embodiment of the invention.
[0104] As shown in FIG. 5 , the current output circuit 40 B is provided with first through fourth output transistor circuits 40 - 1 - 40 - 4 , respectively, in such a way that each of the output transistor circuits has a first current mirror circuit having a fourth predetermined mirror ratio Q and controlled by a respective one of the current output instruction signals vi, vii, viii, and ix received from the delivery circuit 30 , and a second mirror circuit having a fifth predetermined mirror ratio P and controlled by a respective one of the output currents of the first mirror circuits. That is, in the current output circuit 40 B, the current mirror ratio N of the current output circuit 40 of FIG. 1 is obtained as the product N=Q×P of the fourth predetermined mirror ratio Q and the fifth predetermined mirror ratio, P.
[0105] This can be done as follows. In the case of the first output transistor circuit 40 - 1 , there is provided a third mirror source transistor in the form of a PNP transistor Q 45 b connected between the power supply Vdd and the current output instruction signal vii. The first output transistor circuit 40 - 1 is also provided with a PNP transistor Q 46 b having an emitter connected to the base of the PNP transistor Q 45 b , a base connected to the collector of the PNP transistor Q 45 b , and a collector connected to the ground, and a resistor R 42 b connected between the base of the PNP transistor Q 45 b and the power supply voltage Vcc.
[0106] In this arrangement, the current output instruction signal vii flows via the PNP transistor Q 45 b . A third mirror source voltage proportional to the current output instruction signal vii is generated at the base of the PNP transistor Q 45 b . In response to the third mirror source voltage, a third mirror current Q*vii that is Q times the current output instruction signal vii flows through the PNP transistor Q 47 b serving as the third mirror target transistor, where Q is the fourth predetermined mirror ratio. This third mirror current Q*vii flows through a current mirror circuit that consists of an NPN transistor Q 48 b and an output transistor in the form of an NPN transistor Q 49 b having a fifth predetermined mirror ratio P. Thus, a load current Iout of vii*Q*P is fed to the load 70 . Each of the second through fourth output transistor circuit 40 - 2 - 40 - 4 operate in the same manner.
[0107] It will be understood that, by choosing the mirror ratios Q and P such that P×Q=N, the number of the transistors used and/or the area occupied by the respective transistor can be reduced. This is useful especially when the mirror ratio N must be large as shown in FIG. 1 . Thus, an overall chip area can be minimized. For example, for N=100, the same current mirror ratio can be attained by choosing Q=10 and P=10.
[0108] Although the invention has been described above with reference to the embodiments using bipolar transistors, it should be understood that field effect type transistors such as MOSFETs can be used equally well in constructing a differential current output unit of the invention.
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The invention provides a differential current output unit that has a least number of capacitors and a minimized chip area on one hand, and on the other hand that is capable of providing a smoothly varying output current across a zero-crossing point in accord with an inputted difference input voltage. To do this, the differential current output unit is entirely formed of differential circuits and current mirror circuits having predetermined current mirror ratios. Thus, the unit has a stable output current characteristic. The unit has an inflow output transistor circuit and an outflow output transistor circuit that are operably separated by a delivery circuit. Thus, no penetration current will flow through the inflow- and outflow-output transistor circuits.
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FIELD OF THE INVENTION
[0001] The present invention relates to the field of decoration. More particularly, the present invention relates to a process for making a slab of, e.g., stone, wood, and the like, decorative element.
BACKGROUND OF THE INVENTION
[0002] Ever since the dawn of civilization, stones have been a major component in various aspects of the culture of human beings. For example, stones have long been utilized as memorial markers, for memorializing the deceased. In some cultures, stones, having random shape and sizes, were just put over burial sites, to mark the burial location. In other cultures, the memorial stones were embellished in various ways, for example, by carving, or etching, the stones. Carved stones and wood have also been utilized for adorning the exterior and interior sides of buildings, and as ‘stand-alone’ pieces of art.
[0003] Stone slabs have also been utilized as tiles, for paving roadways, covering floors of apartments and for covering walls. In some cases, in order to adorn, for example, a holy place, mosaic-based patterns were incorporated into its floor or walls, or portions thereof. The mosaic comprises small pieces of colored stones and/or glass, which, when combined in a particular way, create the required pictorial, or artistic, effect.
[0004] The mosaic technique has also been used in other applications in stone. For example, U.S. Pat. No. 4,036,929 discloses a method for embellishing memorial stones by the addition of a mosaic on the surface. The mosaic is produced by cutting a cavity in the stone, placing a base resin and mortar resin into the cavity, and inserting decorative chips into the mortar resin to form the desired embellishment. Each decorative figure that is made according to U.S. Pat. No. 4,036,929 has essentially the shape of a flat mosaic.
[0005] With the increasing level of living standard in the modern world, a lot of intention has been drawn to tiles for covering the floor and walls of apartments. Improvements in the industrialization of the making of tiles have made available a large selection of inexpensive tiles of various standard sizes and colorful patterns, from which one can choose for covering his apartment's floor, or walls. Such tiles are mostly made of ceramic materials, and their thickness largely depends on the application. However, ceramic tiles are usually thin and therefore can not include three dimensional ornamental elements. In some cases, ceramic tiles are painted with a thick layer of paint, in order to impart some depth to the pattern that is painted on the ceramic tile(s).
[0006] Sandblasting techniques are conventionally used in various industrial fields, including for artistic purposes. For example, sandblasting is used for carving decorative patterns in glass and in other materials. According to the above mentioned U.S. Pat. No. 4,036,929, a sandblasting technique is used for cutting the shallow cavity into which the mosaic is placed.
[0007] Laser techniques are also utilized for cutting in various materials for various purposes. In general, the output energy of a laser device is concentrated to a very narrow beam, which makes it very effective for cutting most accurate lines in various materials. For example, laser technology is currently utilized for cutting out the same ornamental pattern from two slabs having different colors, and ‘implanting’ in each slab the pattern with the other color. The output energy of a laser beam can be utilized for treating the surface of objects, and also for creating cavities therein, provided that the energy of the laser beam is tuned to the correct level. Despite of the wide range of uses of laser technology, the inventor is not aware of using laser technology for creating deep cavities in hard materials, such as Porcelain Granite, for creating decorative objects in the way disclosed in the present invention. In addition, laser technology is expensive, which would render the ornamental slabs, produced by its utilization, expensive.
[0008] Conventional techniques are generally characterized in that they teach utilizing ceramic tiles for covering floors and walls, or they teach how two dimensional mosaic decorations could be formed for various goals. Other prior art publications teach using sandblasting techniques to make cavities in a stone. However, sandblasting techniques are conventionally used for treating a relatively thin layer near the surface of a material. In addition, none of the prior art publications teaches either how to rapidly sandblast deep cavities in a stone or the like., in particular in White Granite (known by its commercial names as Porcelain Granite, White Ironstone, Pearl China, Pearl Granite, Flintware, and Opaque China) or in other materials having similar hardness, or how to incorporate three dimensional decorative elements into a deep cavity created in a stone, wood or the like, which could then be utilized, for example, to cover a floor or a wall of an apartment, or be used as a ‘stand-alone’ decorative element.
[0009] It is therefore an object of the present invention to provide a method for rapidly making deep cavities in hard materials, such as White Granite, while imparting to them artistic appearance.
[0010] It is another object of the present invention to provide decorative tiles and objects by using the method of the present invention.
[0011] Other objects and advantages of the invention will become apparent as the description proceeds.
SUMMARY OF THE INVENTION
[0012] The following definitions are used in this application:
By ‘slab’ is generally meant a piece of a thick plate or slice (as of stone, clay, wood, metal, polymer and similar materials). With respect to the present invention, the wording ‘slab’ refers also to a slab-like element that consists of two or more individual slices. Therefore, by ‘slab’ is meant herein to a slab that consists, in some cases, of one plate or slice, and in other cases of two or more plates or slices. By ‘cavity’ is meant herein a deep recess that is formed in the surface of a slab by sandblasting (‘deep’—about 8 millimeters minimum). By ‘sandblasting’ is generally meant a known process that includes spraying a jet of sand onto the surface of a material, for cleaning and carving purposes. With respect to the present invention, the term ‘sandblasting’ refers to spraying a jet of sand, or fine particles of other materials, onto the surface of a material, whose hardness is at least 7. By ‘hardness’ is meant the measure of a mineral's resistance to abrasion, which reflects the atomic structure of the mineral. By ‘7’ is meant a hardness of quartz, according to Mohs hardness scale. By ‘covering sheet’ is meant herein a piece of a transparent or semi-transparent (in whole or in parts), or colored (in whole or in parts) plate that fully covers the slab or only the open side (‘opening’) of the cavity, to protect ornamental elements placed in the cavity. The covering sheet can be made of glass (hardened/reinforced or not, depending on the desired application), polymer, or any other substance suitable for the purposes of the present invention. By ‘ornamental slab’ it is meant herein a slab with a cavity containing ornamental elements. The ornamental slab, or only its cavity, can be sealed with a covering sheet, or left uncover.
[0020] The inventor of this invention has found that a relatively deep cavity (e.g., 15 mm) can be rapidly formed in a hard material such as White Granite by sandblasting using a jet of particles having at least hardness 7. An exemplary kind of sand, the characteristics of which are described herein below, is capable of rapidly creating cavities in, e.g., White Granite if carried by a stream of air pressurized to seven atmospheres minimum.
[0021] The inventor of this invention has also found, that PVC (Poly Vinyl Chloride) is resistant to the projected sand, and therefore, use of a PVC based mask protects the surfaces of the slab that are not intended to be sandblasted, and allows obtaining a deep cavity without having to frequently replace the mask due to wear. In addition, using a PVC based mask allows obtaining cavities with edges that have contour lines that are essentially identical to the contour lines of the windows in the mask. Utilization of PVC masks impart to the cavities conspicuous artistic appearance, thereby beatifying the appearance of the ornamental slab.
[0022] The present invention provides a method for rapidly making deep cavities in a scab, the method comprising:
a) Providing the slab with a desired shape and dimensions, and into which a cavity is to sandblasted; b) Creating a mask made of Poly Vinyl Chloride (PVC) by creating one or more windows in the PVC material, each window having predetermined shape and size to define desired surface of the corresponding cavity; c) Releasably adhering the PVC mask onto the surface of the slab, by, e.g., using a glue agent commonly known as “Super Glue”. The Super Glue includes cyanoacrylate (C 5 H 5 NO 2 ) as one of its ingredients, which ingredient is an acrylic resin that cures (forms its strongest bond) almost instantly when triggered by hydroxyl ions in water; d) Sandblasting one or more cavities of predetermined depths in the slab through corresponding windows in the PVC mask; and e) Removing the PVC mask from the slab by peeling it off the slab.
[0028] The present invention also discloses an ornamental slab, which is obtained by incorporating (two/three) dimensional ornamental elements into a cavity that is created in a slab. The cavities in the slab can be formed by either utilizing the sandblasting process described above, or by any alternative method. For example, the cavities can be created by utilizing drilling machine, laser beam, the energy of which can be tuned according to the desired depth of the cavity, or chemicals, or any combination thereof. In addition, a slab can be molded, with the desired cavities, using polymer materials, plasters, clay materials, or any combination thereof, or other suitable moldable material.
[0029] Preferably, the ornamental slab of the invention is obtained by:
a) Inserting into the one or more cavities in the slab two and/or three dimensional ornamental elements (e.g., dried flowers, shells of various kinds, clams, cockles, scallops, great scallops, blue mussels, various colored stones, metal elements, wood elements, plastic elements, mirrors, pearls, light sources, etc.). The ornamental elements occupy only some portion of the space of the cavity, and are, preferably, though not necessarily, secured (by, for example, the use of epoxy resin) to desired places in the cavity, and optionally, to one another, by optionally utilizing supporting elements and adhering agent. In another embodiment, some or all of the ornamental elements are not fixed to the cavity and/or to one another; b) Covering the whole slab, or only the openings of the cavities thereof, with a covering sheet, or covering sheets, for protecting the ornamental elements residing within the cavities; and c) Fixing the covering sheet(s) to the slab, or to the cavities thereof, using water resistant adhering agent, for providing sealing between the covering sheet and slab, in order to prevent water and moisture from entering the cavity.
[0033] According to an aspect of the present invention, the openings of the cavities are left uncovered, and one or more of the ornamental elements extend outwardly from the cavities, either surpassing the surface of the slab or not.
[0034] According to one embodiment of the present invention, the covering sheet is placed in a ledge that is sandblasted or otherwise formed, such as by being cut, in the upper portion of the walls of the cavity, for providing support to the covering sheet.
[0035] Preferably, the ledge is made such that the upper surface of the covering sheet; i.e., the side facing outwardly and away from the cavity, when placed on the ledge, is a continuation of the surface of the slab in the same plane. If desired, gaps can exist, or be left, between the covering sheet and the walls of the cavity, in order to fill them with caulking material, such as epoxy glue, which serves to secure the covering sheet to the ledge and for sealing the cavity, or cavities, within which the ornamental elements reside.
[0036] The external shape of the slab is selected from the group of {polygonal, circle, ellipse, oval}. Optionally, the external shape of the slab can be made such as that it conforms to any other desired shape.
[0037] The shape of the opening of each cavity may be selected from the group of {polygonal, circle, ellipse, oval}. Optionally, the shape of the opening can conform to any other desired shape.
[0038] The substance of the slab is preferably selected from the group consisting of: stone, marble, White Granite, wood, polymer, metal, clay.
[0039] Preferably, the sickness of the slab is about 8 millimeters minimum, for allowing sandblasting cavities that are deep enough to contain the desired decorative elements. However, in some cases, where the decorative elements are flat and occupy relatively very small space, slabs having thickness less than 8 millimeters can be used as well.
[0040] The substance of the mask can be selected from the group consisting of: Poly Vinyl Chloride (i.e., PVC), metal, rubber and polymer, though the PVC has been found by the inventor of the present invention to be the preferred material due to its resistance to the jet of sand and, in addition, because PVC is relatively easy to handle (i.e., cut, adhere, etc.).
[0041] According to one preferred embodiment of the present invention, ornamental slabs produced by the present invention are utilized as tiles, to cover walls or a floor of an apartment.
[0042] According to another preferred embodiment of the present invention, ornamental slabs produced by the present invention are individually incorporated into existing floors or walls of an apartment, or into other parts or elements thereof, for decoration purposes.
[0043] According to another preferred embodiment of the present invention, individual ornamental slabs produced according to the present invention are used as stand-alone decorative elements.
[0044] The covering sheet may be fully transparent or semi-transparent, in whole or in part(s) of it.
[0045] The covering sheet may be colored in whole or in parts. In this respect, the covering sheet may be mono-colored or multicolored, in whole or in part(s).
[0046] According to an aspect of the present invention, the covering sheet is glass, whether reinforced or hardened, or neither reinforced nor hardened. Optionally, the covering sheet may be made of a material commonly known as Perspex. According to yet another option, the covering sheet may be made of metal.
[0047] According to one embodiment of the present invention, the covering sheet includes one or more openings, which fully pass through the covering sheet. Each one of the openings is located in desired location relative to the location of the other openings, and relative to the circumference of the covering sheet. The openings may be irregularly distributed, or they may be distributed on a regular manner, or they may have any desired repeating pattern(s). The shape of the openings can be rounded, or it can conform to other shapes.
[0048] In another aspect, ornamental elements are secured in the openings and are partially protruding inwardly, viz. in the direction towards the cavity interior, and partially protruding outwardly, viz. towards a generally opposite direction and away from the cavity interior. Such ornamental element(s) can be, for example, a metal ball(s). Optionally, the ornamental elements can protrude only inwardly, or only outwardly, or not protrude at all.
[0049] In another embodiment of the invention, the surface of one side of the covering sheet is sandblasted to obtain desired carvings, and the sandblasted, or carved, side thereof faces inwardly, in a direction towards the cavity, or cavities.
[0050] According to another embodiment of the invention, the walls of the cavity are colored. The walls can be wholly or partially coated with a mono-colored or multicolored layer or film, or the desired color(s) can be applied to the walls such as by painting, spraying, or by any other suitable way. The color of the walls of the cavity may essentially match, or resemble, the general, dominant, color of the slab, or it can differ from it. According to an aspect of the invention, the color of the walls is the color of Gold.
[0051] According to another preferred embodiment of the present invention, at least one of the ornamental elements in a cavity is a light source, and if the cavity is covered with a covering sheet, the covering sheet is made of heat-resisting material (e.g., glass), and the covering sheet is releasably attached to the slab, for example, by drilling holes through the covering sheet and the slab and using screws, for allowing replacing the light source, should the need arise for any reason.
[0052] According to a first aspect of this embodiment, the ornamental slab includes one slab with a cavity large enough to contain a light source with its accessories (e.g., housing, support means, electrical cable, etc.). The ornamental slab could be utilized as decorative lighting source when standing alone, or when incorporated as a tile into a wall/floor cover. The cavity is formed in the slab in a way that the thickness of the wall of the slab (being the ‘bed’ of the cavity) has a width of only a few millimeters, making the bed of the cavity semi-transparent, for allowing at least a portion of the light radiated by the light source to pass through the bed of the cavity.
[0053] According to a second aspect of the latter embodiment, the ornamental slab includes two individual slabs that are joined to one another so that the open side of the cavities of the individual slabs face each other to form a common cavity capable of containing a light source with its accessories, thus utilizing the slab as a decorative lighting source when standing alone, or when incorporated as a tile into a wall, or floor. The light source and its related accessories (e.g., supporting means, electrical cable) are placed and secured in the cavity of the slab prior to them being sealed in the cavity.
[0054] According to an embodiment of the present invention, the light source is external to the cavity, and radiates light through the thin bed of the cavity.
[0055] According to an aspect of the present invention, the light source is selected from the group of: {Light Emitting Diode (LED), optical fiver, fluorescent lamp, phosphorescent materials, light bulb}.
[0056] According to an aspect of the present invention, some or all of the ornamental elements in a cavity are fixed to a corresponding place in the cavity, or loosely reside therein.
[0057] According to another embodiment, a slab-like element consists of two or more slices made of stone, stone-like material, or any other sliceable solid material, where the slices are adhered to one another, or secured to one another in any suitable way, after which the cavity, or cavities, is/are formed therein as described herein.
[0058] The planes of the slices can be, according to one aspect, perpendicular, or generally perpendicular, to the plane of the slab-like element, and parallel, or generally parallel, to one another. According to another aspect, each one the planes of the slices can be parallel, or generally parallel, to the plane of the slab, and parallel, or generally parallel, to one another.
[0059] Each one of the slices, from which the slab is consisted, may be made of a different material, and/or it may have a different thickness, width, length, color and/or shape.
[0060] According to yet another embodiment, one or more channels (hereinafter ‘light channels’) are made in the cavity or cavities, by drilling holes that pass through the slab, to allow light, which is emitted from a light source outside the ornamental slab, to penetrate, via the light channels, into the cavity or cavities for lightning the cavities and/or the ornamental/decorative elements residing therein, to obtain visual effects that are interested and appealing to a viewer.
[0061] In yet another embodiment, the covering sheet is supported by, and secured to, a ‘ledge element’, which provides the ledge needed to support and secure the covering sheet, and, being in itself a separate and intermediating element, secured to the wall(s) of the cavities, such as by being adhered to them. The ledge element may protrude with respect to the surface of the slab or not, and the ledge may be located in such a way that the upper surface of the covering sheet (i.e., the surface not facing the interior of the cavities) and the surface of the slab essentially lay wholly in the same geometrical plane. Alternatively, the ledge(s) may be so located, that the latter two surfaces lay in two different planes that may be either equidistantly spaced from one another, or not. For example, the surface of the covering sheet can be raised comparing to the surface of the slab, or it can be, according to another example, lower than the surface of the slab.
BRIEF DESCRIPTION OF THE DRAWINGS
[0062] FIG. 1 a is a sectional view of an exemplary ornamental slab, according to the principles disclosed in the present invention,
[0063] FIG. 1 b shows a clearer picture of pattern of the exemplary ornamental element shown partially in FIG. 1 a;
[0064] FIG. 1 c is a perspective view of the exemplary ornamental slab shown in FIG. 1 a;
[0065] FIG. 2 is a sectional view of another exemplary ornamental slab obtained according to the principles disclosed the present invention;
[0066] FIG. 3 a schematically illustrates incorporation of a light source into a cavity, according to one preferred embodiment of the present invention;
[0067] FIG. 3 b schematically illustrates incorporation of a light source into a cavity, according to another preferred embodiment of the present invention;
[0068] FIG. 4 a is a schematic three dimensional illustration of a partial ledge formed in a cavity, according to one preferred embodiment of the present invention;
[0069] FIG. 4 b is a cross-sectional view depicting the covering sheet placed on the ledge shown in part in FIG. 4 a;
[0070] FIG. 4 c shows a another view of the covering sheet placed on the ledge that was created in a slab;
[0071] FIGS. 5 a to 5 d schematically illustrate steps in making an exemplary ornamental slab, according to another preferred embodiment of the present invention;
[0072] FIGS. 6 a to 6 d schematically illustrate other exemplary ornamental slabs, according to some preferred embodiment of the present invention;
[0073] FIG. 7 schematically illustrates a covering sheet with openings, according to a fist example of the present invention;
[0074] FIG. 8 schematically illustrates a covering sheet with openings, according to a second example of the present invention;
[0075] FIGS. 9 a and 9 b schematically illustrate an example of a decorative element that is secured to an opening in the covering sheet, according to the present invention;
[0076] FIGS. 10 a and 10 b schematically illustrate an exemplary covering sheet where one of its surfaces had been carved, according to the present invention;
[0077] FIGS. 11 a and 11 b schematically illustrate two exemplary slab-like elements, with cavities, consisting of slices, according to the invention;
[0078] FIG. 12 schematically illustrates an exemplary slab with exemplary ‘light channels’, according to the invention; and
[0079] FIG. 13 schematically illustrates exemplary utilization of a ‘ledge element’, according to the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0080] FIG. 1 is a sectional view of an exemplary ornamental slab, according to the principles disclosed in the present invention. Ornamental slab 10 comprises, e.g., stone 11 , in which cavity 12 is cut, preferably by sandblasting stone 11 . Ornamental element 13 (best shown in FIG. 1 b ) is secured in cavity 12 by utilizing supporting elements 14 . The proximal end of supporting elements 14 (in this example, a total of three supporting elements) is adhered ( 17 ) to bed 15 of cavity 12 , by utilizing corresponding adhering agent (e.g., Epoxy resin). Then, ornamental element 13 is put in its place in cavity 12 and adhered ( 18 ) to the distal end of supporting elements 14 . Covering sheet (e.g., made of glass) 19 is then put against the open side of cavity 12 , for providing sealing (i.e., against water and moisture) and mechanical protection to ornamental element 13 . Covering glass 19 , which could be fully transparent in whole or in part, fully colored, or a combination of transparent and colored, has a shape and dimensions (i.e., ‘w’ and ‘l’) that essentially match those of the surface of stone 11 , as clearly shown in FIG. 1 c . Of course, the glass can be replaced with any suitable material, for example, by Perspex or other type of plastic. Covering glass 19 is, then, secured to its position on stone 11 , by utilizing a layer 19 / 1 of water resistant glue, which completes the sealing of the content of cavity 12 (in this example, ornamental element 13 ). Other types of, two or three dimensional, ornamental elements could be placed in cavity 12 , and the number, size, shape and relative location in cavity 12 , of supporting elements, would conform to the characteristics of the ornamental element(s) inserted into cavity 12 , and, optionally, on the desired artistic effect.
[0081] The cavity is obtained by releasably adhering a wear proof mask (not shown) onto the surface of the slab 11 , which wear proof mask having a window with the preferred shape and size (i.e., of the desired cavity opening), and sandblasting slab 11 through the window in the wear proof mask. The wear proof mask is preferably PVC.
[0082] The characteristics of the sand used in the sandblasting process are as follows:
1. Distribution of the granular sizes: at least 60% of the particles have a size ranging from 0.60 to 0.85 millimeter. In addition: Granular size larger than 0.85 millimeter—30% (maximum); Granular size smaller than 0.60 millimeter—30% (maximum); 2. Chemical characteristics of the sand: SiO 2 (98.5%, minimnum); Fe 2 O 3 (0.15%, maximum); Al 2 O 3 (0.4-0.6%); CaO+MgO (0.1-0.2%); and NaO+K 2 O (0.10%, maximum). 3. Mineralogical characteristics of the sand: the sand particles contain a very high percentage of quartz. 4. Hardness of the particles: 7 (according to Mohs hardness scale).
[0089] The covering sheet is adhered to the slab, by wrapping both the perimeters of the slab and covering sheet, as schematically shown in FIGS. 1 a and 1 c (reference numeral 19 / 1 ), by utilizing the 5300 Acrylic Double Sided glue agent (manufactured by Scapa Tapes Company), which is an acrylic adhesive with a solid acrylic core and a white siliconized release liner.
[0090] Exemplary but not limiting dimensions of slab 11 are: thickness=‘d’ (d=15-25 mm), Width=‘w’, Length=‘l’, wherein ‘w’ and ‘l’ are taken from the group: {5 cm, 10 cm, 15 cm, 20 cm, 16.5 cm, 25 cm, 30 cm, 33 cm, 40 cm, 45 cm, 50 cm, 55 cm, 60 cm, 80 cm}. For example, ‘w’ and ‘l’ could be 15 cm and 55 cm, respectively. Of course, the slabs could essentially have any other practical dimensions. For example, a slab can be 2.40 meters wide and 3.60 meters long. FIG. 1 c is a perspective view of the exemplary ornamental slab shown in FIG. 1 a;
[0091] If it is desired to utilize an ornamental slab, such as the ornamental slab shown in FIG. 1 c , for covering floors or walls, such as of buildings, swimming pools, etc., it is possible to use a stainless grout known by its commercial name as LATAPOXY SP-100 (manufactured by LATICRETE International, Inc., U.S.A.). LATAPOXY SP-100 is a stainless epoxy grout specifically designed for use in floor and wall applications of ceramic tile, stone and structural glazed block. LATAPOXY SP-100 efficiently resists many acids, alkalis and corrosives.
[0092] FIG. 2 is a sectional view of another exemplary ornamental slab, according to the principles disclosed in the present invention. FIG. 2 shows ornamental slab 20 that includes two sea-shells (i.e., 21 and 22 ) and heart-like ornamental piece (i.e., 23 ). Of course, other, or different, three dimensional ornamental elements could be inserted into a cavity of a slab.
[0093] FIG. 3 a schematically illustrates incorporating a light source into a cavity, according to one preferred embodiment of the present invention. Ornamental slab 30 a comprises slab 11 , into which cavity 12 was sandblasted, covering glass 19 , and light source 31 with its related accessories. Light source 31 is inserted into cavity 12 and secured thereto by supporting means 32 . Slab 11 includes an opening, for allowing insertion of-an electrical cable 33 , to provide the electric energy required to operate light source 31 . Slab 11 includes also ventilation openings 34 , for allowing dissipation of the heat generated by light source 31 . Cavity 12 of slab 11 is so deep, that the thickness (S) of the wall is only a few millimeters, which makes it semi-transparent. In this location, light source 31 will radiate light through the thin wall of slab 11 (S being equal to, e.g., 3 mm) and through covering glass 19 , which could be fully, or partially, transparent, or colored in whole or in portions thereof. Optionally, a reflective surface (e.g., mirror) adhered onto the interior face of covering glass 19 would cause the light generated by light bulb 31 to radiate in one direction only. Ornamental slab 30 a is intended to be utilized as decorative lighting source when standing alone, or when incorporated into a wall, or floor, cover.
[0094] FIG. 3 b schematically illustrates incorporation a light source between two slabs, according to another preferred embodiment of the present invention. Ornamental slab 30 b is formed by joining two slabs, such as slab 11 , together, so that the open side of their cavities faces each other to form a common cavity 39 . Ornamental slab 30 b also comprises light source 31 , with its related accessories (including supporting means 32 and electrical cable 33 ). Light source 31 is secured in place in cavity 39 prior to the joining of the two slabs ( 37 / 1 and 37 / 2 ) together, by means of a water resistant glue (e.g., Epoxy resin), schematically indicated by reference numeral 38 .
[0095] One of slab 37 / 1 or 37 / 2 includes an opening for insertion of an electrical cable 33 , to provide the electric energy required to operate light source 31 . Slab 37 / 1 and/or 37 / 2 also have ventilation openings 34 , for allowing dissipation of the heat that is generated by light source 31 . Cavity 39 of slabs 37 / 1 and 37 / 2 is so deep, that the thickness of the walls (S 1 and S 2 ) is only a few millimeters, which makes the walls semi-transparent. Light source 31 irradiates light through the thin walls of slabs 37 / 1 and 37 / 2 . The two halves of ornamental slab 30 b could have the same or different colored walls. Ornamental slab 30 b is intended to be utilized as decorative lighting source when standing alone, or when incorporated into a wall.
[0096] Ornamental slabs 30 a or 30 b can have a shape other than rectangular, and the ornamental elements can be fixedly positioned in a cavity, or loosely reside therein.
[0097] FIGS. 4 a to 4 c schematically illustrate using a ledge for supporting the covering glass in a slab, according to one preferred embodiment of the present invention. FIG. 4 a shows a cross-sectional view of a slab, for illustrating the relative location of the ledge, with respect to the walls of the cavity. FIG. 4 b shows a cross-sectional view of the slab with the covering glass 43 lying on the ledge 44 . After cutting cavity 42 in slab 41 , a ledge ( 44 ) is cut in the upper portion of the cavity walls 48 (only two opposite walls are shown). Removing the excess material from the walls of cavity 42 , results in formation of the ledge 44 , onto which covering glass 43 is laid (after placing and securing ornamental elements, for example, ornamental elements 45 and 46 , inside cavity 42 ). The height ‘h’ of the ledge 44 essentially matches the thickness of covering glass 43 , and the width w of the ledge 44 is adequate for supporting covering glass 43 . Ideally, the surface of covering glass 43 is a continuation of surface 47 of slab 41 . However, if the upper surface of covering glass 43 is found to be lower than surface 47 the covering glass can be conveniently raised to the correct level. Filling gap 49 with caulking material 50 ( FIG. 4 b ) seals the contact area between covering glass 43 and slab 41 , for protecting ornamental elements 45 and 46 , and also secures covering glass 43 to ledge 44 .
[0098] FIG. 5 a to 5 d schematically illustrates embedding exemplary ornamental element into a slab, according to another preferred embodiment of the present invention. Ornamental element 54 is intended to be embedded into slab 51 . To accomplish this, cavity 55 is created in slab 51 by sandblasting by using mask 52 , which includes a window whose contour line is essentially identical to the contour line of ornamental element 54 . The depth of cavity 55 is more than the thickness ‘d’ of ornamental element 54 , in order to allow cavity 55 to conveniently accept ornamental element 54 ( FIG. 5 d ). Cavity 55 is partially filled with mortar 56 , onto which ornamental element 54 is laid. Caulking 56 is then used to fill the volume around ornamental element 54 securing it in its place, and to beautify the general appearance of the slab and ornament. According to the example shown in FIG. 5 , surface 57 of slab 51 , surface 58 of ornamental element 54 and the surface of caulking 56 form one continuous surface in the same plane. However, this is not necessary, and the relative height of surface 58 , with respect to surface 57 , can be according to the desired artistic effect.
[0099] FIG. 6 a schematically illustrates exemplary tile made according to the present invention. The width, length, and thickness of slab 61 can be, for example, 100×100×30 centimeters. In the middle portion of cavity 63 there is a surface 62 that is raised relative to the bottom of cavity 63 . Surface 63 can be in the same plane as surface 67 of slab 61 , as shown in FIG. 6 b , lower than surface 67 , as shown in FIG. 6 c , or higher than surface 67 , as shown in FIG. 6 d . In the latter case, surface 62 can be utilized as a table or a chair. A light source (not shown) can be incorporated into cavity 63 for decoration purpose. Reference numerals 64 to 66 denote a covering sheet in the respective Figs.
[0100] FIG. 7 schematically illustrates a first example of a covering sheet with openings, according to the present invention. Covering sheet 70 includes, according to this example, nine openings that pass through it (only two of which are designated by numerical references; i.e., openings 71 and 72 ). Covering sheet 70 is shown having a rectangular shape and the openings (e.g., 71 , 72 ) are shown having rounded shape. However, the covering sheet and the openings may desirably have any other shape. According to this example, the openings (e.g., 71 , 72 ) are arranged in a circle-like manner.
[0101] FIG. 8 schematically illustrates a second example of a covering sheet with openings, according to a second example of the present invention. Covering sheet 80 includes, according to this example, thirteen openings that pass through it (only six of which are designated by numerical references; i.e., openings 83 to 88 ). Covering sheet 80 is shown having a rectangular shape and the openings, for example openings 83 and 85 , are shown having rounded shape. However, the covering sheet and the openings may desirably have any other shape.
[0102] According to this example, openings 85 , 86 , 87 and 88 are shown arranged in a desired pattern, which is shown circumscribed by dotted line 81 . Likewise, other openings are shown arranged in another desired pattern, which is shown circumscribed by dotted lines 82 . The pattern circumscribed by dotted line 82 is identical to the pattern circumscribed by dotted line 81 , though it has a different orientation, but this not necessarily so.
[0103] In addition, covering sheet 80 includes a series of openings that are arranged along an imaginary line. Opening 83 is the first, or last, opening in the line, whereas opening 84 is the last, or first, opening in the line.
[0104] FIGS. 9 a and 9 b schematically illustrate an example of a decorative element that is secured in an opening in the covering sheet, according to the present invention. In FIGS. 9 a and 9 b , a ball-like element 91 is the decorative element. FIG. 9 a shows a top view of the ball-like element 91 secured to its place in a rounded opening in cover sheet 90 , whereas FIG. 9 b shows a side cross-sectional view of the cover sheet and element 91 . In the example shown in FIGS. 9 a and 9 b , the decorative element, viz. ball-like element 91 , is shown protruding to both directions with respect to cover sheet 90 (in FIG. 9 b upwards and downwards). As described above, the decorative element may protrude only in one direction, viz. either upwards or downwards), or it may not protrude at all.
[0105] FIGS. 10 a and 10 b schematically illustrate an exemplary covering sheet where one of its surfaces had been carved, according to an embodiment of the present invention. As shown in FIG. 10 a , surface 102 of covering sheet 100 is flat and smooth, whereas surface 101 of covering sheet 100 is schematically shown as having exemplary carvings (i.e., 103 ), and is, therefore, referred to hereinafter as the ‘carved surface’.
[0106] FIG. 10 b shows the carved surface 101 of covering sheet 100 faces downwards; viz. towards the direction of cavity 12 , whereas the smooth surface thereof faces outwardly, viz. in the direction opposite to the direction of cavity 12 and away from it.
[0107] FIG. 11 a schematically illustrates an exemplary slab-like element that consists of slices, the planes of which are parallel to one another and to the plane of slab-like element 110 . Slab-like element 110 consists of slices 111 to 114 , which may be cut from desired solid materials. For example, slice 111 can be sliced from one kind of stone, slice 112 from a different kind of stone, etc. According to another example, one or more slices (e.g., slice 113 ) can be a piece of metal, wood, plastic, and so on.
[0108] After securing slices 111 to 114 to one another, such as by adhering them to one another, a cavity, such as cavity 115 , is formed in slab 110 .
[0109] FIG. 11 b schematically illustrates another exemplary slab-like element that consists of slices, the planes of which are parallel to one another and perpendicular to the plane of slab-like element 116 . Slab-like element 116 consists of slices 116 / 1 to 116 / 6 , which may be cut from desired solid materials. Cavity 117 is formed in slab-like element 116 in a way described herein, and a covering sheet (not shown) is placed thereon using a corresponding ledge (not shown), which may be desirably formed in the walls of the cavity as described herein, or it may be a ledge element, chosen to obtain a slab of some desired appearance.
[0110] FIG. 12 schematically illustrates an exemplary slab with exemplary ‘light channels’, according to the invention. ‘Light channels’, such as light channels 121 to 124 are formed in slab 120 , by drilling there through corresponding holes. Light, whether natural or artificial, is allowed to pass through light channels 121 to 124 to allow the light to enter cavity 126 to light it up, as well as ornamental element 125 , whereby to render the appearance of slab 120 appealing to a viewer (not shown).
[0111] FIGS. 13 a to 13 c schematically illustrate exemplary utilization of a ‘ledge element’, according to the invention. In FIG. 13 a , ledge elements 133 and 134 are shown not protruding from the surface 140 of slab 130 , and covering sheet 135 is secured to them in a way that the external surface of the covering sheet (i.e., surface 135 / 1 ) and the surface of slab 130 (i.e., surface 140 ) essentially lay in the same geometrical plane, which is shown also in FIG. 13 b , except that in FIG. 13 b , the ‘ledge elements’ (numerically referenced as 136 and 137 ) protrude from the surface 140 .
[0112] In FIG. 13 c , the ledges of ‘ledge elements’ 138 and 139 are so located, that surfaces 131 / 1 and 140 do not lay in the same plane, but, rather, they lay in two, different planes that are essentially equidistantly spaced from one another, though their planes may otherwise relate to one another.
[0113] While some embodiments of the invention have been described by way of illustration, it will be apparent that the invention can be carried into practice with many modifications, variations and adaptations, and with the use of numerous equivalents or alternative solutions that are within the scope of persons skilled in the art, without departing from the spirit of the invention or exceeding the scope of the claims.
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A process for making a slab of, e.g., stone, wood, White Granite and the like, decorative element, by sandblasting therein a relatively deep cavity, using a jet of particles having at least hardness 7 that are forced through a resilient PVC (Poly Vinyl Chloride) mask, which protects the surfaces of the slab that are not intended to be sandblasted. Using the PVC mask allows obtaining a rather deep cavity in the slab without having to frequently replace the mask due to wear, and also allows obtaining cavities with edges that have contour lines that are essentially identical to the contour lines of the windows in the mask. Utilization of PVC masks impart to the cavities conspicuous artistic appearance, thereby beatifying the appearance of the ornamental slab. Then, the slab is made an ornamental slab, by incorporating two and/or three dimensional ornamental elements (e.g., dried flowers, shells of various kinds, clams, cockles, scallops, blue mussels, various colored stones, metal plastic or wood elements, mirrors, pearls, light sources, etc.) into the cavity. Then, the cavities are covered with a covering sheet for protecting the ornamental elements residing therein. The covering sheet is made of a desired material, which may be transparent or semi-transparent, and may have different shapes and colors.
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RELATED APPLICATIONS
[0001] This application claims benefit under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 60/957,434, filed Aug. 22, 2007, which is incorporated in its entirety by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This application is directed toward fire-rated wall construction components for use in building construction.
[0004] 2. Description of the Related Art
[0005] Fire-rated wall construction components and assemblies are commonly used in the construction industry. These components and assemblies are aimed at preventing fire, heat, and smoke from leaving one portion of a building or room and entering another, usually through vents, joints in walls, or other openings. The components often incorporate the use of some sort of fire-retardant material which substantially blocks the path of the fire, heat, and smoke for at least some period of time. Intumescent materials work well for this purpose, since they swell and char when exposed to flames, helping to create a barrier to the fire, heat, and smoke.
[0006] One example of a fire-rated wall construction component is the Firestik™ design. The Firestik™ design incorporates a metal profile with a layer of intumescent material on its inner surface. The metal profile of the Firestik™ design is independently and rigidly attached to a wall component, such as the bottom of a floor or ceiling, and placed adjacent to other wall components, such as a stud and track. The intumescent material, which is adhered to the inner surface of the metal profile, faces the stud and track, and the space created in between the intumescent material and the stud and track allows for independent vertical movement of the stud in the track when no fire is present.
[0007] When temperatures rise, the intumescent material on the Firestik™ product expands rapidly. This expansion creates a barrier which encompasses, or surrounds, the stud and track and substantially prevents fire, heat, and smoke from moving through the spaces around the stud and track and entering an adjacent room for at least some period of time.
[0008] While the Firestik™ design serves to prevent fire, heat, and smoke from moving through wall joint openings, it also requires independent attachment and proper spacing from wall components. It would be ideal to have wall components and systems which themselves already incorporate a fire-retardant material.
[0009] An additional problem regarding current fire-rated wall components concerns ventilation. Exterior soffits for balconies or walkways are required to be fire rated. However, these soffits need to be vented to prevent the framing members from rotting. The rot is caused when airflow is taken away and condensation forms inside the framing cavity. The moisture from the condensation attacks the framing members and destroys them from the inside out. In many cases, the deterioration is not noticed until the framing is completely destroyed. Therefore, a fire-rated wall component is needed which accommodates proper ventilation during times when no fire or elevated heat is present, and seals itself when fire or elevated heat is present.
SUMMARY OF THE INVENTION
[0010] The present invention is directed toward fire-rated wall construction components and systems for use in building construction. The term “wall,” as used herein, is a broad term, and is used in accordance with its ordinary meaning. The term includes, but is not limited to, vertical walls, ceilings, and floors. It is an object of the invention to provide wall components and systems which have fire-retardant characteristics. It is also an object of the invention to provide wall components and systems which allow for needed ventilation during times when no fire or elevated heat is present.
[0011] To achieve these objects, the present invention takes two separate components, a wall component and intumescent material, and combines the two for use in building construction. The present invention includes at least one surface on a wall component capable of accepting intumescent material. In some embodiments, the outer surface of the intumescent material sits flush with a second surface of the wall component. This allows the wall component to retain its general shape and geometry without creating unwanted edges, protrusions, or uneven shapes. It also removes the need for a separate product or wall component to be installed outside or adjacent to a stud or track.
[0012] In an embodiment which resembles a vent or ventilation system, the intumescent material includes a set of holes. The term “holes,” as used herein, is a broad term, and is used in accordance with its ordinary meaning. The term includes, but is not limited to, holes, mesh, and slots. When the vent is in use, the combination of the holes in the intumescent material and the holes in the vent surface allow for continuous air flow through the vent. The holes need not match up co-axially, as long as air flow is permitted. In some embodiments, the holes in the intumescent material may line up co-axially with the holes in the vent surface. Additionally, in some embodiments a flat strap sits above the intumescent material. The flat strap may be a discrete piece attached separately, or may already be an integral part of the vent itself. The flat strap has its own set of holes which, when in use, allow for continuous air flow through the vent. In some embodiments the holes may be aligned co-axially with both the holes in the vent surface and the holes in the intumescent material. By having three sets of holes, air can flow through the vent, intumescent material, and strap during times when there is no fire or elevated heat. When the temperature rises, however, the intumescent material will expand quickly and block air pathways. In this manner, the entire vent will be sealed, substantially preventing fire, heat, and smoke from reaching other rooms or parts of the building for at least some period of time.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] These and other features, aspects and advantages of the various devices, systems and methods presented herein are described with reference to drawings of certain embodiments, which are intended to illustrate, but not to limit, such devices, systems, and methods. The drawings include 5 figures. It is to be understood that the attached drawings are for the purpose of illustrating concepts of the embodiments discussed herein and may not be to scale.
[0014] FIG. 1 illustrates a cross-sectional view of an embodiment of a fire-rated wall component connected to a floor and stud element.
[0015] FIG. 2 illustrates a perspective view of an embodiment of a fire-rated wall component with annular portions.
[0016] FIG. 3 illustrates a perspective view of an embodiment of a fire-rated wall component with annular portions, including intumescent material.
[0017] FIG. 4 illustrates a perspective view of an embodiment of a fire-rated wall component with slots and intumescent material in the slots.
[0018] FIGS. 5A and 5B illustrate perspective views of embodiments of a fire-rated wall component including holes for ventilation.
[0019] FIG. 6 illustrates a perspective view of an embodiment of a fire-rated wall component including holes for ventilation.
[0020] FIG. 7 illustrates a bottom perspective view of an embodiment of a fire-rated wall component including holes for ventilation.
[0021] FIG. 8 illustrates a cross-sectional view of an embodiment of a fire-rated wall component with intumescent material on its top surface.
[0022] FIG. 9 illustrates a cross-sectional view of an embodiment of a fire-rated wall component with intumescent material on both its top and side surfaces.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] The present invention is directed toward fire-rated wall construction components and systems for use in building construction. Fire-rated wall construction components and assemblies are commonly used in the construction industry. These components and assemblies are aimed at preventing fire, heat, and smoke from leaving one portion of a building or room and entering another, usually through vents, joints in walls, or other openings. The components and assemblies often incorporate the use of some sort of fire-retardant material, such as intumescent material, which substantially blocks the path of the fire, heat, and smoke for at least some period of time.
[0024] FIG. 1 illustrates a cross-sectional view of an embodiment of a fire-rated wall component 10 connected to a floor or ceiling element 18 and stud element 20 . The wall component 10 is used as a track for holding a stud within a vertical wall, and may include slots along its sides. The slots provide areas for connection with the studs and allow for vertical movement of the attached studs during an earthquake or some other event where vertical movement of the studs is desired.
[0025] As can be seen in FIG. 2 , wall component 10 has both a flat top surface 28 and two annular surfaces 24 and 26 . Top surface 28 is flat for ease of attachment to the bottom surface of a floor or ceiling 18 . The two annular surfaces 24 and 26 are designed to receive intumescent material. The intumescent material, identified as 12 and 14 in FIGS. 1 and 3 , is bonded to annular surface 24 and 26 . The term “bonded,” as used herein, is a broad term, and is used in accordance with its ordinary meaning. The term includes, but is not limited to, mechanically bonded or bonded using adhesive. In some embodiments, when the intumescent material is bonded, an outer surface of the intumescent material will be flush with top surface 28 . This allows top surface 28 to remain flush, or at least partially flush, with the bottom of floor element 18 , and may aid in the installation of wall component 10 to a floor or ceiling. This flush attachment additionally allows the wall component 10 to retain a fluid or smooth-shaped geometry free of added edges, overlaps, or protrusions.
[0026] By incorporating intumescent material onto a wall component such as a track for studs in the manner shown, it becomes unnecessary to use or attach additional features or devices to the wall component. Instead, when the temperature rises near the wall component 10 , the intumescent material 12 and/or 14 will heat up. At some point when the intumescent material becomes hot enough, it will quickly expand to multiple times its original volume. This intumescent material will expand towards the floor or ceiling element 18 and outwards toward any open space. This helps to substantially prevent fire, heat, and smoke from moving past, through, or around wall component 10 and stud 20 for at least some period of time.
[0027] FIG. 4 illustrates another embodiment of a fire-rated wall component 32 . In this embodiment, the wall component 32 again takes the form of a track member for use in holding studs in place within a vertical wall. However, here the wall component 32 has two slots, shown as 34 and 36 , wherein the intumescent material 40 and 42 is attached. As can be seen in the drawing, the top surface layers of intumescent material 40 and 42 are flush with the top surface 38 of wall component 32 . This allows the top surface 38 of wall component 32 to maintain a smooth geometry, which may aid in the installation of wall component 32 to a floor, ceiling or intersecting wall. This flush attachment additionally allows the wall component 10 to retain a fluid or smooth-shaped geometry free of added edges, overlaps, or protrusions. However, a flush attachment as described above is not essential to the success of the present invention.
[0028] It is possible that more than two slots could be used in the type of embodiment shown in FIG. 4 , or even as few as one. The purpose of having the intumescent material located in the slots 34 and 36 is to create fire protection areas. When the intumescent material 40 and 42 becomes hot, it will expand rapidly into the open areas around it. Much as in the embodiment shown in FIGS. 1-3 , this expansion will help to create a barrier, or seal, substantially preventing fire, heat, and smoke from moving from one area of a building to another for at least some period of time.
[0029] FIGS. 5A and 5B illustrate other embodiments of a fire-rated wall component 46 . Here, the wall component takes the form of a vent. The wall component 46 has a lower ventilation area 48 which includes a set or series of ventilation holes. These holes, which are hidden from view in FIGS. 5A and 5B , but are shown in FIG. 7 , allow air and other matter to travel between floors and rooms in a building, or between the outside of a building and the interior of a building.
[0030] As can be seen in FIG. 5A , a strip of intumescent material 50 is attached adjacent to and above ventilation area 48 . The top surface of the intumescent material is flush with the top surface 54 of wall component 46 . This allows for easy installation and use of a flat strap 52 . A flush fit, however, is not essential to the success of the present invention.
[0031] The intumescent material 50 has a series of surfaces defining holes. These holes are hidden from view in FIGS. 5A and 5B but are shown in FIG. 6 . The holes allow air and other matter to continue to travel between floors and rooms in a building, or between the outside of a building and the interior of a building. Flat strap 52 also has a series of holes 60 located in its center area. This series of holes, much like the ventilation and intumescent material holes, allows air and other matter to travel between floors and rooms in a building, or between the outside of a building and the interior of a building..
[0032] When the intumescent material 50 becomes hot, it will expand rapidly into the open areas around it. Much as in the embodiments shown in FIGS. 1-4 , this expansion will help to create a barrier, or seal, substantially preventing fire, heat, and smoke from moving from one area of a building to another for at least some period of time.
[0033] FIG. 6 illustrates another embodiment of a fire-rated wall component 56 . In this view, intumescent material holes 58 are visible, and the intumescent material 50 extends along the sides of vent area 48 . When the intumescent material 50 becomes hot, it expands rapidly, filling much if not all of the space underneath the flat strap 52 . This expansion substantially cuts off any air movement through the vent surface 48 , and substantially prevents fire, heat, and smoke from moving through the vent for at least some period of time. As can be seen in the embodiment in FIG. 6 , the flat strap 52 is formed as an integral part of the wall component 56 . In other embodiments, the flat strap 52 may be a discrete piece attached separately.
[0034] FIG. 7 illustrates a bottom view of an embodiment of a fire-rated wall component 66 . Here, ventilation holes 68 can be seen in the vent area 48 . The intumescent material 50 is attached to both the vent area 48 and along its extended sides.
[0035] FIG. 8 illustrates another embodiment of a fire-rated wall component 72 . In this embodiment, the wall component 72 resembles a simple track for holding a wall stud 20 beneath a ceiling 18 . Here, the intumescent material 74 is attached to the top surface of the wall component 72 . During installation, it is possible to install the wall component 72 and intumescent material 74 to the ceiling 18 . In some embodiments, this may be accomplished by threading a screw through both the wall component and intumescent material. Additionally, in some embodiments the intumescent material may extend down one or both sides of the wall component 72 .
[0036] FIG. 9 illustrates another embodiment of a fire-rated wall component 80 . In this embodiment, the wall component 80 resembles a simple track for holding a wall stud. However, here the intumescent material 84 extends both along a portion of the top and side surfaces of the wall component 80 . In some embodiments, an outer surface of the intumescent material 84 may be flush with the top surface 82 .
[0037] The present application does not seek to limit itself to only those embodiments discussed above. Other embodiments resembling tracks, vents, or other wall components are possible as well. Various geometries and designs may be used in the wall components to accommodate the use of fire-retardant material. Additionally, various materials may be used. The wall component material may comprise steel or some other material having at least some structural capacity. The fire-retardant material may comprise intumescent material or some other material which accomplishes the same purposes as those described above.
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The present invention is directed toward fire-rated wall construction components for use in building construction. The invention provides wall components and systems which have fire-retardant characteristics, as well as wall components which allow for needed ventilation in a building throughout times when no fire is present. Embodiments include tracks for holding studs which incorporate various geometries capable of receiving intumescent material. When the intumescent material becomes hot, it expands rapidly and fills its surrounding area, blocking fire, heat, and smoke from traveling to other areas of a building. Other embodiments
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to foreign French patent application No. FR 1552334, filed on Mar. 20, 2015, the disclosure of which is incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The invention pertains to a method for automatically focusing a camera, or to an autofocus. The invention also pertains to an automatic focusing system implementing such a method, and to a camera—and more specifically a digital camera—equipped with such a system.
BACKGROUND
[0003] In the literature and on the market, many automatic focusing methods exist, which may be grouped into two big families: open-loop and the closed-loop approaches.
[0004] Open-loop approaches require a distance sensor, for example a time-of-flight sensor; for this reason they are also known as “active” approaches. An open-loop controller receives, as input, a signal issued from this sensor, representing the distance of a subject to be imaged, and uses it to generate a signal for controlling an actuator that acts upon a focusing parameter of the camera. The latter may be the distance between a lens and an image sensor, or indeed the vergence of the lens if the latter is deformable. Typically, the controller merely applies a predefined lookup table matching a distance measured by the sensor to a voltage or current level, delivered to the actuator. One advantage of this approach is that it is very fast. However, it has many drawbacks: the extra cost linked to the use of an active distance sensor, the need for a calibration to be carried out in order to construct the lookup table of the open-loop controller and for it to be repeated periodically in order to compensate for the drift of the optical module and of the actuator, and sensitivity to non-measurable disturbances that prevent a level of precision from being guaranteed (lack of robustness). An exemplary open-loop, or active, autofocus is given in the document U.S. Pat. No. 6,292,256.
[0005] Closed-loop approaches do not make use of a distance sensor (they are therefore known as “passive” approaches), but rather of a module for estimating quality, which extracts a quality metric—typically sharpness—from the obtained image. This estimation is compared to a reference value in order to deliver an error signal; a closed-loop controller acts upon an actuator in such a way as to minimize this error signal. Among the advantages of this approach, mention may be made of the absence of an active distance sensor, and the fact that disturbances and drift are taken into account without the need for calibration. In contrast, if the performance of the system is to be robust in the face of uncertainties in optical module performance (for example linked to technological variability), the control law must be chosen wisely, this requiring a certain level of expertise on the part of the designer. Furthermore, speed is reduced with respect to open-loop systems.
[0006] There are a wide variety of closed-loop approaches.
[0007] One conventional solution consists in carrying out a search for a maximum sharpness (an indicator of the image quality) using a so-called “climbing” method on a sharpness curve. For this, the image sharpness estimator receives a matrix of signals from the image sensor and uses it to calculate a sharpness indicator “n” according to a chosen metric. Next (considering, for the sake of simplicity, the single case of a system with a variable focus lens), the value y=∂n/∂f of the sharpness gradient is calculated with respect to the focal length of the lens f; this makes it possible to determine the direction of the control to be applied. An integral-type control law is subsequently used, this allowing the lens to be deformed in such a way as to approach the maximum of the sharpness. This solution has a certain number of drawbacks. First of all, the calculation of the sharpness gradient is, by nature, very sensitive to noise. Furthermore, the signal for controlling the actuator is typically quantized, implying that all of the focal lengths in a given continuous interval [f min , f max ] are not actually attainable, leading to a degradation of the focusing precision. Decreasing the quantization step size allows focusing precision to be improved, but at the cost of increasing convergence time and power consumption. Parasitic oscillations may also occur about the optimum sharpness value.
[0008] The paper by Jie He et al. “ Modified Fast Climbing Search Auto - focus Algorithm with Adaptive Step Size Searching Technique for Digital Camera ”, IEEE Transaction on Consumer Electronics, 49(2): 257-262 (2003) describes a refinement of this approach, in which the quantization step size is chosen depending on the proximity to the maximum (larger far away from the maximum, and increasingly small as proximity thereto increases). This makes it possible, at least in principle, to improve response time and power consumption. However, reliably determining the proximity of the maximum is not simple: specifically, the sharpness gradient is generally low both close to the optimum focusing conditions and far away therefrom. In practice, the rules for readapting the gain are chosen assuming a priori knowledge of the behaviour of the optical module, whereas in cases of actual use, this behaviour is often different from that modelled—owing to, for example, technological variability and temperature drift—thereby leading to a loss of focusing performance.
[0009] Another possibility consists in using a PID (proportional-integral-derivative) controller with two additional degrees of freedom with respect to the purely integral control considered above. One advantage of this approach is that many proven methods for designing PID controllers are described in the literature. However, this type of control is worth considering only when the digital image sensor and the block for analyzing image sharpness operate at a speed comparable to or greater than that of the actuator of the lens (“slow lens”). Moreover, the model for which the PID controller has been setup does not allow the response time of the focusing system to be minimized because the model of the optical module changes depending on the scene in question. Furthermore, technological variability or even temperature drift implies that the actual module follows a model that is different to that used to set up the controller.
[0010] Yet another possibility consists in adopting a predictive approach, see, for example, the paper by L.I.-C. Chiu et al. “ An efficient auto focus method for digital still camera based on focus value curve prediction model ”, Journal of Information Science and Engineering, 26(4): 1261-1272, (2010). In this approach, the sharpness as a function of the position of the lens given by a sum of bell curves is assumed to be mathematically modelled, the parameters of which must be identified. The presented results suggest that this method allows a very fast convergence to be obtained, at least in the presence of a single sharpness peak—this, typically, corresponding to the presence of a single object in the imaged scene. However, in the presence of a plurality of objects, the identification of the parameters of the model is a non-linear and, in general, non-convex problem, the computational complexity of which risks becoming prohibitive.
[0011] The invention aims to overcome, entirely or in part, at least some of the aforementioned drawbacks. More precisely, the invention aims to provide an automatic focusing method that is both robust and fast and that does not require the use of an active distance sensor. The invention aims in particular to provide such a method that is well suited to the case of a “fast lens”, i.e. to a camera in which the response time of the actuator and of the optical module is less than the time required for the acquisition of the images and for the calculation of a sharpness metric.
SUMMARY OF THE INVENTION
[0012] One subject of the invention, allowing this aim to be achieved, is a method for automatically focusing a camera comprising an image sensor, at least one lens configured to project an image onto said sensor and an actuator configured to modify a focusing parameter of the lens, the method comprising:
[0013] a first phase comprising:
an open-loop control of said actuator, so that said focusing parameter successively takes a plurality of predefined values; the acquisition of a plurality of images by means of said sensor, each corresponding to one said predefined value of the focusing parameter; and the calculation of a sharpness indicator on the basis of each of said images;
[0017] and
[0018] a second phase of controlling, in a closed loop, said actuator so as to maximize said sharpness indicator;
[0019] said second closed-loop control phase being implemented by making use of a control law and starting conditions determined on the basis of the sharpness indicators calculated during said first phase.
[0020] Another subject of the invention is a system for automatically focusing a camera comprising:
[0021] an actuator configured to modify a focusing parameter of a lens of the camera; and
[0022] a processor configured to receive, as input, a signal representative of an image acquired by an image sensor of the camera and to produce, at its output, a signal for controlling said actuator;
[0023] characterized in that said processor is configured or programmed to implement such a method.
[0024] Yet another subject of the invention is a camera comprising an image sensor, at least one lens configured to project an image onto said sensor and such an automatic focusing system the actuator of which is configured to modify a focusing parameter of said lens and the processor of which is configured to receive, as input, a signal representative of an image acquired by said sensor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Other features, details and advantages of the invention will be brought to light upon reading the description given with reference to the appended drawings which are given by way of example and which show, respectively:
[0026] FIG. 1 , the block diagram of a camera according to one embodiment of the invention;
[0027] FIG. 2 , a flow diagram of a method according to one embodiment of the invention;
[0028] FIG. 3 , a block diagram illustrating a control law according to one embodiment of the invention;
[0029] FIGS. 4 a , 4 b and 4 c , graphs illustrating three possible embodiments of the first open-loop control phase.
[0030] FIGS. 5 a and 5 b , illustrations of the implementation of the second closed-loop control phase according to two alternative embodiments of the invention; and
[0031] FIGS. 6 a , 6 b , 7 a , 7 b , 8 a and 8 b , graphs illustrating the technical result of the invention.
DETAILED DESCRIPTION
[0032] FIG. 1 shows a simplified block diagram of a digital camera with closed-loop automatic focusing, able to be adapted to the implementation of the invention. This camera essentially comprises an optical module MO, a matrix image sensor CMI and a processor PR. As for the optical module, it comprises at least one lens L and an actuator AC that allows at least one optical parameter of the module to be modified. In the example of the figure, the lens L is deformable and the actuator AC allows the vergence thereof to be modified; in other embodiments, the actuator could move the lens along its focal axis with respect to the sensor CMI. The lens forms an image on the sensor CMI, which produces an electronic signal I(x,y), where x and y are discrete indices identifying the pixels of the sensor. This signal is delivered to the processor PR which uses it, among other things, to generate a signal V for controlling the actuator, in accordance with the closed-loop autofocus principle. The camera may be integrated in another device, such as a mobile phone.
[0033] The idea on which the invention is based consists in using an automatic focusing method comprising two phases: a first open-loop phase not using an active distance sensor, and a second closed-loop phase. The first phase consists in a summary exploration of a space of focusing configurations; typically, it is a question of trialling a series of predefined values of the vergence of the lens, the position thereof or any other parameter representative of the focusing conditions. An image is acquired for each of these focusing configurations, and its sharpness value is calculated by the processor. This makes it possible:
[0034] 1) to determine a starting condition sufficiently close to the optimum sharpness;
[0035] 2) to determine an optimum control law.
[0036] FIG. 2 shows a flow diagram of a method implementing this principle. In the discussion of this flow diagram, the case will be considered in which focusing is achieved by moving the lens, but this is only a predefined example.
[0037] Step i consists in positioning the lens in a first predetermined position (or in adjusting its vergence to a first predetermined value). Next (ii), an image corresponding to this position of the lens is acquired and the sharpness value thereof is calculated. Multiple sharpness metrics that may be applied to the invention are described in the paper by S. Pertuz et al. “ Analysis of focus measure operators for shape - from - focus ” Pattern Recognition, 46(5): 1415-1432, 2013. Next (iii), a counter i, initially set at 1, is incremented, and these operations are iterated for as long as its value does not exceed a predefined maximum N (iv). Typically, the number of iterations is between 3 and 7, or even 10. At the end of this first open-loop phase, N sharpness measurements corresponding to as many different lens positions, have therefore been obtained. It is therefore possible to determine the maximum of the measured sharpness values (vi), thereby allowing a starting condition V max , i.e. the value attributed to the signal for controlling the actuator at the start of the closed-loop control phase (vi), to be calculated.
[0038] It is worth noting that, during the open-loop phase, the sampling of the space of focusing parameters is not necessarily uniform. By way of example, a still camera may be considered in which the user may select a “landscape” mode, a “macro” mode and a “portrait” mode. In “landscape” mode (cf. FIG. 4A ), the region of low focal lengths “f” is very roughly sampled, and the majority of the predefined values tested are close to infinity, where, in all likelihood, the maximum sharpness n will be found. Stated otherwise, the rate of advance of the lens gradually decreases. In contrast in “macro” mode low focal lengths are preferentially sampled ( FIG. 4B ). In “portrait” mode ( FIG. 4C ) the majority of the sampled focal lengths have intermediate values. In FIGS. 4A-4C , the sharpness n may equally be expressed as a function of the focal length f or of the control signal V FF (“FF” for “feed-forward”), these two quantities being linked by a (not necessarily linear) relationship specific to the actuator. The expression “focusing parameter” will be used below to signify, either an optical parameter such as the vergence of a lens or its distance from the image sensor, or the corresponding value of the signal for controlling the actuator.
[0039] If, for example, the case in FIG. 4C is considered, it will be noted that 9 focal length values are sampled (N=9); they are considered to be sampled in order, from the lowest focal length (for i=1) to the highest (i=N=9). The maximum sharpness corresponds to the case i=5. In order to get there from the end condition i=N=9, it would be necessary to move the lens backwards (i.e. in a direction opposite to that of the movement carried out during the open-loop phase). However, some actuators exhibit hysteresis; it may therefore be preferable, from the point of view of precision, to bring the lens back to its starting position (i=1), which typically corresponds to an end stop, and to move it forward to the optimum position. This approach to reducing the influence of hysteresis is of interest only if the lens has a response time much shorter than the operating rate of the imager, as the time limitation will come from the time required to position the lens in a stable state (i.e. after the transitional states). Nowadays, camera imagers generally operate at a speed of 60 frames per second (fps), corresponding to an interval between image acquisitions that is equal to 17 ms.
[0040] Next begins the closed-loop control phase. Returning to FIG. 2 , it may be seen that the first step of this second phase is the calculation of the “optimum” gain of the closed-loop control law (vi) on the basis of the “focusing parameter/image sharpness” pairs acquired beforehand. The implementation of this step according to one advantageous embodiment of the invention will be described in detail below with reference to FIG. 5 . Next, the lens is moved (viii) depending on the gain calculated in the preceding step, an image is acquired and the corresponding sharpness is calculated (ix). If the maximum sharpness is reached (which is typically determined by verifying that the last movement was smaller than a threshold), the method is stopped; otherwise, a new iteration is started (x). It is important to note that, during iterations other than the first, the calculation of the gain (step vii) is performed while also taking into account the sharpness measurements carried out during the closed-loop phase.
[0041] FIG. 3 illustrates a block diagram of an automatic focusing system implementing the method of FIG. 2 . The assembly composed of the optical module and the image sensor receives, as input, a spatial light intensity distribution I 0 , a noise br, and a control signal V that determines at least one focusing parameter; at its output it delivers an electronic signal I, representative of an image.
[0042] A switch makes it possible to choose between open-loop control (position 1) and closed-loop control (position 2). The open-loop controller corresponds to a static gain block K FF receiving, as input, a ladder signal, which allows the lens L of the optical module MO to be moved in a predetermined manner. The closed-loop controller is much more complex. It comprises a quality evaluation module EQ, which receives, as input, the signal I generated by the image sensor, and, at its output, delivers a sharpness measurement n. The closed-loop control block K FB first comprises a block for calculating the sharpness gradient ∇n (more precisely, the derivative of the sharpness with respect to the focusing parameter used for the control), a “sign” block for determining the sign of this gradient, a gain k i that changes from one iteration to another depending on the value of the gradient and an integrator.
[0043] In the figure, “V FF ” is the open-loop control signal, “V FB ” the closed-loop control signal and “V” the control signal actually applied to the actuator AC; V is equal to V FF or to V FB depending on the position of the switch. Typically, the processor PR, programmed in an appropriate manner, performs the functions of the closed-loop and open-loop controllers and of the switch: these elements therefore do not necessarily correspond to identifiable hardware elements: this is referred to as a software implementation. As a variant, the controllers may be implemented as hardware, using dedicated programmable logic circuits and/or integrated circuits. A hybrid software/hardware implementation is also possible.
[0044] The steps for calculating the closed-loop gain will now be described in detail with the aid of FIGS. 5 a and 5 b.
[0045] One advantageous aspect of the invention is the use of a quadratic approximation to locally model the sharpness characteristic in the vicinity of the maximum, this allowing the calculations to be performed during the closed-loop phase to be simplified most considerably.
[0046] The sharpness n is then modelled by:
[0000] n ( V )= a·V 2 +b·V+c (1)
[0047] where a, b, c are the parameters of the model. It will be assumed below—although this in no way constitutes a limitation—that the control signal V (or V FB , as it is the closed-loop control phase that is under consideration) represents a voltage applied to an AC actuator that modifies the vergence or the position of the lens L.
[0048] This hypothesis as to the shape of the sharpness curve in the vicinity of the maximum is not been rigorously verified in the general case. Nonetheless, it makes it possible to obtain an effective and easy-to-implement method allowing the maximum sharpness to be rapidly converged upon once the control loop is closed. Specifically, the parameters a, b and c of the quadratic model of the sharpness curve may be obtained analytically from three sharpness measuring points acquired during the open-loop phase.
[0049] As a variant, it is possible to choose a more complex model, but, taking account of the limited number of measuring points obtained in the open-loop phase, this runs the risk of over-parameterization. In order to limit this risk, it is possible, by making use of all of the sharpness measurements acquired in the open-loop phase, to determine a cubic spline type model (which may or may not be constrained). However, this alternative embodiment entails an additional computational cost. The retained quadratic model also has the appeal of being determinable analytically from the judicious choice of three measuring points obtained in the open-loop phase. Alternatively, and in particular if more measurements are taken during the open-loop phase, it is possible to make use of a least squares-type method to determine the model of the sharpness curve, although this is computationally more costly.
[0050] Another advantageous aspect of the invention is the use of an adaptive closed-loop control law in which the gain of the integrator of the closed-loop controller (or corrector) and, consequently, the step size of the actuator, vary depending on the proximity to the maximum sharpness. More precisely, in one embodiment of the invention, the information measured in the closed-loop phase is used to initialize the gain of the controller. This information is found in the gradient of the sharpness curve, the latter being modelled by the quadratic function of equation 1. This gradient is given by:
[0000]
∂
n
(
V
)
∂
V
=
2
aV
+
b
(
2
)
[0051] It is apparent that there is only one voltage V* corresponding to a zero gradient:
[0000]
V
*
=
-
b
2
a
(
3
)
[0052] Applying this voltage to the actuator allows it to be moved to the theoretical maximum sharpness, assuming a quadratic sharpness variation.
[0053] In practice, the parameters a and b of the quadratic model are unknown; in contrast, a few measuring points of the sharpness acquired for predefined voltages (open-loop phase) are available. Thus, in order to find the parameters a and b, it is possible to use a standard least squares type identification method. This method entails a non-negligible computational cost. However, the aim is to roughly determine the voltage range in which the voltage corresponding to the actual maximum sharpness is located. For this reason, as a first approximation, it is proposed to dispense with a least squares type of technique for identifying parameters. For this, three measuring points of the sharpness obtained in the open-loop phase, n max , n left , n Right , are retained, these points respectively being the open-loop measuring point having maximum sharpness, the point directly to the left and the point directly to the right (see the top part of FIG. 5 a , in which the voltage V* calculated by equation 3 is denoted by V 0 * for reasons that will be explained below). These three points are enough to define a parabola in a unique manner. This approach is very simple, but it does not allow measurement noise to be filtered out.
[0054] It is known that the abscissa for which the derivative of a parabola is equal to zero is located at the overall maximum (minimum). Knowing that the function that describes the sharpness is upwardly convex, then the term “a” in equation 1 is smaller than zero. In this case, it is known that the zero gradient corresponds to the overall maximum because the second derivative is negative. H is questionable whether it would be better to use the sharpness gradient (∇n, in FIGS. 5 a and 5 b ) instead of measuring the sharpness (n) directly. The problem with measuring the sharpness directly is that the absolute values are completely unpredictable and necessarily depend on the environment of the shot, whereas the absolute values of the gradient always converge towards zero when the voltage approaches the voltage corresponding to maximum sharpness. This advantage opens up the possibility of applying systematic determination methods for closed-loop control.
[0055] The first problem to be solved to implement the closed-loop control therefore consists in determining the voltage corresponding to the maximum sharpness, given three points measuring absolute sharpness, and under the assumption that the sharpness, curve as a function of the voltage applied to the actuator is quadratic.
[0056] This problem may be resolved by turning to Lagrange's theorem on the mean of a function: namely a continuous function fε defined over the interval [x 1 , x 2 ]ε ; there then exists a point x*ε[X 1 , x 2 ] such that:
[0000]
f
(
x
)
x
|
x
*
=
f
(
x
2
)
-
f
(
x
1
)
x
2
-
x
1
(
4
)
[0057] More precisely, the following corollary of this theorem is employed: let f(x)=ax 2 +bx+c, where x,a,b,cε ; then
[0000]
f
(
x
)
x
|
x
*
=
f
(
x
2
)
-
f
(
x
1
)
x
2
-
x
1
(
5
)
[0058] if and only if
[0000]
x
*
=
x
2
+
x
1
2
(
5
′
)
[0059] In the context of finding the zero gradient, this corollary is very useful as it makes it possible to obtain the voltages corresponding to levels of the gradients calculated from the sharpness measurement under the quadratic assumption. The three points measuring sharpness transform into two gradient points:
[0000]
left
=
∂
n
∂
V
|
V
=
V
grad
left
=
n
max
-
n
left
V
max
-
V
left
right
=
∂
n
∂
V
|
V
=
V
grad
right
=
n
right
-
n
max
V
right
-
V
max
(
6
)
[0000] where the voltages V grad left and V grad right are determined by applying the corollary:
[0000]
V
grad
left
=
V
max
+
V
left
2
V
grad
right
=
V
max
+
V
right
2
(
6
′
)
[0060] The estimated “zero” gradient is therefore located on a straight line defined by the voltages calculated to generate the gradients of the measurement. This straight line is defined by:
[0000]
∂
n
∂
V
-
∂
n
(
V
grad
left
)
∂
V
∂
n
(
V
grad
right
)
∂
V
-
∂
n
(
V
grad
left
)
∂
V
=
V
-
V
grad
left
V
grad
right
-
V
grad
left
(
7
)
[0061] In order to simplify the notation,
[0000]
=
∂
n
(
V
)
∂
V
[0000] is posited and the following is obtained:
[0000]
-
left
right
-
left
=
V
-
V
grad
left
V
grad
right
-
V
grad
left
(
7
′
)
[0062] It follows that the voltage V* corresponding to this zero gradient (and therefore to the estimated maximum sharpness) is given by:
[0000]
V
*
=
V
grad
left
-
left
right
-
left
(
V
grad
right
-
V
grad
left
)
(
8
)
[0063] By eliminating intermediate variables, the following is obtained:
[0000]
V
*
=
1
2
⌈
V
max
+
V
left
-
(
n
max
-
n
left
)
(
V
right
-
V
left
)
(
V
right
-
V
max
)
n
left
(
V
right
-
V
max
)
+
n
max
(
V
left
-
V
right
)
+
n
right
(
V
max
-
V
left
)
⌉
(
9
)
[0064] This is illustrated by the graphs in the top part of FIG. 5 a , in which the value V* given by the equations (8) and (9) is denoted by V 0 *.
[0065] Returning to FIG. 3 , it will be recalled that the closed-loop control block K FB comprises an integrator (symbol “f”) and a variable gain k 1 , adjusted at each instant “i” of sampling. The control law implemented by the block K FB may therefore be written:
[0000]
K
FB
:
V
FB
=
k
i
int
∑
l
=
0
i
sign
(
l
)
Δ
t
[0066] where k i int is the value of the adjusted gain at the instant i, G l is the gradient calculated from two neighbouring voltages at the input of the optical module and corresponding sharpness values n and Δt is the temporal step size sampling. As operation is in discrete time, the integration is in fact a sum weighted by Δt.
[0067] As the quadratic assumption is not always realistic, it is proposed, in accordance with one advantageous embodiment of the invention, to use a gain k i int that is modified at each instant of sampling (i.e. each time the sharpness indicator is calculated in closed-loop operation) while taking into account all of the measurements carried out over the course of the closed-loop phase, in which the sharpness gradient may be considered to be linear. This approach is radically different from the adaptive control methods known from the prior art, as the gain k i int is chosen in such a way as to cancel out the gradient calculated from direct measurements, under the assumption of a quadratic sharpness variation.
[0068] Thus, the adaptive gain k i int for closed-loop operation is calculated using the approach of searching for the zero gradient using the approach presented in FIG. 5 a . It will be noted that in this figure, the measured sharpness values are represented by stars, whereas the calculated values of the gradients and the estimated sharpness values corresponding to these gradients are represented by circles, and that a triangle represents the estimation of the voltage value corresponding to the maximum sharpness.
[0069] The starting condition of the closed-loop phase is given by the voltage V max tested in the open-loop phase, that maximizes the sharpness. Next, applying equation 9 allows the voltage value V 0 *=V*, which corresponds to a zero sharpness gradient, and therefore to the theoretical maximum sharpness under the quadratic assumption, to be found.
[0070] Thus, the optimum integrator gain, which cancels out the theoretical gradient for the first step of advance in the closed-loop phase, is defined by:
[0000] k 0 int =|V 0 *−V FF end | (10)
[0000] where V 0 * is given by
[0000]
V
0
*
=
1
2
[
V
max
+
V
left
-
(
n
max
-
n
left
)
(
V
right
-
V
left
)
(
V
right
-
V
max
)
n
left
(
V
right
-
V
max
)
+
n
max
(
V
left
-
V
right
)
+
n
right
(
V
max
-
V
left
)
]
[0000] (cf. equation 9), whereas V FF end is the control voltage at the end of the open-loop phase. If the quadratic assumption were rigorously verified, and if the sharpness measurements were not affected by noise, then the method according to the invention could stop here; however, this is generally not the case.
[0071] By applying the voltage V 0 * to the actuator, it is possible to acquire a new sharpness value. Four sharpness measurements are thus available, allowing three gradient values and the corresponding voltages given by the corollary of Lagrange's theorem (equation 5′) to be calculated; these gradient values are those determined previously (G left , G right ), plus a new value denoted by G 2 . In theory, these three gradient points should be located on the straight line given by equation 7, but that is not the case in practice (as the quadratic assumption is only an approximation and the measurements are affected by noise). As shown by the graphs in the bottom-right part of FIG. 5 a , three unaligned gradient points make it possible to identify three straight lines the mean of which (shown by the dotted line) is chosen as the “straight line of the gradients” for the 2 e iteration of the closed-loop phase. V 1 * denotes the voltage value at which this mean straight line intercepts the axis of the abscissae: this constitutes a new approximation of the zero-sharpness gradient point (and hence maximum sharpness). The new value of the gain of the controller is given by:
[0000] k 1 int =|V 1 *−V 0 *| (10′)
[0072] By applying the voltage V 1 * to the actuator, it is possible to acquire a new sharpness value. Five sharpness measurements are thus available, allowing four gradient values and the corresponding voltages given by the corollary of Lagrange's theorem (equation 5′) to be calculated. As in the preceding iteration, these four points (V, ∇n) are not aligned, and allow six different gradient straight lines to be identified, the mean of which is taken in order to determine a new approximation of the zero-sharpness gradient point (and hence maximum sharpness), denoted by V 3 * and so on. The bottom-right part of FIG. 5 a illustrates the situation after the third iteration.
[0073] Generally speaking, the gain on the i th iteration (where i≧1) is given by:
[0000] k i int =|V i *−V i-1 *| (11)
[0000] where V i * is the voltage value V that cancels out the mean gradient Ĝ.
[0074] It is possible to give a general analytic expression for the straight line of the mean gradient Ĝ for each iteration of the closed-loop phase, and hence also for V i * for all cases where i≧0. To do this, it is first necessary to define the vector V l =(V 0 V 1 , . . . , V i ), the elements V l of which are the values of the control voltage calculated during the preceding iterations of the closed-loop phase, and the “starting” voltages V max , V left and V right obtained during the open-loop phase; it will be understood that the size of the vector V l increases throughout the closed-loop phase. Thus, during the first iteration (i=1): (V 0 =V left ; V 1 =V max ; V 2 =V 0 * ; V 3 =V right ); these data make it possible to calculate V 1 *, which will be integrated into the vector V l (its elements being reorganised in order to retain the ascending order), and so on.
[0075] Thus
[0000]
^
=
1
i
+
1
∑
l
=
0
i
(
l
-
V
l
l
+
1
-
l
V
l
+
1
-
V
l
+
V
l
+
1
-
l
V
l
+
1
-
V
l
)
(
12
)
[0000] where
[0000]
l
=
n
l
+
1
-
n
l
V
l
+
1
-
V
l
[0000] in which n l =n(V l ).
[0076] Thus, the averaged slopes are those of the straight lines that link measurements of sharpness corresponding to adjacent voltage values. This may be seen in the bottom part of FIG. 5 a.
[0077] The sum that appears in equation 12 carries out a low-pass filtering which reduces the influence of the noise affecting the sharpness measurements.
[0078] If the expression for the gradient mean straight line is written as:
[0000] Ĝ=â i V+{circumflex over (b)} i ;
[0000] then the mean slope â i is given by:
[0000]
a
^
i
=
2
i
+
1
∑
l
=
0
i
l
+
1
-
l
V
l
+
1
-
V
l
=
2
i
+
1
∑
l
=
0
i
(
V
l
+
1
-
V
l
)
(
n
l
+
2
-
n
l
+
1
)
(
V
l
+
2
-
V
l
+
1
)
(
n
l
+
1
-
n
l
)
(
V
l
+
2
-
V
l
+
1
)
(
V
l
+
1
-
V
l
)
(
V
l
+
2
-
V
l
)
(
13
)
[0000] and the y-intercept {circumflex over (b)} i by:
[0000]
b
^
i
=
1
i
+
1
∑
l
=
0
i
(
l
-
V
l
l
+
1
-
l
V
l
+
1
-
V
l
)
=
1
i
+
1
∑
l
=
0
i
(
n
l
+
1
-
n
l
V
l
+
1
-
V
l
-
(
V
l
+
V
l
+
1
)
(
V
l
+
1
-
V
l
)
(
n
l
+
2
-
n
l
+
1
)
-
(
V
l
+
2
-
V
l
+
1
)
(
n
l
+
1
-
n
l
)
(
V
l
+
2
-
V
l
+
1
)
(
V
l
+
1
-
V
l
)
(
V
l
+
2
-
V
l
)
)
(
14
)
and
V
i
*
=
-
b
^
i
a
^
i
(
15
)
[0079] Equation 15, and equations 13 and 14, makes it possible to calculate the values of V i * for all cases where i≧0; specifically, equation 9 is obtained as a special case of equation 15 for i=0.
[0080] It is worth noting that in general the mean gradient straight line (equations 12 to 14) does not coincide exactly with the linear approximation of the gradient in the sense of the least squares method. Nevertheless, it has empirically been found that the greater the number of measurements, the closer the mean straight line gets to that calculated by the least squares method, thereby justifying the proposed method.
[0081] In order to reduce the influence of the small number of measurements on the proximity of the mean straight line to the linear estimation of the conventional least squares type, one alternative embodiment proposes the use of the median straight line, the slope of which may be estimated using the following equation:
[0000]
a
^
i
=
1
M
∑
(
i
,
j
)
∈
Ω
i
-
j
V
i
-
V
j
(
16
)
[0082] and the median bias by
[0000]
b
^
i
=
1
N
-
1
∑
l
=
1
N
-
1
(
l
-
a
^
V
l
)
.
(
16
′
)
[0083] M being the number of lines connecting N points in an “each to every other” manner defined by M=i(i−1)/2 and Ω is the set of all of the non-repeated pairs of indices i and j.
[0084] The control may be considered as having reached the point of optimum functioning (i.e. the optimum focus where reached) in the case the increment of the voltage V* is negligible from one instant of sampling to another, or else this increment is smaller than the discretization used for the supply voltages of the lens actuator.
[0085] It is now necessary to consider two cases in which the implementation of the invention may prove to be problematic.
[0086] The first—seemingly favourable—is that in which the voltage corresponding to the maximum sharpness measured during the open-loop phase, V max , is close to (or even identical to, taking account of the fact that the voltages are discretized) that calculated during the first application of the quadratic model, V 0 *. Since the behaviour of the sharpness curve in real cases is highly sensitive to noise, the calculated gradient may be heavily disrupted and the position of the zero gradient sought may be heavily skewed. One possible solution in order to overcome this problem is to apply a control V 0 +ΔV for the initialization of the closed loop, where ΔV would be a minimum applicable voltage to the left or right of the voltage V 0 *=V max . Stated otherwise, if the calculated voltage V 0 * proves to be too close to V max , then it is changed slightly. The sign of ΔV is defined as:
[0000] sign(Δ V )=sign( V max −V 0 *).
[0087] In the event that the quadratic assumption for the sharpness is confirmed, i.e. if the sharpness measured for a control voltage V 0 *+ΔV is sufficiently close to that measured in relation to V 0 *, the closed-loop control phase is stopped. Otherwise, the previously described iterative process is applied in order to find the voltage that corresponds to a sharpness gradient of (approximately) zero.
[0088] The second case is that in which the quadratic assumption is not verified, even in an approximative manner. This may be the case not only because of a particular configuration of the scene or of the optical module, but also when objects present in the area of interest are moving. In this case, the variation of the sharpness as a function of the voltage applied to the actuator, modelled by a parabola (quadratic curve), does not make it possible to converge towards the maximum sharpness in an efficient manner, as the choice of the gain in the closed-loop phase is made so that the peak of mean sharpness is moved towards, which implies a weak bias (movement) of the parabola for each measurement. This implies that the focal power that will ultimately be chosen for the focus will not be that which maximizes the sharpness.
[0089] In order to avoid this situation, it is suggested that the closed-loop gain be chosen as a moving average, i.e. to take into consideration only the L last measurements that were carried out during the closed-loop phase. This approach makes it possible to achieve a low-pass filtering effect on the modification of the voltage V i * from one instant to another. The measurements that were carried out outside the preceding L instants are not taken into account for the calculation of the gain k i int . The calculation of the gain is therefore performed in the following manner (for the embodiment using one mean straight line for the gradients, cf. FIG. 5 a and equations 13 to 15):
[0000]
a
^
i
=
2
L
+
1
∑
l
=
0
L
i
-
l
+
1
-
i
-
l
V
i
-
l
+
1
-
V
i
-
l
=
=
2
L
+
1
∑
l
=
0
L
(
V
i
-
l
+
1
-
V
i
-
l
)
(
n
i
-
l
+
2
-
n
i
-
l
+
1
)
-
(
V
i
-
l
+
2
-
V
i
-
l
+
1
)
(
n
i
-
l
+
1
-
n
i
-
l
)
(
V
i
-
l
+
2
-
V
i
-
l
+
1
)
(
V
i
-
l
+
1
-
V
i
-
l
)
(
V
i
-
l
+
2
-
V
i
-
l
)
(
17
)
b
^
i
=
1
L
+
1
∑
l
=
0
L
(
i
-
l
-
V
i
-
l
i
-
l
+
1
-
i
-
l
V
i
-
l
+
1
-
V
i
-
l
)
=
=
1
L
+
1
∑
l
=
0
L
(
n
i
-
l
+
1
-
n
i
-
l
V
i
-
l
+
1
-
V
i
-
l
--
(
V
i
-
l
+
V
i
-
l
+
1
)
(
V
i
-
l
+
1
-
V
i
-
l
)
(
n
i
-
l
+
2
-
n
i
-
l
+
1
)
-
(
V
i
-
l
+
2
-
V
i
-
l
+
1
)
(
n
i
-
l
+
1
-
n
i
-
l
)
(
V
i
-
l
+
2
-
V
i
-
l
+
1
)
(
V
i
-
l
+
1
-
V
i
-
l
)
(
V
i
-
l
+
2
-
V
i
-
l
)
)
(
18
)
V
i
*
=
-
b
^
i
a
^
i
(
19
)
[0000] where 1<L<i defines the size of the moving window in terms of number of samples. The choice of L makes it possible to impose a bandwidth of greater or lesser size (and hence to modulate the effect of the low-pass filtering) depending on the optical module used (noise level of the image sensor, optical characteristics of the lenses). The use of this improvement in the choice of the closed-loop gain allows the method to be made more robust with respect to the behaviour of the sharpness when the quadratic assumption is not satisfied.
[0090] It may be noted that equations 13 to 15 may be considered to be a special case of equations 17 to 19, corresponding to the case L=i.
[0091] The use of a moving window is also possible for the embodiment using a median straight line for the gradients, cf. FIG. 5 b and equations 16, 16′. In this case:
[0000]
a
^
i
=
1
M
∑
(
i
,
j
)
∈
Ω
i
-
j
V
i
-
V
j
(
20
)
b
^
i
=
1
L
-
1
∑
l
=
1
L
-
1
(
l
-
a
^
V
l
)
(
20
′
)
[0092] Ω henceforth being defined as the set of all the non-repeated pairs of indices, while considering only the L last indices (indices between “i−L” and “i” for i>L, and all of the indices for i≦L).
[0093] The technical result of the invention will now be illustrated with the aid of FIGS. 6 a to 8 b.
[0094] FIG. 6 a shows the sharpness curve (relative sharpness, normalized to 1, as a function of the analogue control voltage of the actuator) of a camera, measured by moving the lens at a very fine rate of advance. The black dots correspond to the acquisitions carried out during the open-loop control phase and the grey dots to the various iterations of the closed-loop phase. Due to noise, these dots are not located exactly on the curve. FIG. 6 b shows the gradient of the sharpness, obtained by taking the derivative of the sharpness curve (continuous curve) and calculated during the closed-loop phase on the basis of the quadratic assumption (broken line). It will be noted that even though the approximation of the gradient is relatively rough, the estimation of the voltage that cancels out ∇n is remarkably good.
[0095] FIG. 7 a shows how the sharpness of an image varies over time (the edge of a door at a distance of 3.5 m from the lens of the camera) during the focusing method of the invention (black lines) and a method known from the prior art (grey lines) known as binary search, in which the rate of advance is divided by two each time the sharpness peak is exceeded: see N. Kehtarnavaz and H.-J. Oh “ Development and real - time implementation of a rule - based auto - focus algorithm ” Real-Time Imaging, 9(3): 197-203, 2003. FIG. 7 b shows the variation of the analogue control voltage of the actuator for these two cases in point. It may be seen that, in the case of the method according to the invention, the 5 first clock ticks correspond to the open-loop phase, over the course of which the lens moves in one direction. At the time t=6, the lens is positioned at the “provisional” maximum identified during the open-loop phase; 6 closed-loop iterations follow. Focusing was repeated multiple times with the two methods; a lesser degree of variability may be noted in the case of the invention, which translates into a decreased sensitivity to noise.
[0096] FIGS. 8 a and 8 b correspond to the case where the imaged object is a test card located 5 m away from the lens. In this case it may be noted that the method of the invention leads to a much quicker convergence than that known from the prior art (binary search, as in the case of FIGS. 7 a , 7 b ).
[0097] In order to produce FIGS. 7 a to 8 b , a sharpness measurement based on the Haar transform and on the concept of local contrast was used. See, for example, the paper by M. Trivedi, A. Jaiswal and V. Bhateja “ A no - reference image quality index for contrast and sharpness measurement ”, 3rd International Advance Computing Conference (IACC), 2013 IEEE, pages 1234-1239, February 2013.
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A method for automatically focusing a camera comprising an image sensor, at least one lens configured to project an image onto the sensor and an actuator configured to modify a focusing parameter of the lens, comprises: a first phase of controlling the actuator in an open loop so the focusing parameter successively takes a plurality of predefined values, images being acquired for each value of the focusing parameter and a sharpness indicator being calculated on the basis of each image; and a second phase of controlling the actuator in a closed loop to maximize the sharpness indicator, the second closed-loop control phase being implemented by making use of a control law and starting conditions determined on the basis of the sharpness indicators calculated during the first phase. A system for automatically focusing a camera for implementing the method, and a camera equipped with such a system is provided.
| 6
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to flexible sign panel assemblies.
2. Description of the Related Art
Roadside warning signs are required for temporary worksite activities such as utility repair and accident investigation. With increased traffic speeds and higher volumes of vehicle and pedestrian traffic temporary warning signs are employed in greater numbers. Accordingly, work crews carry larger numbers of lightweight temporary warning signs for ready deployment upon arrival at a worksite. It is important that the temporary warning signs of this type be lightweight and afford compact storage. Today, temporary warning signs typically employ message panels made of a flexible fabric such as a plastic mesh of polyethylene or vinyl material. The sign panels are typically reinforced by flexible ribs of lightweight material, such as glass fiber composition. In use, the flexible sign panels are stretched taut to maintain a generally flat message display position. Wind gusts and traffic induced wind bursts put substantial strain on the flexible panel and it is important that these applied forces be resolved by a sign panel support. It is important that the sign panel support be configurable for compact storage, to complement the compact storage of the sign panel.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a support base for a message panel, particularly message panels of the flexible type employed, for example, to provide roadside warnings.
Another object of the present invention is to provide a sign stand assembly with a support base which can be collapsed into a compact package for storage.
Yet another object of the present invention is to provide a support base having one or more upright coil springs adapted for flexural loading.
These and other objects according to principles of the present invention are provided in a resilient support assembly for use in assign stand assembly to support a mast which carries a message panel and which has a lower end extending below the message panel, the resilient support assembly comprising:
a coil spring;
an upper spring mounting adapter;
a lower spring mounting adapter;
the upper spring mounting adapter having external threads threadingly engaged with the upper end of the coil spring;
the upper spring mounting adapter including a lower threaded end carrying the external threads and an upper end having a keyed portion;
the keyed portion including a mounting surface and a pair of key members upwardly protruding therefrom, the key members located on either side of a threaded bore, with the key members and mounting surface together comprising a concave socket for support receiving a support for the mast with a close tolerance fit preventing rotation of the support with respect to the resilient support assembly and the threaded bore for maintaining the support in engagement with the mounting surface, in keyed engagement with the keyed portion of the spring mounting adapter;
the lower spring mounting adapter having external threads threadingly engaged with the lower end of the coil spring;
the lower spring mounting adapter including an upper threaded end carrying the external threads and a lower end having a mounting surface, the lower end defining a threaded bore and a pin receiving hole extending from the mounting surface;
a threaded fastener engaging the threaded bore to maintain the leg mount in engagement with the mounting surface; and
a pin received in the pin-receiving hole for engaging apparatus supporting the resilient support assembly to prevent rotation relative thereto.
Other objects according to principles of the present invention are provided in a sign stand assembly comprising:
a message panel;
a panel support including a cross rib supporting the panel;
a mast connected to the cross rib and having a lower end extending below the message panel;
a support base including a clevis having a bight portion, a resilient support assembly and a leg mount, with the resilient support assembly connected to the leg mount;
a mast clamp coupled to the lower end of the mast to provide support therefor;
the clevis coupled to the lower end of the mast to provide support therefor;
ground-engaging members coupled to the leg mount to provide support therefor;
the resilient support assembly including a coil spring and a spring mounting adapter having external threads threadingly engaged with the upper end of the coil spring; and
the spring mounting adapter including a lower threaded end carrying the external threads and an upper end having a keyed portion including a mounting surface and a pair of key members upwardly protruding therefrom, the key members located on either side of a threaded bore, with the key members and mounting surface together comprising a concave socket for receiving the bight portion with a close tolerance fit preventing rotation of the bight portion with respect to the resilient support assembly and a threaded fastener engaging the threaded bore to maintain the bight portion in engagement with the mounting surface, in keyed engagement with the keyed portion of the spring mounting adapter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of a sign stand assembly;
FIG. 2 is a fragmentary view of a lower portion of the sign stand assembly;
FIG. 3 is a perspective view of the support base thereof;
FIG. 4 is a perspective view of a leg mount assembly thereof;
FIG. 5 is a perspective view of the spring mount adapter thereof;
FIG. 6 is a another perspective view thereof;
FIG. 7 is bottom plan view thereof;
FIG. 8 is a top plan view thereof;
FIG. 9 is a side-elevational view thereof;
FIG. 10 is cross-sectional view taken along the line 10 — 10 of FIG. 8;
FIG. 11 is a side elevational view similar to that of FIG. 9 showing the tapered construction thereof;
FIG. 12 is a cross-sectional view similar to that of FIG. 10, showing engagement with spring coils;
FIGS. 13 and 14 are perspective views of the resilient support assembly;
FIG. 15 is a perspective view of a leg mount;
FIG. 16 is a top plan view of an alternative arrangement of support base components;
FIG. 17 is a cross-sectional view taken along the line 17 — 17 of FIG. 16;
FIG. 18 is a fragmentary bottom plan view of an alternative sign stand assembly; and
FIG. 19 is a perspective view of another embodiment of a sign stand assembly.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Turning now to FIGS. 1-15 and initially to FIG. 1 a first embodiment of a sign stand assembly is generally indicated at 10 . Included is a message panel assembly generally indicated at 12 having a flexible message panel 14 made of any suitable material such as a plastic mesh of polyethylene or vinyl plastic. As will be seen herein, panel 14 is supported by a plurality of interconnected ribs. In the embodiment shown in FIG. 1, a conventional fiberglass cross member 16 is pinned at 18 to an upright fiberglass member or mast 24 . The lower end of mast 24 is clamped in a mast coupler assembly 30 illustrated, in FIG. 2 . Mast coupler assembly 30 is of conventional construction and includes a rigid metallic body 32 and a clamp member 34 . Mast 24 , which as mentioned, preferably comprises a fiberglass rib is inserted downwardly past clamp member 34 to the bottom of the mast coupler assembly. The lower end of the mast coupler assembly is secured to a clevis 36 using conventional bolt fasteners passing through apertures 38 .
Referring to FIG. 3, a bottom portion 42 of the sign stand assembly is illustrated. Included is the clevis 36 secured by a bolt fastener 46 to a resilient support assembly generally indicated at 50 . The resilient support assembly is in turn mounted to a leg mount 52 which is illustrated in FIG. 15 . Leg mount 52 includes a pair of side plates 54 joined to a saddle or center member 56 . Center member 56 includes an upper surface 58 recessed below the top of the side plates 54 . An aperture 60 is formed in center member 56 to receive a bolt fastener similar to bolt fastener 46 . Side plates 54 provide mounting for legs 64 in a conventional manner (see FIGS. 1 and 18 ).
Referring to FIGS. 13 and 14, resilient support assembly 50 includes a coil spring 64 . Spring 64 is of conventional helical wound wire design having cut ends 66 as can be seen for example in FIG. 14 . Resilient support assembly 50 includes one or more spring mount adapters generally indicated at 70 .
Referring to FIGS. 5-12 and initially to FIG. 5, spring mount adapter 70 includes a threaded body portion 72 and an enlarged end portion 74 including a keyed portion 78 and an extension portion 80 . The keyed portion 78 includes upstanding key members or protrusions 82 , 84 . As illustrated in FIG. 5, protrusions 82 , 84 are located on either side of a threaded bore 88 which receives the bolt fastener 46 mentioned above with reference to FIG. 3 .
When the spring mounting adapter 70 is employed at the bottom of the resilient support assembly, as illustrated in FIGS. 13 and 14, a bolt fastener, similar to bolt fastener 46 is passed through aperture 60 in leg mount 52 to engage threaded bore 88 , thereby securing the bottom of the resilient support assembly. The upper surface 58 of the leg mount of this first embodiment shown in FIGS. 1-15 engages the upper surface of end portion 74 located between keyed portions 82 , 84 . Generally flat sides 92 of the spring mounting adapter 70 (see FIG. 5) engage both portions of side plates 54 which protrude above surface 58 (see FIG. 15 ). Thus, with the flats 92 of the spring mounting adapter engaging side plates 54 and with the protrusions 82 , 84 engaging opposed sides of center member 56 the spring mounting adapter 70 is securely interlocked or keyed with the leg mount 52 . Surface 58 and the upper portions of the side plates 54 can be seen to cooperate to form a socket for receiving the spring mount adapter. Further, the surface 78 and protrusions 82 , 84 can be seen to comprise a socket for receiving the saddle or middle portion 58 of the leg mount 52 .
Referring again to FIGS. 3 and 5, the central portion of clevis 36 engages the keyed portion 78 with edges of the clevis being located immediately adjacent to or alternatively engaging, protrusions 82 , 84 to provide a secured well-defined angular alignment between the clevis and the resilient support assembly, and in turn the leg mount 52 and supporting legs 64 (see FIG. 1 ). With the arrangement illustrated in FIG. 3, it is generally preferred that identical spring mounting adapters 70 be used at each end of the resilient support assembly.
Referring again to FIG. 2, the mast coupler assembly 30 includes a rectangular cross-section body portion 32 which provides rotationally-defined keyed interlocking with clevis 36 . A defined rotational orientation is thereby provided between the mast coupler assembly and the leg mount and support legs. As will be seen, the relative angular or rotational positioning of the sign panel is defined with respect to the lower portion of the sign stand assembly.
As mentioned, the upright mast 24 is preferably comprised of a fiberglass rib of conventional construction. Such ribs typically have a rectangular cross-sectional configuration. The sign stand support according to principles of the present invention provides further alignment features while protecting the lower end of mast 24 . Mast 24 (see FIG. 1) is passed between clamp 34 and body 32 of the mast coupler assembly (see FIG. 2) and is lowered until contact is made with the upper surface of extension portion 80 . This arrangement provides a ready visual cue for the assembly operation and if preferred desired alignment can be accomplished with a tactile indication by gently lower the mast 24 into engagement with extension portion 80 . As can be seen in FIG. 5 and the other figures extension portion 80 is generally flat and with reference to FIG. 2 is readily aligned at a 90° angle to the longitudinal axis of the mast 24 which is clamped against body portion 32 . The present invention thereby provides improved protection against splitting the bottom end of the fiberglass rib comprising mast 24 . Assuming the bottom end of mast 24 is trimmed at a right angle to the mast longitudinal axis substantially all of the free end of the mast engages extension 80 at the moment of contact.
Referring to FIG. 19, mast 24 can be replaced by a metallic flat bar or more preferably, can comprise rigid, hollow metallic tubing 224 of the type employed for the base 32 of mast coupler assembly 30 (see FIG. 2 ). Engagement between the bottom of rigid metallic tubing 224 and the clevis are as described above with reference to FIG. 2 . Preferably, the spring mounting adapter 70 with a socket defined by surface 58 and protrusions 82 , 84 is employed to provide angular locking with the clevis, to provide a defined rotational or angular orientation between the mast (and hence the message panel) and the lower portion of the sign stand assembly. As shown in FIG. 19 a cross coupler 218 joins the upper end of mast 224 to panel supports 216 .
Referring now to FIGS. 5-12 and initially to FIG. 10, the spring mounting adapter preferably comprises a casting having a hollow bottom portion disposed beneath the solid keyed portion 78 . Threaded portion 88 may be formed directly in the casting or may comprise an insert of steel or other material. Cavities 102 (see FIG. 10) extend from the bottom of the spring mounting adapter upwardly to surround the threaded portion, and to thin out or reduce the mass of the outer wall of the casting.
As can be seen in FIGS. 9-12, spring mounting adapter 70 includes an outer wall with a helical cavity defining threads 104 . As can be seen in FIGS. 5 and 11, for example, the threads 104 are broken by flat surface portions 108 . As indicated in FIG. 12, it is generally preferred that the coils of spring 64 are fully seated or at least substantially seated in the root depressions formed between teeth 104 . With reference to FIG. 11, it is generally preferred that the threaded outer wall of the spring mounting adapter be tapered with an angle a ranging between 4 and 5°. The spring mounting adapters are screwed or threaded into the open ends of coil springs 64 . Preferably, with reference to FIG. 12, the coils engaged with the spring mounting adapter are progressively opened or enlarged in diameter such that the resulting frictional engagement effectively prevents unintentional “back-out” of the spring mounting adapter.
Turning now to FIGS. 16-18, in an alternative embodiment, the lower spring mounting adapter 70 is replaced by a spring mounting adapter 120 having a smooth surface 122 . The leg mount 52 of the preceding embodiment is replaced with a leg mount 126 having a saddle or center portion 128 disposed at the top of side plates 130 . Hence, the recess illustrated in FIG. 15 is lacking in the leg mount 126 which has a flush or generally planar upper surface (see FIG. 17 ). As with the preceding embodiment, a threaded fastener 46 is inserted through an aperture 134 so as to engage the internal threaded bore 136 of spring mounting adapter 120 . When assembled, the smooth surface 122 is allowed free rotational movement about the upper surface of spring mounting adapter 126 . This allows the ready angular or rotational positioning of the upper spring mounting adapter as desired. A hole 138 is formed in the spring mounting adapter 126 preferably at the time of manufacture. When the desired rotational alignment of the upper spring mounting adapter is attained, a reference mark is made in the surface 122 and a hole is drilled to allow fitting of a pin 142 . Upon reassembly, the pin 142 is inserted in hole 138 to lock the members 120 , 126 in desired rotational alignment. Other assembly options are possible. For example, a hole 143 formed in surface 122 of mounting adapter 120 is formed according to a reference mark relating to the predefined positioning of pin 142 received in hole 138 of the spring mounting adaptor. As a further option, pin 142 can be struck from the center portion 128 of the spring mounting adapter so as to protrude beyond its upper surface. The struck-out pin is then received in hole 143 formed in spring mounting adapter 120 .
The drawings and the foregoing descriptions are not intended to represent the only forms of the invention in regard to the details of its construction and manner of operation. Changes in form and in the proportion of parts, as well as the substitution of equivalents, are contemplated as circumstances may suggest or render expedient; and although specific terms have been employed, they are intended in a generic and descriptive sense only and not for the purposes of limitation, the scope of the invention being delineated by the following claims.
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A sign stand assembly having a message panel and a mast. A mast clamp is coupled to the lower end of the mast and a clevis is coupled to the mast clamp. A resilient support assembly includes a coil spring and a spring mounting adapter threadingly engaged with the upper end of the coil spring. A keyed portion including a mounting surface and a pair of key members upwardly protruding therefrom, comprising a concave socket for receiving the clevis with a close tolerance fit preventing rotation of the clevis.
| 4
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This application is a continuation-in-part of Ser. No. 799,502 filed May 23, 1977 now U.S. Pat. No. 4,136,711.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an acoustic mounting for a valve assembly such as a ball cock valve for controlling the height of liquid in a tank.
2. Description of the Prior Art
U.S. Pat. Nos. 2,681,661; 2,911,000; and 3,335,747 show pipe and valve assemblies mounted in a tank. A deficiency of the prior art, particularly in connection with installations such as flush tanks has been that of undesirable noise. It has been found that when the water enters the tank it acts as a drum accentuating the noise which is undesired. If a pipe containing a flow of water is in actual physical contact with the tank acting as a drum, the vibrations set up noise which is amplified by the tank. The prior art arrangements leave room for improvement in the manner of mounting the inlet pipe with respect to the tank in a manner such as to reduce or overcome unnecessary noise. The herein invention seeks to meet this problem by way of a constructional arrangement as described in detail hereinafter.
SUMMARY OF THE INVENTION
In accordance with this invention, a pilot operated ball cock valve controls the level of fluid in a tank through the combination of a diaphragm valve and a rotary pilot valve. The rotary pilot valve contains an inlet port where fluid under pressure which has bypassed the diaphragm valve enters the rotary valve and may thereafter discharge through an outlet port contained in the rotary valve through a fluid channel communicating with a pressure chamber above the diaphragm. A lip seal contained in the outlet port is positioned such that when the outlet port is out of communication with the channel leading into the pressure chamber, fluid pressure will force the lip seal against the wall of the valve housing. This seals off the fluid channel within the rotary valve and precludes transmission of pressure through the outlet port of the rotary valve. At a predetermined neight of fluid in a tank, the rotary valve is positioned such that fluid pressure is transmitted through the aligned outlet port of said valve with a channel leading into a pressure chamber adjacent and spaced to the diaphragm valve. The fluid pressure acting upon the diaphragm closes the diaphragm and prevents fluid from entering into the tank. A decrease in height of fluid will cause rotation of the rotary valve and the outlet port of said valve will move out of communication with the fluid channel leading into the pressure chamber. The pressure will be relieved in the pressure chamber by fluid leading from said chamber in the valve periphery and the diaphragm valve opens allowing fluid to flow into the tank and as the fluid level rises the rotary valve again rotates until the predetermined fluid level is reached whereby fluid pressure is again transmitted into the pressure chamber which closes the diaphragm precluding further discharge of fluid into the tank.
The diaphragm valve and the rotary pilot valve are carried by an inlet pipe which is supported from a wall of the tank by way of an acoustic mounting. The purpose of the acoustic mounting is the elimination of noise. It has been found that the tank acts as a drum. If a pipe containing water or a flow of water is in actual physical contact with the drum, the vibrations will set up noise which will be amplified with the tank acting as a drum. The acoustic mounting includes an elastomeric or rubber ring, which is secured to the tank wall by a spud having a flange. The elastomeric ring includes an annular part which is not tensioned and which carries a mounting ring which supports the inlet pipe and valve assembly. The mounting is acoustic in a manner to eliminate or at least to reduce the noise to a minimum.
A further feature is that a restricted nozzle for the incoming water within the inlet pipe that supports the valve. The nozzle provides a restricted orifice which controls the volume of flow. This acts as a regulator of the volume of flow, only flow at a certain rate being permitted through the pipe and the valve, since otherwise the noise would be excessive. This construction contributes to the elimination of noise.
In the light of the foregoing the primary object of the invention is to make available an acoustic mounting for an inlet pipe in a tank, particularly one that carries a valve for purposes of eliminating or suppressing excessive noise which would otherwise result from the flow of water into the pipe and through the valve.
A further object is to realize an improved acoustic mounting, as in the foregoing object, wherein an elastomeric mounting ring is provided, which is clamped to an opening in the tank, the ring having an untensioned annular part, carrying a mounting ring which supports the inlet pipe.
Further objects and additional advantages of the invention will become apparent from the following detailed description and annexed drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-section of a tank showing a general configuration of a valve assembly embodying the invention.
FIG. 2 is a cross-section of the valve assembly illustrating the acoustic mounting of the assembly.
FIG. 3 is a sectional view taken along the line 3--3 of FIG. 2.
FIG. 4 is a sectional view taken along the line 4--4 of FIG. 3, showing the range of rotary movement of the pilot valve.
FIG. 5 is a sectional view along the line 5--5 of FIG. 3.
FIG. 6 is a sectional view taken along the line 6--6 of FIG. 2.
FIG. 7 is a sectional view taken along line 7--7 of FIG. 2.
FIG. 8 is a sectional view taken along the line 8--8 of FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings, an inlet fluid supply tube 12 as shown in FIG. 1 is connected by a fastener 13 to a sound reducing member 14 which is coupled to the inflow pipe 15 at a point spaced exterior to the fluid tank 6. Tube 16 is positioned horizontally in member 14 for sound reducing purposes.
As more particularly shown in FIG. 2, inflow pipe 15 is acoustically mounted to the tank 6 by an acoustic bushing 20 made of an elastomeric material such as rubber, or the like, the bottom surface of which rests against the internal wall of tank 6. Acoustic bushing 20 has an annular lip 21 which interfits with the annular flange of a mounting spud 22, said spud having a longitudinal bore therein 23 through which the inflow pipe 15 passes. Mounting spud 22 passes through the tank wall and engages a mounting nut 24 exterior to the tank wall and upon tightening of mounting nut 24 the acoustic bushing 20 firmly seats against the interior of the tank wall. An upper acoustic riser mounting ring 26 snugly fits around the peripheral surface of the inflow pipe 15; the outer circumference of the acoustic riser has gripping serrations which engage acoustic bushing 20. Acoustic riser ring 26 and acoustic bushing 20 are pressed together by a compression ring 27 along the upper periphery of acoustic bushing 20.
From the foregoing it may seen that bushing 20 is cup-shaped; the annular part 20 is not stressed by tension, this part holding the mounting ring 26, so that it forms a sound eliminating member. It has been found that the tank itself acts as a drum. If a pipe containing water or a flow of water is in actual physical or close contact with the drum, the vibrations will set up noise which will be amplified with the tank acting as a drum. The structure as described serves to acoustically isolate the pipe from the tank.
As shown in FIG. 2, inflow pipe 15 has a bore at its inlet end 30 which tapers into a bore 32 of smaller diameter forming an internal nozzle 33 within the central bore 34 of inflow pipe 15. Nozzle 33 forms an orifice 36 which discharges fluid into the central bore 34 into which nozzle 33 protrudes where said nozzle is spaced so as to provide a void between the external surface of the nozzle 33 and the internal wall of inflow pipe 15.
The nozzle 32 within the pipe forms a restricted orifice which controls the volume of flow. The purpose of this is to act as a regulator of the volume of flow, inasmuch as flow at only a certain rate can be permitted through the head and through the valve and through the pipes without causing excessive noise. Thus, this construction acting as a flow regulator serves to eliminate noise.
At the discharge end of inflow pipe 15, the internal bore tapers to a larger diameter for engagement with boss 39 extending from lower housing 40. Within lower housing 40 there is an evacuation chamber 41 through the bottom of which there are a plurality of equally spaced anti-siphon air holes 42. A flexible ring seal 43 is firmly attached around the periphery of the boss 39 of the lower housing where the bottom surface of flexible ring seal 43 covers the plurality of anti-siphon air holes 42. In operation, the flexible ring 43 will allow atmospheric pressure to vent into evacuation chamber 41 should atmospheric pressure be greater than the pressure in the evacuation chamber. Flexible ring 43 unseals when atmospheric pressure exiting through the siphon air holes 42 flexes member 43 so as to allow air to pass into the evacuation chamber.
Located at the periphery of the evacuation chamber is an overflow nozzle 44 with a threaded end for connection with an overflow tube 46 where said overflow tube is shown in FIG. 1. Also located at the periphery of the evacuation chamber, as shown in FIG. 2, is an evacuation nozzle or nipple orifice 48 protruding from the lower housing 40 and integrally associated with evacuation chamber 41. The outer periphery of the evacuation orifice engages a flexible refill tube 49 through which fluid evacuates into the fluid tank. See FIG. 1.
At the top of lower housing inlet 46, there is a discharge orifice 50 at the end of bore 46 through which fluid passing through lower bore 46 is subsequently discharged into evacuation chamber 41. Spaced above said discharge orifice 50 is a diaphragm valve 51 made of a flexible material which is securely held between the upper housing 52 and the lower housing 40. The upper face of the diaphragm valve 51 is exposed to pressure chamber 53 which is contained within upper housing 52. A threaded valve collar 54 screws onto the threaded portion of lower housing 40 where valve collar 54 contains an internal peripheral flange surface 55 which presses against an annular lip 57 on the periphery of upper housing 52 such that when the collar 54 is tightened upper housing 52 is securely fastened to lower housing 40.
FIG. 8 shows the internal construction of lower housing part 40. Its wall construction has angularly spaced recesses 58. Numeral 59 designates one of a plurality of angularly spaced radial webs between which water can pass down to diaphragm 43.
A bypass channel 60 is formed within both lower housing 40 and upper housing 52. Inlet 61 to the bypass channel is situated in the lower housing inlet bor 46 and bypass channel 60 terminates at charging port 62 located in upper housing 52. See FIG. 2. Charging port 62 is a cylindrical void into which the bypassing fluid discharges before entering inelt passage or bore 63 of pilot valve 64 which is more particularly shown in FIG. 3 of the drawings.
Referring to FIG. 3, pilot valve 64 has an annular groove 66 which contains an O-ring 67 therein to seal and to prevent the escape of fluid from charging port 62 into the peripheral space between the pilot valve 64 and the wall of bore 65 of upper housing 52 in which valve 64 is positioned. Fluid entering charging port 60 passes through valve inlet port 68 into inlet passage 63 where said fluid continues to pass without obstruction into a cylindrical right angle bore or recess 69 within pilot valve 64. A resilient means such as spring 70 is inserted into cylindrical bore 69 and engages upon a lipseal puck 71 which seals against the bore 65 in housing 52. Lipseal puck 71 has a tapered countersunk bore at its upper surface which receives spring 70, where spring 70 acts so as to urge the lipseal puck 71 against the valve housing bore. The outer periphery of lipseal puck 71 contacts the wall of cylindrical bore 69 in flush relationship. The tapered inside periphery 72 of the countersunk bore in lipseal puck 71 permits fluid pressure acting along the surface of the taper 72 to seal lipseal puck 71 flushly against the wall of cylindrical bore 69. A bore 73 extends through the interior of lipseal puck 71 to an outlet port 74 at the articulating surface of lipseal 71 with the upper valve housing wall.
Pressure chamber 53 contains a connecting fluid channel 75 connecting pressure chamber 53 to cylindrical bore 69 such that communication between the pressure chamber and cylindrical bore 69 occurs when outlet port 74 is aligned with fluid channel 75. An annular groove 76 located in the pilot valve 64 contains an O-ring 77 preventing leakage between the outer periphery of pilot valve 64 and the upper housing wall when connecting channel 75 and valve outlet port 74 are out of communication. See FIG. 3.
Pilot valve 64 is rotatably mounted in the upper housing 52 and is retained within said upper housing with stud or screw 78 which passes through the pilot valve 64 and fastens at its threaded end in lower housing 40. Rotation of pilot valve 64 is limited through an angle defined by intersecting radial bores 79 and 79 through the pilot valve, as shown in FIG. 4, creating opposing slots on the periphery of the valve through which stud 70 passes.
Spaced between the annular grooves 76 and 66 on the outer surface of the valve 64 are symmetrical grooves 101 and 102 diametrically opposed on the surface of valve 64. See FIG. 6. Groove 102 communicates with a fluid channel 103 which passes through the upper housing 52, through port 105 in the diaphragm 51 and communicates with the evacuation chamber 41 at evacuating chamber channel port 104 as is shown in FIGS. 5 and 7.
The float 1 is linked to valve 64 by an arm 2 which fastens to valve 64 at hole 105. By referring to FIG. 1, the operation of the system as described may now be viewed in an overall perspective. When the fluid level in the tank is at its normal level the diaphragm valve 51 responds to fluid pressure in pressure chamber 53 and closes discharge orifice 50. Under these circumstances, fluid is unable to flow into the evacuation chamber for ultimate discharge into the tank. When fluid is removed from the tank, the water level is lowered, thereby lowering float 1 which in turn rotates the valve 64 into a position such that the valve outlet port 74 moves out of communication with the connecting chamber 75, thereby allowing the pressure in the pressure chamber to be relieved and the diaphragm valve opens. As the diaphragm valve opens discharge orifice 50, fluid then begins to flow through the inlet supply tube 12 and the inflow pipe 15 causing fluid to subsequently flow into the evacuation chamber 41 from which it is evacuated through evacuation orifice 48 into the tank. When the water level again reaches the predetermined height at which height fluid valve outlet port 74 communicates with connection channel 75, fluid pressure is transmitted to the upper surface of the diaphragm which closes the discharge orifice 50 preventing further fluid flow into the evacuation chamber or tank.
By reference to FIG. 2 in the drawings, the operation of the invention may be further understood. Fluid enters the system through inlet fluid supply tube to 12, passes into acoustic housing 14 and thereafter enters into the inlet inflow pipe 15. During the fluid passage through inflow pipe 15, internal bore 30 carries the fluid to nozzle 33 with an orifice which is of smaller diameter than that of inlet bore 30. The fluid therefore increases in velocity as it approaches nozzle 33 from which the fluid discharges into bore 34 which is of a larger diameter than the inlet bore 30. Vibrations occurring as a result of velocity changes of the fluid within the system are substantially dampened by the use of acoustic bushing 20 and acoustic upper mount riser 26, thereby reducing vibration transmitted to the fluid tank and substantially eliminating drum noises associated with tank vibration. By use of the nozzle 33 in conjunction with a surrounding void between the nozzle and the wall of inflow pipe 15 water surging is avoided which also contributes to the lowering of the noise level during the operation of the system.
Continuing the trace of fluid flow through the system, fluid enters inlet 61 of the bypass or pilot channel 60 and flows into charging port or bore 62. The fluid enters pilot valve 64 at inlet port 68. Fluid passes through the inlet passage 63 and enters the cylindrical bore 69 of pilot valve 64. When the valve outlet port is in communication with connecting channel 75 leading into pressure chamber 53, fluid will enter the pressure chamber increasing the fluid pressure against the diaphragm. The increased pressure against the disphragm 51 will cause the diaphragm to close against the discharge orifice 50 thereby preventing fluid to discharge into the evacuation chamber 41. Siphoning into evacuation chamber 1 is prevented since the anti-siphon airholes 42, located in the base of the evacuation chamber, will equalize atmospheric pressure with the pressure in the evacuation chamber.
When the fluid level in the tank is lowered, the corresponding movement of the float which is transmitted through linkage arm 2 to the pilot valve 64 will cause the pilot valve to rotate. As the rotation progresses, the outlet valve port 74 moves out of alighment with connecting channel 75 to the pressure chamber. The lipseal puck 71 is so positioned that fluid pressure will force the lipseal against the wall of the bore 65 of the valve housing sealing off the fluid channel within the rotary valve thereby precluding transmission of fluid pressure or the flow of fluid through the outlet port of the pilot valve. The pressure in pressure chamber 53 is relieved into an area around the periphery of the pilot valve between O-rings 67 and 77 by fluid reaching slots 101 and 102 in the periphery of the pilot valve where said periphery of the valve now communicates with the evacuation chamber through channel 103 and evacuation chamber channel port 104. See FIGS. 5, 6, and 7. In this configuration, diaphragm valve 51 opens and fluid discharges through the discharge orifice 50 into the evacuation chamber 41 and is subsequently evacuated through evacuation orifice 48 into the tank. As the fluid level in the tank rises, float 1 will again move so as to transmit its movement through the linkage arm 2 to the pilot valve 64 until communication between the valve outlet port 74 and connecting channel 75 recurs, thereby permitting the fluid pressure to again act upon the diaphragm valve which in response to said pressure closes the discharge orifice and no further fluid is evacuated into the tank.
From the foregoing, those skilled in the art will readily understand the nature of the invention, its construction and operation, and the manner in which it achieves and realizes all of the objects and advantages as set forth in the foregoing, as well as its many additional advantages that are apparent from a detailed description.
The foregoing disclosure is representive of a preferred form of the invention and is to be interpreted in an illustrative rather than a limiting sense, the invention to be accorded the full scope of the claims appended hereto.
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An acoustically mounted valve assembly controlling the flow with respect to a tank. The purpose is to eliminate noise. An elastomeric or rubber ring is provided around an inlet pipe and is secured to the tank wall by a spud. The elastomeric ring has an untionsioned annular part which carries a mounting ring which supports the inlet pipe and the valve assembly. The mounting eliminates or reduces noise to a minimum and prevent the tank from acting as a drum.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application 61/389,075, filed Oct. 1, 2010, which is incorporated by reference herein.
STATEMENT OF GOVERNMENT SUPPORT
[0002] The invention described and claimed herein was made in part utilizing funds supplied by the U.S. Department of Energy under Contract No. DE-0E0000223. The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION
Field of the Invention
[0003] This invention relates generally to a method of functionalizing high molecular weight polyethylene oxide.
[0004] Increased demand for lithium secondary batteries has resulted in research and development to improve their safety and performance. Many batteries employ liquid electrolytes and are associated with high degrees of volatility, flammability, and chemical reactivity. With this in mind, the idea of using a solid electrolyte with a lithium-based battery system has attracted great interest.
[0005] The lithium solid polymer electrolyte rechargeable battery is an especially attractive technology for Li-ion batteries because, among other benefits, the solid polymer electrolyte exhibits high thermal stability, low rates of self-discharge, stable operation over a wide range of environmental conditions, enhanced safety, flexibility in battery configuration, minimal environmental impacts, and low materials and processing costs. Moreover, solid polymer electrolytes may enable the use of lithium metal anodes and other high capacity anodes, which offer higher energy densities than traditional lithium ion anodes.
[0006] Despite their many advantages, the adoption of solid polymer electrolytes has been curbed by the inability to develop an electrolyte that exhibits both high ionic conductivity and good mechanical properties. This difficulty arises because according to standard mechanisms, high ionic conductivity calls for high polymer chain mobility. But high polymer chain mobility, according to standard mechanisms, tends to produce mechanically soft polymers.
[0007] As an example, a prototypical polymer electrolyte is a polyethylene oxide (PEO)/salt mixture. PEO generally offers good mechanical properties at room temperature. However, PEO is also largely crystalline at room temperature. The crystalline structure generally restricts chain mobility, reducing conductivity. Operating PEO electrolytes at high temperature (i.e., above the polymer's melting point) solves the conductivity problem by increasing chain mobility and therefore improving ionic conductivity. However, the increased conductivity comes at the cost of deterioration of the material's mechanical properties. At higher temperatures, the polymer is no longer rigid.
[0008] Block copolymers have been proposed as materials that can have both good mechanical properties and good conductivity. By using microphase-separated block copolymers of two or more carefully selected blocks, at least one block can impart mechanical integrity while at least one block can impart high conductivity. One example of such a material is a polystyrene/polyethylene oxide (PS/PEO) block copolymer. There is an optimum temperature range in which this block copolymer electrolyte exhibits good conductivity without sacrificing mechanical integrity. It would be useful to find a way to manufacture this block copolymer electrolyte material in large amounts, both economically and reproducibly, in order to assure its commercial viability.
SUMMARY
[0009] In one embodiment of the invention, a method for preparing functionalized, high molecular weight polyethylene oxide (HWPEO) is provided. The method involves reacting the HWPEO with an acylating reagent and an organic base. The mixture is then added to isopropanol, and the HWPEO is allowed to precipitate. The HWPEO is then filtered from the solvent. Various acylating reagents can be used in the reaction depending on the kind of functionalization desired.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The foregoing aspects and others will be readily appreciated by the skilled artisan from the following description of illustrative embodiments when read in conjunction with the accompanying drawing.
[0011] FIG. 1 is a block diagram showing the novel steps in a HWPEO functionalization process according to an embodiment of the invention.
DETAILED DESCRIPTION
[0012] The embodiments of the invention are illustrated in the context of preparing high molecular weight PEO for subsequent reactions, such as formation of block copolymers. The materials and methods disclosed herein have application in a number of other contexts where functionalization of high molecular weight PEO is desirable, particularly where purity and simplicity are important.
[0013] The aforementioned needs are satisfied by the embodiments of the present invention which describe methods to functionalize high molecular weight PEO for subsequent reactions safely, with a minimum of process steps, using commonly available starting materials, at low cost, and with good reproducibility.
[0014] In one arrangement, the HWPEO has a molecular weight greater than about 50 kDa. In another arrangement, the HWPEO has a molecular weight greater than about 100 kDa. In yet another arrangement, the HWPEO has a molecular weight greater than about 200 kDa. In yet another arrangement, the HWPEO has a molecular weight greater than about 500 kDa.
[0015] In one embodiment of the invention hydroxyl end groups of high molecular weight poly(ethylene oxide) (HWPEO) are transformed into other functional groups. As the concentration of —OH (hydroxyl) groups in HWPEO is quite low, it is useful to choose an efficient reaction for transformation. One easy way to transform hydroxyl groups is by reaction with acylating reagents in the presence of an organic base to form an ester bond. This reaction, shown in scheme (1), is thermodynamically favorable and can proceed quantitatively at room temperature.
[0000]
[0016] Once the reaction is complete, the newly functionalized HWPEO is in a dissolved state and there are generally three reaction byproducts—unreacted acylating reagent, unreacted base, and a salt byproduct. It is useful to isolate pure functionalized HWPEO as a solid and free of such reaction byproducts.
[0017] When low molecular weight PEO is functionalized, the same undesirable byproducts are produced, but isolation and purification of such a low viscosity solution is straightforward. Purification can be accomplished by techniques such as filtration, solvent-solvent extraction, and dialysis. But these methods are not very useful for HWPEO: filtration is difficult for highly viscous solutions as are created when HWPEO is dissolved; HWPEO is a surfactant and can create an intractable emulsion if a solvent-solvent extraction is attempted; and dialysis is very slow and uses large amounts of solvent.
[0018] Typically non-polar solvents (e.g., hexane) are used as non-solvents for precipitation of polymers, but such solvents would cause the salt byproduct of reaction (1) to co-precipitate with the functionalized HWPEO, which is undesirable. We have found that after the functionalization reaction of HWPEO with acylating reagent and organic base, mixing the still-liquid crude reaction solution with isopropanol effectively causes precipitation of the desired functionalized HWPEO product. At the same time, the isopropanol dissolves any residual salts, acylating reagent, and organic base, thereby easily providing isolated and purified functionalized HWPEO in the precipitate. Furthermore, the functionalization reaction benefits because a large excess of the acylating and base reagents can be used to ensure that the reaction is not limited. Any unreacted remains can be removed easily later by the isopropanol precipitation steps.
[0019] In one embodiment of the invention, the PEO is rinsed with isopropanol and then with ethyl acetate before participating in reaction (1) above. The rinsing may help to remove water and low molecular weight contaminants which can adversely affect reaction (1) by reacting competitively with the acid halide and the organic base.
[0020] The steps of a method of functionalizing HWPEO, according to an embodiment of the invention, are shown in FIG. 1 . In optional step 100 , HWPEO is washed using a solvent that does not dissolve HWPEO and then dried. Examples of useful solvents for this step include ethyl acetate, isopropanol, and acetone. In some arrangements, the HWPEO can be washed multiple times with the same or various solvents. Vacuum drying can be used. This is especially useful if the HWPEO contains low molecular weight contaminants or moisture.
[0021] In step 110 , HWPEO is dissolved and reacted with an acylating reagent and an organic base. Any solvent that is non-reactive with the acylating and basic reagents in reaction (1) can be used in this reaction. Examples of such solvents include, but are not limited to any one or more of benzene, anisole, acetonitrile, toluene, methylene chloride, chloroform, and xylene. The solubility of the HWPEO can be increased and the viscosity of the reaction mixture as a whole can be decreased by heating to temperatures of 50° C. or higher.
[0022] In one arrangement, the organic base is added to the HWPEO with the solvent. In another arrangement, the organic base is added to the HWPEO after it is dissolved in the solvent. In yet another arrangement, the acylating reagent is added to the mixture last.
[0023] Various acylating reagents can be used in the reaction depending on the kind of functionalization desired. In one arrangement, the acylating reagent includes a dye. In another arrangement, the acylating reagent includes a fluorescing group. In another arrangement, the acylating reagent includes an azido or acetylene group. In yet another arrangement, the acylating reagent includes a controlled radical polymerization initiator. In one embodiment of the invention, the acylating reagent is 2-bromoisobutyryl bromide. Examples of other acylating reagents that can be employed in the embodiments of the invention, either singly or in combination with others, include such compounds as alkyl chloroformates, acyl chlorides, acyl bromides, acid anydrides (linear or cyclic), acyl nitriles/cyanides, acyl azides, acyl imidazolates, acyl N-hydroxysuccinimidates, acyl 4-nitrophenolates, acyl pentafluorophenolates, sulfonyl chlorides/bromides, and phosphoryl chlorides/bromides. The reaction can be used to attach or introduce functional groups with additional utility, including reactive alkenes/olefins, alkynes, azides, aldehydes; disulfide groups, reducible to form thiols; initiators for radical polymerizations such as a-bromoesters or nitroxide groups; fluorescing groups such as dansyl, anthracene, pyrene; biochemical groups such as biotin for conjugation to biological molecules.
[0024] The following is a partial list of organic bases that can be used either singly or in combination in reaction (1), according to embodiments of the invention:
[0025] trialkylamines NR1R2R3, where R1, R2, R3 are independently chosen from C1-C8 straight-chain, branched-chain, or cyclic alkyl groups; also wherein 2 of R1, R2, and R3 are fused to form a 5-8 membered azacycloalkane;
peralkylated linear or cyclic polyamines, such as N,N,N′,N′-tetralkylethylene-1,2-diamine, N,N,N′,N′-tetralkylpropane-1,3-diamine, N,N,N′,N″,N″-pentaalkyldiaminetriamine, 1,4-dialkylpiperazine, and 1,4-diazabicyclo[2.2.2]octane, where the alkyl groups are independently chosen from C1-C6 straight-chain, branched-chain, or cyclic alkyl groups; pyridine (C5H5N) and 2-alkyl, 3-alkyl, 4-alkyl, 2,3-dialkyl, 2,4-dialkyl, 2,5-dialkyl, 2,6-dialkyl, 3,4-dialkyl, 3,5-dialkyl, and 2,3,4-trialkyl, 2,3,5-trialkyl, 2,3,6-trialkyl, 2,4,5-trialkyl, 2,4,6-trialkyl, and 3,4,5-trialkyl substituted pyridines, where the alkyl groups are independently chosen from C1-C6 straight-chain, branched-chain, or cyclic alkyl groups; N-alkyl, N,2-dialkyl, N,4-dialkyl, N,5-dialkyl, N,2,4-trialkyl, N,2,5-trialkyl, and N,2,4,5-tetraalkyl substituted imidazoles, where the alkyl groups are independently chosen from C1-C6 straight- and branched-chain alkyl groups; N,N-dialkylanilines, where the alkyl groups are independently chosen from C1-C6 straight- and branched-chain alkyl groups; and amidines such as 1,8-diazabicyclo[5.4.0]undecene and 1,5-diazabicyclo[4.3.0]nonene.
[0031] In step 120, the reaction products are added to a solvent that does not dissolve HWPEO but does dissolve the reaction byproducts, such as isopropanol. In one arrangement, ethanol is used instead of isopropanol. In step 130 , functionalized HWPEO is allowed to precipitate. In step 140 , the purified and precipitated HWPEO is filtered from the solvent.
[0032] In one embodiment of the invention, an esterification catalyst such as DMAP (4-dimethylaminopyridine) can be added to the reagents in reaction (1) to accelerate the reaction. Such a catalyst is also soluble in isopropanol and other solvents, so it does not participate in the precipitation of the HWPEO after functionalization.
EXAMPLE
[0033] The following example provides details relating to functionalization of HWPEO in accordance with embodiments of present invention. It should be understood the following is representative only, and that the invention is not limited by the detail set forth in this example.
[0034] Commercially-obtained HWPEO (molecular weight about 100 kDa as determined by viscometry; 60 g, 0.6 mmol) was suspended in toluene (180 mL) and triethylamine (1.32 g, 13 mmol), and the resulting mixture was warmed to 65° C. until the HWPEO had dissolved. A solution of 2-bromoisobutyryl bromide (2.36 g, 10 mmol) in toluene (10 mL) was added, and the mixture was stirred for 18 hours at 65° C. The still-warm mixture was then poured into 2.25 L of stirring isopropanol to give a fibrous precipitate. The precipitate was isolated by filtration, immersed in 1 L fresh isopropanol, filtered again, and dried in vacuum to yield 55 g functionalized HWPEO.
[0035] This invention has been described herein in considerable detail to provide those skilled in the art with information relevant to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by different equipment, materials and devices, and that various modifications, both as to the equipment and operating procedures, can be accomplished without departing from the scope of the invention itself.
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A simple procedure is provided by which the hydroxyl termini of poly(ethylene oxide) can be appended with functional groups to a useful extent by reaction and precipitation. The polymer is dissolved in warmed toluene, treated with an excess of organic base and somewhat less of an excess of a reactive acylating reagent, reacted for several hours, then precipitated in isopropanol so that the product can be isolated as a solid, and salt byproducts are washed away. This procedure enables functionalization of the polymer while not requiring laborious purification steps such as solvent-solvent extraction or dialysis to remove undesirable side products.
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BACKGROUND OF THE INVENTION
This invention relates to a clutch mechanism for use in a fishing reel, and more particularly a clutch mechanism capable of transmitting and interrupting torque between a line winding spool supported by two bearings and a handle for rotating the spool and can be automatically switched from a torque interrupting state to a torque transmitting state when the handle is rotated in the forward direction, that is in a direction for taking up the line.
A prior art clutch mechanism for use in a fishing reel was constituted by a main gear rotated by a handle, a pinion meshing with the main gear and rotatably and axially slidably-fitted on a spool shaft so that when the pinion engages a notch of the spool shaft the pinion can rotate together with the spool shaft, a clutch bar for axially sliding the pinion, and a clutch cam connected to an operating lever and disposed between the clutch lever and a supporting plate so that when the coupling between the pinion and the spool shaft is released by the clutch cam, the pinion is coupled with the spool shaft through a ratchet wheel.
This clutch mechanism, however, is constructed such that when the clutch is switched to an OFF state, the end of a kick pawl is forced into a space between adjacent teeth of the ratchet wheel, so that depending upon the position of a ratchet tooth, the tooth collides against the kick pawl thus making it impossible to attain meshing of the ratchet wheel and the kick pawl. Consequently, the clutch operation is rendered inoperative, or a large force is necessary to engage the kick pawl against the ratchet wheel, the click feeling becomes small when both are engaged, the engaging tone is small with the result that the clutch OFF operation becomes inaccurate.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide an improved clutch mechanism for use in a fishing reel capable of smoothly effecting clutch OFF switching operation and accurately informing to the user of the reel switching to the clutch OFF state by feeling and tone.
According to this invention, there is provided a clutch mechanism for use in a fishing reel of the type wherein a pinion is operated by a clutch cam and a clutch lever, and a handle is connected to and disconnected from a spool shaft by engaging and disengaging the pinion from a notch of a spool shaft acting as a sliding shaft of said pinion, the improvement which comprises a spring for selectively urging said clutch cam to rotate in forward and reverse directions, contact means provided for said clutch cam, a ratchet wheel rotated by said handle, operating means interposed between said clutch cam and said ratchet wheel, said operating means being held by said contact means to be disengaged from said ratchet wheel when said clutch cam is at its ON state, and a spring for urging said operating means in a direction to engage said ratchet wheel, said operating means being released from said contact means and engaging said ratchet wheel when said clutch cam is turned to its OFF state, whereas, when said clutch cam is at its OFF state, said operating means pushes said contact means upon the forward rotation of said ratchet wheel to return said clutch cam to its ON state.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front view of one embodiment of the clutch mechanism for use in a fishing reel according to this invention, in a clutch ON state;
FIG. 2 is a sectional view of the clutch mechanism taken along a line II--II in FIG. 1;
FIG. 3 is front view of the clutch mechanism shown in FIG. 1 but in a clutch OFF state;
FIG. 4 is a front view of the clutch mechanism in an intermediate state to an ON state from an OFF state.
FIG. 5 is a sectional view taken along a line V--V in FIG. 4;
FIG. 6 is a longitudinal sectional view showing the cam member of the clutch cam utilized in the embodiment shown in FIG. 1;
FIG. 7 is a front view showing a modified clutch mechanism in an ON state;
FIG. 8 is a front view of the modified clutch mechanism shown in FIG. 7 in an OFF state;
FIG. 9 is a front view of the clutch mechanism shown in FIG. 7 in an intermediate to the ON state from the OFF state;
FIG. 10 is a front view showing a further modified clutch mechanism in an OFF state;
FIG. 11 is a front view of the clutch mechanism shown in FIG. 10 in an intermediate to the ON state from the OFF state; and
FIG. 12 is a front view of the modified clutch mechanism shown in FIG. 10 in an ON state.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In one embodiment, shown in FIGS. 1 through 6, the clutch mechanism comprises an inner side plate 1, a ratchet wheel 4 mounted on a handle shaft 3 supported by the side plate 1 through a shaft 2 (see FIG. 2), a drag star handle 5 threaded to the handle shaft 3, a main gear 7 disposed between the ratchet wheel 4 and the drag star handle 5 through a drag mechanism 6, and a pinion 8 meshing with the main gear 7 and mounted on a spool shaft 10 to be slidable in the axial direction shown by arrows a and a' in FIG. 2. The pinion 8 is coupled with or released from a notch 10a provided for the spool shaft 10 to connect or disconnect the spool shaft 10 to and from a handle 11.
Furthermore, a clutch lever 12 is engaged in a groove 8a formed on the outer periphery of the pinion 8. Arms 12a symmetrically projecting from the clutch lever 12 are mounted on guide pins 13 secured to the inner side plate 1 to be slidable in the axial direction. Arms 12a are resiliently urged toward the side plate 1 by coil springs 14 surrounding the guide pins 13. A clutch cam 15 is interposed between the side plate 1 and the clutch lever 12. The central cylindrical portion 15a of the clutch cam 15 is fit in an opening 1a of the side plate 1 while permitting the free rotation of the clutch cam 15.
A push lever shaft 18 (see FIG. 1) pulled by a tension spring 17 is slidably fit in a slot 16a of the side plate 1. An interlocking lever 19 is rotatably secured to the side plate 1 by a stepped screw 20 or the like. One end of the interlocking lever 19 is urged to selectively swing in opposed directions by a torsion spring 21. One end of the lever 19 and the projection 15b of the clutch cam 15 are interconnected by a pin 22. The bottom end of the pin 22 extends into a slot 100 formed on the side plate 1 so as to limit the swinging rage of the pin 22. When the lever 19 is rotated in the counter-clockwise direction in FIG. 1 beyond the dead point of the spring 21 by manually operating the push lever shaft 18, the lever 19 and the clutch cam 15 would be automatically rotated by the spring 21 to the position shown in FIG. 3 and held at that position.
As shown in FIG. 6, cam members 15e having a substantially larger displacement S than the coupling distance between the pinion 8 and the notch 10a of the spool shaft 10 are provided to the annular portion 15d of the clutch cam 15. When the clutch cam 15 is rotated in the clockwise direction in FIG. 1, the cam members 15e come to engage the clutch lever 12 so that the cam members 15e enter beneath arms 12a as shown in FIG. 3 by utilizing the inclined surfaces thereof, whereby the clutch lever 12 is moved by displacement S together with pinion 8 in the direction a' shown in FIG. 2 against the force of springs 14, thus disengaging the pinion 8 from the notch 10a of the spool shaft 10. Accordingly, the spool shaft 10 is disconnected from the handle 11 and the mechanism is shifted to its clutch OFF state. A projection 15f is provided on the surface of the annular portion 15d of the clutch cam 15.
Between the ratchet wheel 4 and the clutch cam 15, first and second operating levers 23 and 24 are disposed.
The first operating lever 23 has an elongated configuration, and a slot 23a is formed at about the center thereof. A contact member 23b is provided for the front end of the first operating lever 23 while an upwardly bent engaging member 23c is formed at the rear end. The first operating lever 23 is rotatably and slidably supported by a screw 25 extending through the slots 23a and secured to the inner plate 1 (see FIG. 5). Furthermore, the first operating lever 23 is biased to rotate in the counter-clockwise direction in FIG. 1 about the screw 25 by a spring 27 secured between a pin 23d provided on the first operating lever 23 and a pin 26 secured to the side plate 1. Consequently, the operating member 23b is urged against the projection 15f of the clutch cam 15 while the engaging member 23c is caused to disengage the ratchet wheel 4.
One side portion 23g of the first operating lever 23 is prepared to engage against a stopper 29 provided for the inner plate 1 for limiting the counter-clockwise rotation of the first operating lever.
The second operating lever 24 is disposed between the inner plate 1 and the first operating lever 23 and rotatably mounted on the side plate 1 by a screw 28 passing through the base portion of the operating lever 24. An operating member 24a is provided on the front end of the second operating lever 24. At one side of the upper portion of the operating lever 24, an upwardly bent engaging member 24b is formed to contact the operating member 23b of the first operating lever 23. A slot 24c is provided at about the center of the second operating lever 24 for receiving the screw 25 therein.
In FIGS. 1, 3 and 4, a reference numeral 30 designates a reverse rotation preventing pawl meshing with the ratchet wheel 4.
The above constructed mechanism operates as follows. In the state shown by solid lines in FIGS. 1 and 2, the mechanism is in the clutch ON state. When the clutch cam 15 is rotated in the clockwise direction by manually operating the push lever shaft 18, the pinion 8 is disengaged from the spool shaft 10 by the clutch lever 12 moved in the axial direction by cam members 15e so as to bring the clutch to the OFF state. At this time, the first operating lever 23 is rotated in the counter-clockwise direction until the side portion 23g engages the stopper 29 by the biasing force of the spring 27, so that the engaging member 23c will project between the adjacent teeth 4a of the ratchet wheel 4. Further, since the operating member 24a of the second operating lever 24 is being urged by the projection 15f, the second kick lever 24 would be rotated in the counterclockwise direction. Even when the engaging member 23c of the first operating lever 23 does not enter into a space between adjacent teeth 4a but stops at a position engaging a tooth 4a, the clutch cam 15 would not be influenced by the first operating lever 23 so that the clutch can be smoothly shifted.
To shift the clutch from the OFF state shown in FIG. 3 to the ON state shown in FIG. 1, the ratchet wheel 4 is to be forwardly rotated by the handle 11. With this rotation of the ratchet wheel 4, the engaging member 23c of the first operating lever 23 is pushed as shown in FIG. 4 by a tooth 4a of the ratchet wheel 4, to be moved upwardly and obliquely in FIG. 4 and the engaging member 24b of the second operating lever 24 comes to engage the shoulder 23f of the first operating lever 23, so that the second operating lever 24 is rotated in the clockwise direction about the screw 28. Even when the engaging member 23c has not been entered between adjacent teeth 4a, upon the rotation of the ratchet wheel 4 the engaging member 23c is caused to enter between the next adjacent teeth 4a and then pushed. Then, the operating member 24a pushes the projection 15f of the clutch cam 15 in the counter-clockwise direction whereby the clutch cam 15 is rotated in the counter-clockwise direction.
When the clutch cam 15 is rotated to a point beyond the dead point of the spring 21, the operating member 23b of the first operating lever 23 is urged by the projection 15f so that the first operating lever 23 is rotated in the clockwise direction against the force of the spring 27. As a consequence, the engaging merber 23c disengages from the ratchet wheel 4 and returns to the position shown in FIG. 1 by the biasing force of the spring 27. Further, the cam members 15e of the clutch cam 15 disengage from arms 12c of the clutch lever 12 so that the spring 14 causes the clutch lever 12 to return to the position shown by solid lines in FIG. 2 together with the pinion 8. Thus, the pinion 8 and the spool shaft 10 is again coupled and thereby bringing the clutch to the ON state.
FIGS. 7 through 9 show another embodiment of this invention. While in the first embodiment two operating levers were provided, in this modification, only one operating lever is used.
As shown in FIGS. 7 through 9, similar to the above described first operating lever 23, the operating lever 223 of this modification is rotatably and slidably secured to the inner plate 1 by a step screw 225 passing through a slot 223a at the center and resiliently urged to rotate in the counter-clockwise direction by a spring 27.
A contact member 223b is provided for one end of the operating lever 223 and an upwardly bent engaging member 223c is provided for the other end. An additional operating 223e which functions in the same manner as the second kick lever 24 of the first embodiment is projected from one side thereof so as to position the projection 15f of the clutch cam 15 between two members 223b and 223e.
When the clutch is ON, the first operating member 223b is pushed by the projection 15f of the clutch cam 15 so that the operating lever 223 is rotated in the clockwise direction as shown in FIG. 7 against the force of the spring 27 whereby its engaging member 223c is disengaged from the ratchet wheel 4. When the clutch is turned OFF by rotating the clutch cam 15, the projection 15f releases the pressure of the first operating member 223b so that the operating lever 223 is rotated in the counter-clockwise direction by the spring force as illustrated in FIG. 8.
Then, when the ratchet wheel 4 is rotated by the handle 11 for the purpose of switching the clutch to the ON state, the tooth 4a of the ratchet wheel 4 pushes the operating lever 23 upwardly and obliquely in FIG. 8. against the force of the spring 27 as shown in FIG. 9, whereby the operating member 223e pushes the projection 15f to rotate the clutch cam 15 to a position beyond the dead point of the spring 21. Thereafter, the spring 21 rotates the clutch cam 15 to the position shown in FIG. 7, thereby bringing the clutch to the ON state and the operating lever 223 returns to its original position by the biasing force of the spring 27.
Other parts and operations are the same as those of the previous embodiment.
FIGS. 10 through 12 show still other embodiment of this invention. While in the second embodiment, the single projection 15f of the clutch cam 15 is positioned between the pair of contact members 223b and 223e, in this modification, a single contact member 102c formed on an operating lever 102 is, on the contrary, positioned between a pair of projections 101a and 101b provided on a clutch cam 101.
With this modified embodiment, in the clutch ON state shown in FIG. 12, the operating lever 102 is biased to rotate in the counter-clockwise direction by a spring 106 but its rotation is prevented by the projection 101b of the clutch cam 101. When the clutch cam 101 is rotated in the clockwise direction in FIG. 10 to bring the clutch to the OFF state, the projection 101b is moved and operating lever 102 is rotated in the counter-clockwise direction by the spring 106 until it engages a stopper 104, so that the contact member 102a enters into a space between the teeth 103a of a ratchet wheel 103 as shown in FIG. 10. Even when the member 102a collides upon a tooth 103a and does not enter into the space, it enters into the space upon the rotation of the ratchet wheel 103. When the ratchet wheel 103 is rotated in the clockwise direction in FIG. 10, a tooth 103a pushes the operating member 102a while the shoulder 102b pushes the projection 101a, so that the clutch cam 101 rotates in the counter-clockwise direction as shown in FIG. 11. When the clutch cam 101 passes through the dead point of the spring force and returns to the state shown in FIG. 12, the projection 101b of the clutch cam 101 pushes the contact member 102c of the operating lever 102 so that the contact member 102a disengages from the ratchet wheel 103 and returns to its original position shown in FIG. 12.
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A clutch mechanism for use in a fishing reel of the type wherein a pinion is operated by a clutch cam and a clutch lever, and a spool shaft is operated by a handle is disclosed. The mechanism comprises contact means provided for the clutch cam and operating means interposed between the clutch cam and a ratchet wheel. The operating means is spring-biased in a direction to mesh with the ratchet wheel, but is held by the contact means to disengaged from the ratchet wheel when the clutch cam is at its ON state. The operating means is released from the contact means and engages with the ratchet wheel when the clutch cam is turned to its OFF state, whereas, when the clutch cam is at its OFF state, the operating member pushes the contact means upon the forward rotation of the ratchet wheel to return the clutch cam to its ON state.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to data transmission networks, and specifically to coupling separated networks together.
BACKGROUND OF THE INVENTION
[0002] Methods for transferring data within networks, such as local area networks (LANs) and storage area networks (SANs), rely on standard protocols describing how the data are transferred. Typically the data for a specific network are transferred as data-frames having a format defined by the protocol governing the functioning of the network. Two protocols which are used for transferring data at gigabit/s (Gbps) rates are the IEEE 802.3(Z) Ethernet protocol, issued by the Institute of Electrical and Electronics Engineers, Inc., New Jersey, and the FC-PH Fibre Channel protocol, issued by the American National Standards Institute, Washington, D.C.
[0003] Extending a network such as a Fibre Channel (FC) network by coupling it to other like networks is typically performed by coupling the networks together using one or more private lines.
[0004] Methods for transferring data between networks operating under different protocols operating at Gbps rates are known in the art. For example, Dell Computer Corporation of Round Rock, Tex., provides a PowerVault Fibre Channel family of products which may be configured to transfer data between a Fibre Channel network and a gigabit Ethernet (GBE) network. Data transfer between the networks requires a suitably-adapted server.
SUMMARY OF THE INVENTION
[0005] It is an object of some aspects of the present invention to provide a system for coupling separate data transmission networks to form a wide area network.
[0006] It is a further object of some aspects of the present invention to provide a system for coupling separate data transmission networks in a manner substantially transparent to clients of the networks.
[0007] In preferred embodiments of the present invention, a plurality of networks which are separate from each other are coupled together via a central distributed wide area network (WAN). Each of the separate networks preferably operates according to a Fibre Channel (FC) protocol. These networks are herein termed FC networks, “FC islands,” or “islands.” The central WAN and the islands most preferably transfer data at a rate of the order of 1 gigabits/s (Gbps). The central WAN supports data transfer in the form of Internet Protocol (IP) frames, and communicates with the FC islands according to an Ethernet protocol, most preferably a gigabit Ethernet (GBE) protocol. Data is transferred between the islands and the WAN by encapsulating an FC data-frame as an IP frame with an Ethernet header, so forming an Ethernet/IP data-frame. Each island is coupled to the central WAN via a respective interface which converts data between Ethernet/IP and FC protocols. Thus, a client of one of the islands is able to communicate with a client of another of the islands using the FC protocol, so that the separate FC islands appear as one FC network to clients of the islands despite the intervening Ethernet/IP link, averting the need for one or more private lines as is used in the art.
[0008] Each interface comprises a memory, containing a look-up table, which is controlled by a dedicated central processing unit (CPU). The interface is implemented using industry-standard devices and/or one or more custom or semi-custom devices, such as application specific integrated circuits (ASICs). Most preferably, the interface for each FC island is implemented as a component within a switch coupling clients of the island. Further preferably, the switch comprises the dedicated CPU. When interfaces are implemented using dedicated components and/or ASICs, data transfer between FC islands is significantly faster than data transfer using a server.
[0009] In preferred embodiments of the present invention, a transmitting client, herein termed the transmitter, comprised in a first FC island, sends data in the form of an FC data-frame to a receiving client, herein termed the receiver, comprised in a second FC island. The FC data-frame is received by the interface to the central network in the first FC island, which converts the data-frame to one or more Ethernet/IP data-frames addressed to the interface in the second FC island. If data-frame size restrictions within the central WAN necessitate, the FC data-frame is fragmented into a plurality of ordered, encapsulated Ethernet/IP data-frames by the interface of the first island. The interface stores a temporary copy of the one or more Ethernet/IP data-frames in a buffer comprised in the interface. The interface also stores respective pointers to the one or more Ethernet/IP data-frames, and transmits the Ethernet/IP data-frames via the central network to the interface of the second island.
[0010] The interface of the second island sends an acknowledgment of correct reception of each Ethernet/IP data-frame to the interface of the first island, which checks each acknowledgment against the buffer. When there is more than one Ethernet data-frame, the interface of the second island also arranges the received data-frames in order. If one of the acknowledgments is not received by the interface of the first island, the interface resends the data. The interface of the second island checks whether it has already received the resent data, and if it has, it ignores the resent data. Once the interface of the second island has received all the Ethernet/IP data-frames formed from the FC data-frame, it reconstructs the FC data-frame and forwards it to the receiver in its island. Neither the FC transmitter nor the FC receiver is aware of the intermediate conversion to an Ethernet protocol, so that the data transmission is effectively transparent to both The process of resending unacknowledged data, and ignoring the resent data if has already been received, improves the reliability of data communication over FC communication systems known in the art.
[0011] In preferred embodiments of the present invention, Ethernet/IP data-frames are configured so as to optimize their length. Each data-frame is set to be less than or equal to a maximum length allowed by the Ethernet protocol, or to a maximum length allowed by a router or other active element within the central network. By reconfiguring data-frame length as necessary, an overall rate of data transmission is improved. Furthermore, Ethernet/IP data-frames produced in an interface can be routed according to a specific, selected path, i.e., via one or more specific routers comprised within the central WAN. By routing data-frames according to a specific path, the reliability and/or security and/or speed of data transmission is improved.
[0012] There is therefore provided, according to a preferred embodiment of the present invention, apparatus for transferring data between first and second networks via a central network therebetween, including:
[0013] a first interface coupled between the first network, which operates according to a Fibre Channel protocol, and the central network, which operates according to a protocol different from the Fibre Channel protocol, the first interface comprising a memory containing a look-up table that includes a second-network-destination-address, and being adapted to receive from a client on the first network an initial data-frame comprising the second-network-destination-address, and to derive a second-interface-address from the look-up table using the second-network-destination-address as an index to the table, and to concatenate the second-interface-address to the initial data-frame so as to form a concatenated data-frame, and to convert the concatenated data-frame to a plurality of sub-frames responsive to a length of the concatenated data-frame, each sub-frame comprising a respective counter, and to convey the plurality of sub-frames to the central network for delivery to the second-interface-address; and
[0014] a second interface coupled between the central network and the second network, which operates according to the Fibre Channel protocol, the second interface being adapted to receive the plurality of sub-frames at the second-interface-address, and to convey a respective acknowledgment of receipt of each of the plurality of sub-frames to the first interface, and to recover the initial data-frame from the plurality of sub-frames responsive to the respective counters, and to convey the recovered data-frame to the second network for delivery to the second-network-destination address;
[0015] wherein the first interface is adapted to resend one or more of the plurality of sub-frames to the second interface responsive to not receiving the acknowledgment of the respective sub-frame, and wherein the second interface is adapted to check if a resent sub-frame has already been received therein, and responsive thereto, to ignore the resent sub-frame.
[0016] Preferably, the second interface includes a second-interface memory containing a second-interface look-up table that includes a first-network-destination-address, the second interface being adapted to receive from a second-network client on the second network a second-network initial data-frame including the first-network-destination-address, and to derive a first-interface-address from the second-interface look-up table using the first-network-destination-address as an index to the second-interface look-up table, and to concatenate the first-interface-address to the second-network initial data-frame to form a second-network concatenated data-frame, and to convey the second-network concatenated data-frame to the central network for delivery to the first-interface-address, and wherein the first interface is adapted to receive the second-network concatenated data-frame at the first-interface-address, and to recover the second-network initial data-frame from the second-network concatenated data-frame and to convey the recovered second-network data-frame to the first network for delivery to the first-network-destination address.
[0017] Preferably the apparatus includes a central processing unit (CPU) which is coupled to the first interface and which is adapted to control the first interface.
[0018] Further preferably, the CPU is adapted to generate the look-up table in the memory.
[0019] Preferably, the first interface is adapted to set a length of each of the plurality of sub-frames to be no greater than a predetermined maximum transmit unit length of one of the networks.
[0020] Preferably, the protocol different from the Fibre Channel protocol comprises an Ethernet protocol.
[0021] Preferably, the memory comprises a content addressable memory.
[0022] There is further provided, according to a preferred embodiment of the present invention, a method for transferring data between first and second networks via a central network therebetween, including:
[0023] coupling a first interface between the first network, which operates according to a Fibre Channel protocol, and the central network, which operates according to a protocol different from the Fibre Channel protocol, the first interface including a memory containing a look-up table that includes a second-network-destination-address;
[0024] receiving an initial data-frame including the second-network-destination-address from a client on the first network at the first interface;
[0025] deriving from the look-up table a second-interface-address using the second-network-destination-address as an index to the look-up table;
[0026] concatenating the second-interface-address to the initial data-frame;
[0027] converting the concatenated data-frame to a plurality of sub-frames responsive to a length of the concatenated data-frame, each sub-frame comprising a respective counter;
[0028] conveying the plurality of sub-frames to the central network for delivery to the second-interface-address;
[0029] receiving the plurality of sub-frames at the second-interface-address of a second interface coupled between the central network and a second network operating according to the Fibre Channel protocol;
[0030] conveying a respective acknowledgment of receipt of each of the plurality of sub-frames to the first interface;
[0031] resending one or more of the plurality of sub-frames from the first interface responsive to the first interface not receiving one or more of the respective acknowledgments of receipt;
[0032] checking if a resent sub-frame has already been received at the second interface;
[0033] ignoring the resent sub-frame responsive to the check;
[0034] recovering the concatenated data-frame from the plurality of sub-frames in the second interface responsive to the respective counters;
[0035] generating a recovered initial data-frame from the concatenated data-frame; and
[0036] conveying the recovered initial data-frame to the second network for delivery to the second-network-destination address.
[0037] Preferably, the method includes:
[0038] receiving a second-network initial data-frame including a first-network-destination-address from a second-network client on the second network at the second interface;
[0039] deriving from a second-interface look-up table comprised in a second-interface memory in the second interface a first-interface-address using the first-network-destination-address as an index to the second-interface look-up table;
[0040] concatenating the first-interface-address to the second-network initial data-frame;
[0041] conveying the concatenated second-network data-frame to the central network for delivery to the first-interface-address;
[0042] receiving the concatenated second-network data-frame at the first interface responsive to the first-interface-address;
[0043] recovering the second-network initial data-frame in the first interface; and
[0044] conveying the recovered second-network initial data-frame to the first network for delivery to the first-network-destination address.
[0045] Preferably, the method includes coupling to the first interface a central processing unit (CPU) which is adapted to control the first interface.
[0046] Further preferably, the method includes generating the look-up table in the CPU.
[0047] Preferably, converting the concatenated data-frame to a plurality of sub-frames includes setting a length of each of the plurality of data-frames to be no greater than a predetermined maximum transmit unit length of one of the networks.
[0048] Preferably, the memory comprises a content addressable memory.
[0049] The present invention will be more fully understood from the following detailed description of the preferred embodiments thereof, taken together with the drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0050] [0050]FIG. 1 is a schematic block diagram of a wide area network (WAN) coupled to a plurality of Fibre Channel (FC) networks, according to a preferred embodiment of the present invention;
[0051] [0051]FIG. 2 is a flowchart of a process for transferring a data-frame which does not require an acknowledgment between a first client in a first FC network and a second client in a second FC network, according to preferred embodiments of the present invention;
[0052] [0052]FIG. 3 is a schematic diagram of structures of the data-frame during the transfer process of FIG. 2, according to preferred embodiments of the present invention;
[0053] [0053]FIG. 4A is a flowchart showing a process for transferring FC data which is to be acknowledged from a first client in a first FC network to a second client in a FC second network, according to a preferred embodiment of the present invention; and
[0054] [0054]FIG. 4B is a timing diagram for the process of FIG. 4B, according to a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0055] Reference is now made to FIG. 1, which is a schematic block diagram of a coupled network system 10 , according to a preferred embodiment of the present invention. System 10 comprises a plurality of separated networks each having at least one end-user client. Clients of the separated networks communicate with each other via their respective networks and a central wide area network (WAN) 18 . Each of the plurality of separated networks, herein by way of example assumed to be a first network 12 comprising a first end-user client 13 and a second network 24 comprising a second end-user client 25 , preferably operates according to a Fibre Channel (FC) protocol, and is able to operate substantially independently of the other separated networks. Networks 12 and 24 are also termed herein “FC islands” or “islands.” WAN 18 comprises one or more routers 19 which are used for transferring data within network 18 . WAN 18 is able to transfer data in an Internet Protocol (IP) format within the WAN, and operates according to any industry-standard data transfer protocol such as an Ethernet protocol. WAN 18 is able to receive and transmit data formed according to an Ethernet protocol, and most preferably, the Ethernet protocol is a gigabit Ethernet (GBE) protocol supporting data transmission at a rate of at least 1 gigabit/s (Gbps). Further most preferably, the FC protocol also supports data transmission at a rate of at least 1 Gbps.
[0056] FC island 12 is coupled to WAN 18 by a dedicated interface 14 A. A suitable interface is the GFS-8 interface produced by SanCastle Technologies Ltd., Yokneam, Israel. Interface 14 A comprises a memory 20 A comprising a look-up table, a wait for acknowledge (WFA) memory 15 A, and a buffer memory 17 A. In some preferred embodiments of the present invention, memory 20 A comprises a content addressable memory (CAM), such as a MUAA co-processor produced by Music Semiconductors of Eygelshoven, The Netherlands. Interface 14 A is most preferably installed in a switch 21 A, which couples client 13 to other clients of island 12 and which is controlled by a central processing unit (CPU) 16 A, preferably an Intel 960 produced by Intel Corporation, of Santa Clara, Calif. CPU 16 A also controls at least some of the operations of memory 20 A, WFA 15 A, and buffer 17 A, whose functions are explained hereinbelow. FC island 24 is coupled to WAN 18 by a dedicated interface 14 B, which is substantially similar in implementation and operation to interface 14 B, comprising a look-up memory 20 B, a WFA memory 15 B, and a buffer memory 17 B. Interface 14 B is most preferably installed in a switch 21 B, which is substantially similar in implementation and operation to switch 21 A, and which couples client 25 to other clients of island 24 . A CPU 16 B controls the operation of switch 21 B and also controls at least some of the operations of memory 20 B, WFA 15 B, and buffer 17 B. Interfaces 14 A and 14 B are also referred to hereinbelow as interface 14 , and switches 21 A and 21 B are also referred to hereinbelow as switch 21 . Similarly, corresponding components of the interfaces and switches are also referred to hereinbelow without suffixes A or B.
[0057] A detailed description of the implementation of an interface substantially similar in operation to interface 14 is provided in U.S. patent application Ser. No. 09/712,616, which is assigned to the assignee of the present invention and which is incorporated herein by reference. Patent application Ser. No. 09/712,616 also provides a description of the operation of a switch substantially similar in operation to switch 21 .
[0058] [0058]FIG. 2 is a flowchart of a process for transferring a data-frame which does not require an acknowledgment between client 13 and client 25 , and FIG. 3 is a schematic diagram of structures of the data-frame during transfer, according to preferred embodiments of the present invention. The flowchart of FIG. 2 applies to a data-frame which is transmitted from client 13 , typically to announce an initial presence of the client in FC island 12 . It will be understood that the process described with reference to FIG. 2 substantially applies to other data-frames which do not require acknowledgment. Such data-frames include network control or management data-frames, or data-frames announcing the continuing presence of a network client, which are not directed data-frames from one client of system 10 to another client of the system.
[0059] Initially client 13 generates an FC data-frame 50 (FIG. 3) according to an FC standard protocol, preferably according to a routing level Internet Protocol (IP). Alternatively, data-frame 50 is generated according to another routing level protocol. Data-frame 50 comprises a header section 52 , a data payload section 54 , and an FC end-of-frame (EOF) section 56 . Preferably, header section 52 comprises a source identity (ID) field 58 and a source media access control (MAC) address field 60 of client 13 , as well as a type field 62 indicating that the data-frame is a data-frame which does not need to be acknowledged. Header section 52 also preferably comprises a destination field 64 , described in more detail below, which is used to point to a specific client when data-frame 50 is used as a directed data-frame. Alternatively, data section 54 comprises some or all of the information in the ID, MAC, Type and destination fields. Clients in FC island 12 , other than client 13 , receive data-frame 50 , and record values of ID field 58 and MAC field 60 by methods known in the art, for use in transmitting data-frames to client 13 .
[0060] The data-frame from client 13 is also received by interface 14 A, which decodes the source ID and MAC of the client, preferably using CPU 16 A. The source ID and MAC are entered into a look-up table comprised in memory 20 A, and routing information to client 13 is also entered into the look-up table. It will be appreciated that the routing information indicates that client 13 is comprised in FC island 12 .
[0061] Interface 14 A then encapsulates data-frame 50 into an Ethernet/IP standard protocol format by adding an Ethernet header 71 and a data-transparent header 72 to data-frame 50 , in order to generate an Ethernet/IP data-frame 70 . Ethernet header 71 is most preferably a GBE header. Alternatively, header 71 is any other Ethernet protocol standard header. Data-transparent header 72 comprises an IP section 74 and a transport layer section 76 . Most preferably, transport layer section 76 is implemented according to a User Datagram Protocol (UDP). Alternatively, section 76 is implemented according to another industry-standard protocol which supports IP data transmission, such as a Transport Control Protocol (TCP). It will be appreciated that using a UDP reduces the number of bytes needed to be generated in data-frame 70 compared to using a TCP. Header 72 also comprises an address of interface 14 A and/or of switch 21 A as a source address of Ethernet data-frame 70 . Header 72 further comprises a transmit pointer field 78 and a counter field 80 , whose functions are explained hereinbelow, and which are typically not utilized when data-frame 70 is a data-frame not requiring an acknowledgment.
[0062] Interface 14 A conveys Ethernet/IP data-frame 70 to one or more routers 19 comprised in WAN 18 , which broadcast the data-frame within the network, so that interface 14 B in FC island 24 receives the data-frame. (Other interfaces between FC islands and central network 18 receive the data-frame, and act substantially as described herein with respect to FIG. 2.)
[0063] Interface 14 B reads the address of interface 14 A and/or of switch 21 A from header 72 , and enters the addresses as routing information for client 13 into a look-up table comprised in memory 20 B. Interface 14 B then regenerates FC frame 50 by stripping headers 71 and 72 from frame 70 , reads the address of client 13 from the regenerated frame, and enters the address of client 13 into the look-up table.
[0064] In a final step, interface 14 B transmits regenerated frame 50 to FC island 24 , so that clients, such as client 25 , comprised in island 24 are able to record values of ID field 58 and MAC field 60 of client 13 . The recording is implemented in substantially the same manner as clients in island 12 record the values.
[0065] The process described hereinabove with respect to FIG. 2 is implemented for all clients in all FC islands coupled to WAN 18 , so that each interface generates a look-up table comprising address information and corresponding routing information for each client in its respective look-up memory. The process also supplies each client with respective addresses of all other clients in system 10 .
[0066] Those skilled in the art will appreciate that other methods for generating look-up tables in the look-up memories of each interface, comprising routing information substantially similar to that described above, may be implemented in system 10 . For example, a CPU of a specific switch may transfer data comprised in the look-up table of a first interface to the look-up memory of a second interface, via WAN 18 . The transferred data is then incorporated in the look-up table of the second interface's look-up memory.
[0067] The process described with respect to FIG. 2 typically applies for FC data-frames which are considerably smaller in length than the maximum 2112 bytes allowed by the FC protocol, since the data-frames have little or no data payload. Similarly, the Ethernet/IP data-frames generated are also considerably smaller than the maximum 1500 bytes allowed by the Ethernet protocol. In WAN 18 , one or more routers 19 may only be able to accept data-frames having a shorter length than the maximum allowed by the Ethernet protocol. For example, some routers known in the art accept data-frames up to a maximum length of 572 bytes. The maximum transmit unit (MTU) of a path of a network is defined as the smallest data-frame length acceptable by all active components of the path chosen for transmission. Typically, Ethernet/IP frames generated for data-frames which do not require an acknowledgment are significantly shorter than any MTU of the network. However, in some circumstances such frames may exceed a specific MTU. A process described hereinbelow with reference to FIG. 4A and FIG. 4B can be adapted by those skilled in the art for cases where the Ethernet/IP frames generated in the process of FIG. 2 are larger than an MTU of the network.
[0068] [0068]FIG. 4A is a flowchart showing a process for transferring FC data from client 13 (FIG. 1) in first FC island 12 to client 25 in second FC island 24 , and FIG. 4B is a timing diagram 90 for the process, according to a preferred embodiment or the present invention. The process described herein is implemented after look-up tables have been generated in memory 20 A and memory 20 B, and after client 13 has been supplied with the address of client 25 , preferably as described above with reference to FIG. 2. Client 13 generates an FC data-frame according to any protocol acceptable to clients within FC island 12 . The FC data-frame is substantially similar in form to data-frame 50 (FIG. 2), including the address of client 25 in destination field 64 of the FC header, and comprises data to be transferred from client 13 to client 25 in data field 54 . Client 13 then transmits the FC data-frame at a time 82 into FC network 12 , wherein interface 14 A receives the FC data-frame.
[0069] Interface 14 A uses the look-up table of memory 20 A to determine routing information for the FC data-frame, and is thereby provided with the address of interface 14 B, by using the address of client 25 as an index to the look-up table. Interface 14 A encapsulates the FC data-frame to an Ethernet/IP data-frame substantially similar in form to data-frame 70 , incorporating the address of interface 14 B into transmit pointer field 78 comprised in header 72 .
[0070] Interface 14 A determines if the length of the Ethernet/IP data-frame is greater than the MTU of a transmission path in WAN 18 selected by the interface, prior to transmitting the Ethernet/IP data-frame, by methods known in the art. If the length is greater than the MTU, interface 14 A converts the data-frame into a plurality of ordered Ethernet/IP sub-frames, each having a length less than the MTU. The sub-frames are substantially similar in form to data-frame 70 , and comprise the order of each sub-frame in a counter field 80 of header 72 . Interface 14 A stores a copy of the Ethernet/IP data-frame or sub-frames in buffer 17 A, and one or more pointers, as needed, to the data-frame or sub-frames in WFA memory 15 A. At a time 84 interface 14 A then transmits the Ethernet/IP data-frame or sub-frames to interface 14 B.
[0071] Preferably, at times 86 interface 14 B receives the frames sent by interface 14 A, and returns an acknowledgment for each frame received to interface 14 A, which thereupon clears buffer 17 A and WFA memory 15 A. Alternatively, one or more acknowledgments, not necessarily in a one-one correspondence for the frames sent, are returned after time 84 . For example, one acknowledgment may be utilized to acknowledge a plurality of sub-frames. If interface 14 A has not received an acknowledgment for one or more specific frames by a predetermined time interval 88 , the interface utilizes the pointers stored in WFA 15 A and the respective frame copies in buffer 17 A to resend the one or more unacknowledged frames at a time 92 . The process of waiting for an acknowledgment and repeating the resending of unacknowledged frames continues for a predetermined number, preferably four, of resends for each unacknowledged frame.
[0072] Interface 14 B compares counter fields 80 of received frames to check if a resent frame has already been received (as may happen if the frame has been received by interface 14 B but the acknowledgment has not been received by interface 14 A). The resent frame is ignored if it has already been received, and is accepted by interface 14 B if it has not been previously received.
[0073] Interface 14 B converts the Ethernet/IP data-frame or sub-frames, using counter field 80 in the latter case to correctly order the sub-frames, to an FC data-frame corresponding to the FC data-frame transmitted by client 13 . Interface 14 B then transmits the FC data-frame to client 25 at a time 94 .
[0074] In some preferred embodiments of the present invention, interface 14 A acting together with its CPU 16 A is implemented to be able to select a particular route for transmission of data from FC island 12 to a client in another FC island. For example, interface 14 A may select one or more specific routers 19 in WAN 18 to enable more secure transmission, and/or to enable speedier transmission, and/or to enable use of a larger frame or sub-frame size. The selection is implemented by incorporating routing information to the selected routers in Ethernet header 71 and/or data-transparent header 72 , by methods known in the art.
[0075] It will be appreciated that the preferred embodiments described above are cited by way of example, and that the present invention is not limited to what has been particularly shown and described hereinabove. Rather, the scope of the present invention includes both combinations and subcombinations of the various features described hereinabove, as well as variations and modifications thereof which would occur to persons skilled in the art upon reading the foregoing description and which are not disclosed in the prior art.
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Apparatus for transferring data between first and second networks, each operating according to a Fibre Channel (FC) protocol, via a central network which operates according to a different protocol. The apparatus consists of a first interface between the first network and the central network, and a second interface between the second network and the central network. Each interface has a memory containing a look-up table, and each interface is adapted to receive an FC data-frame from a client on its FC network. The data-frame is converted, using the table, to a data-frame compatible with the central network. The first interface receives an FC data-frame and converts the data-frame to one compatible with the central network. The converted data-frame is transmitted via the central network to the second interface, wherein the FC data-frame is recovered and transmitted within the second FC network.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a U.S. National Phase patent application of PCT/SE2011/051547, filed on Dec. 20, 2011, which claims priority to Swedish Patent Application No. 1001216-9, filed on Dec. 22, 2010, each of which is hereby incorporated by reference in the present disclosure in its entirety.
TECHNICAL FIELD
The present invention relates to a method of providing, by high-frequency welding of at least two construction parts containing polymer material weldable by high-frequency welding to an assembled large unit in which said construction parts are comprised, fastener means on said unit, said fastener means being intended for anchoring and building up said unit.
The invention also relates to anchoring parts for that purpose.
BACKGROUND
A variety of different end products are manufactured in the above-mentioned way. Examples of end products include truck tarps, boat tarps, tarpaulins, tents, doors, fabric ceilings, inflatable products, liquid tanks, advertising signboards, sun shading, projection screens, sports facilities, storage facilities, tribune roofs, oil containment booms, valve drums, lifesaving equipment, rescue stretchers, water beds, bathing pools, etc.
High-frequency welding of polymer material is a well-known method that has been used since the 1940ies and has now been greatly developed and refined in terms of control processes, material combinations and design of process tools, such as electrodes. By means of state-of-the art process methods it is possible to obtain even, leak-proof and durable welding seams for even the widest variety of uses, such as the ones mentioned above.
In principle, high-frequency welding of two layers of polymer material is performed such that both materials are, in an overlapping welding area, pressed together between two welding electrodes or between a welding electrode and a ground plane and are exposed to a high-frequency electromagnetic field, usually 27.12 MHz. The combination of the heat generated and pressure brings about a welding seam. Four important factors that influence the final welding result are compression pressure, welding effect, welding time, and cooling time. Those parameters may be adjusted and combined in various ways to arrive at an optimal welding result for a specific material or a specific material combination.
Usually high-frequency welding is used for joining of polyvinyl chloride (PVC) and polyurethane (PU).
Obviously, it is important in the context of many of the end products listed above that they are leak-proof.
It is a substantial problem in the manufacture of said end products that, in addition to being joined, the constituent construction parts are also to be anchored in the bearing structures, and that it has so far been very difficult, cumbersome, and time-consuming to locate fastener means by way of high-frequency welding of weldable polymer material, while simultaneously applying the fastener means such that the structure becomes leak-proof. Examples of hitherto known methods of anchoring combined construction parts in bearing structures include tailored pockets on the construction parts, said pockets being intended for the introduction of carrier lists that are subsequently coupled to bearing structures. The difficulty of anchoring, in a simple and in all respects satisfactory manner, combined construction parts in bearing structures has lead to the end products becoming complex and expensive to manufacture and assemble.
For a long time there has been a very great need, in the building up of end products of the above-mentioned kind, for simplified solutions for the anchoring to bearing structures by means of units joined by high-frequency welding.
There is also a need for making manufacturing and mounting processes more efficient, eg within car manufacturing or within the building industry, to reduce the time consumption involved in the mounting and/or manufacturing processes.
BRIEF DESCRIPTION OF THE INVENTION
The present invention provides a solution to the above-referenced problem.
According to the invention, the method described in the introductory part for anchoring fastener means is characterised in that the fastener means are made of an electrically conductive material; that a primer layer is arranged on a surface of the fastener means and is bonded by means of a first hardening; that a material weldable by high-frequency welding is arranged on top of said primer layer and is bonded thereto by means of a second hardening for building up a connecting layer.
According to an embodiment, the invention is characterised in that the fastener means are applied in intended positions on the construction parts with the connecting layer on the respective fastener means in direct abutment on the construction parts and connected thereto by high-frequency welding; in that, by the construction of the intended unit, adjoining construction parts in that unit are arranged with overlapping portions; and that said construction parts are joined in said overlapping portions by high-frequency welding.
According to an embodiment, the invention is further characterised in that said weldable material for the connecting layer is selected from among polyvinyl chloride (PVC), polyurethane (PU), or from among said plastics strengthened with reinforcements, eg a glass-fibre reinforcement.
According to an embodiment, the invention is characterised in that fastener means suitable for the intended final application are selected from among a range of pre-manufactured fastener means, all of which are provided with said connecting layer and with said intermediate primer layer.
According to an embodiment, the invention is characterised in that fastener means from said range are used as electrodes in the anchoring through high-frequency welding of the fastener means in question in intended positions on the construction parts.
According to an embodiment, the invention is further characterised in that a fastener means is arranged on at least one of two construction parts arranged adjoiningly in the unit and covering said overlapping portions; and in that said fastener means is used as an electrode in the high-frequency welding.
According to an embodiment, the invention is further characterised in selecting, as said electrically conducting material, eg aluminium, stainless steel, copper, or brass.
According to an embodiment, the invention is further characterised in that said primer layer is provided in the form of a thin layer of a magnitude of 1-25 μm on the fastener means.
According to an embodiment, the invention is characterised by said connecting layer being provided through coating of polyvinyl chloride (PVC) or polyurethane (PU) with or without reinforcement on said primer layer.
According to an alternative embodiment, the invention is characterised in that said coating is applied in a layer of a thickness within the range of 25-750 μm.
According to an embodiment, the invention is characterised in that construction parts forming part of a unit are configured to be connected securely to a fastener means and to an associated connecting layer on a free surface; and that the construction parts are joined to a large unit through said connecting layer on a construction part being arranged directly against the connecting layer on an adjoining construction part, following which the mutually adjoining connecting layers are joined by high-frequency welding.
According to the invention, an anchoring part for use in the construction and/or assembly of a construction is characterised by fastener means in the form of an electrically conductive material; a primer layer arranged on a surface of the fastener means and bonded thereto through a first hardening; and a connecting layer of a polymer material weldable by high-frequency welding, said connecting layer being coated on top of said primer layer and connected thereto by a second hardening.
According to an embodiment, the invention is further characterised in that anchoring parts are made in a product range comprising different geometrical shapes and sizes.
According to an embodiment of said anchoring part, the invention is characterised in that said electrically conductive material is constituted by eg aluminium, stainless steel, copper, or brass.
According to an embodiment of said anchoring part, the invention is characterised in that said electrically conductive material is configured to contain the male part or the female part of a screw joint.
According to an embodiment of said anchoring part, the invention is characterised in that a coupling means, such as a fastener ring or brace, is secured by welding to the fastener means.
DESCRIPTION OF THE INVENTION
In the following, the invention will be described in further detail with reference to the accompanying drawings, wherein:
FIG. 1 is a schematic view showing the principles of the method according to the invention.
FIG. 2 is a schematic view showing an embodiment of the method according to the invention.
FIG. 3 is a schematic view of an exemplary anchoring part according to the invention.
FIG. 4 shows an example of how an anchoring part can be used for the connection of construction parts.
FIG. 5 shows an anchoring part in accordance with a somewhat modified embodiment.
FIG. 6 is a schematic view of a further embodiment of anchoring parts mounted on construction parts.
FIG. 7 shows, in larger scale, an anchoring part of the kind shown in FIG. 6 .
FIG. 8 is a schematic view of the principles of how two anchoring parts can be connected.
DESCRIPTION OF EMBODIMENTS
In FIG. 1 , reference numeral 1 is used to designate a fastener means of an electrically conductive material, eg of aluminium or stainless steel. On the one side of the fastener means, a primer layer 2 is arranged which is bonded to the fastener means 1 through a first hardening. A material which is weldable by high-frequency welding is arranged on top of the primer layer and is bonded thereto by means of a second hardening for building up a connecting layer 3 . That connecting layer which is weldable by high-frequency welding is constituted by a material which is selected from among polyvinyl chloride (PVC), polyurethane (PU), or from among said plastics strengthened by reinforcements, conveniently a glass fibre reinforcement. Said connecting layer is conveniently provided through coating of the primer layer 2 with a layer of polyvinyl chloride or polyurethane with or without reinforcement, which layer is bonded to the primer layer through a second hardening.
In FIG. 2 , reference numeral 4 is used to designate a construction part of a material which is weldable by high-frequency welding. FIG. 2 shows an element according to according to FIG. 1 connected to the construction part 4 . The prerequisite for that connection to take place by high-frequency welding is that the same type of polymer partakes in both the connecting layer 3 and the construction part 4 , ie if the connecting layer is constituted by polyurethane, optionally strengthened with reinforcement, the construction part must consequently consist of polyurethane.
FIG. 3 shows an example of an anchoring part according to the invention. The anchoring part as a whole is designated by 5 . In FIG. 3 , components partaking in the anchoring part 5 are designated by the same references as corresponding parts in FIGS. 1 and 2 .
FIG. 4 shows an anchoring part 5 according to FIG. 3 arranged on a construction part 4 in the form of a cloth or a film of a material which is polymeric and weldable by high-frequency welding. The material can be polyvinyl chloride (PVC) or polyurethane (PU). As will appear from FIG. 4 , two construction parts 4 and 4 ′ are arranged on top of each other with overlapping edge portions. In the exemplary embodiment shown in FIG. 4 , the anchoring part 5 is configured so as to cover said overlapping portions. By welding of said edge portions to one another, the fastener element 1 on the anchoring part can be used as the one electrode when the edge portions are joined by high-frequency welding.
Obviously, the fastener means 1 of a construction according to FIG. 4 also serves as a reinforcement of the end product and as a reinforcement of the welding seam built by the high-frequency welding.
FIG. 5 shows an embodiment which has been somewhat modified relative to the embodiment shown in FIG. 3 . In FIG. 5 , a coupling means has been arranged on the anchoring part 5 in the form of a brace 6 which is welded onto the fastener means 1 .
The anchoring parts shown in FIGS. 3 and 5 have been exemplified as featuring an elongate simple shape. In accordance with the invention anchoring parts may be manufactured in a wide range that comprises various geometrical shapes and sizes. Anchoring parts according to the invention are simple to manufacture, irrespective of shape and size. The range can be widened as needed. The fastener means 1 of aluminium or stainless steel may be made in any shape, eg curved, and may subsequently be coated with a primer layer with subsequent coating with a material which is weldable by high-frequency welding.
The primer layer 2 is arranged in a thin layer of a magnitude of 1-25 μm and bonded to the fastener element by means of a first hardening.
The connecting layer 3 of a polymer material weldable by high-frequency welding is coated onto the hardened primer layer 2 in a layer thickness of a magnitude within the range of 25-750 μm and is connected to the primer layer through a second hardening.
A system with a range of different anchoring parts will be very flexible in the manufacture and/or construction of various end products, such as truck tarps, boat tarps, tarpaulins, tents, doors, fabric ceilings, inflatable products, liquid tanks, advertising signboards, sun shading, projection screens, sports facilities, storage facilities, tribune roofs, oil containment booms, valve drums, lifesaving equipment, rescue stretchers, water beds, bathing pools, etc.
The anchoring parts are easy to store and do not adhere until they are activated by high-frequency welding. The connection between the anchoring parts and material weldable by high-frequency welding which forms part of the construction parts can be made very strong.
FIG. 6 illustrates, in one example of an embodiment, how anchoring parts 5 can be connected to construction parts 4 , 4 ′ forming part of an end product. The construction parts 4 , 4 ′ consist of a polymer material which is weldable by high-frequency welding, eg cloths of PU or PVC. The construction parts 4 , 4 ′ are joined by welding through high-frequency welding in the overlapping edge portions. At a corner of respective construction parts 4 , 4 ′, anchoring parts 5 are fastened, which are provided with fastener braces 6 for connection to bearing parts in the end product.
FIG. 7 shows, in larger scale, the anchoring parts 5 forming part of the embodiment according to FIG. 6 . The anchoring parts 5 consist of fastener means 1 of an electrically conductive material, a primer layer 2 applied on a surface of the fastener means and bonded thereto through a first hardening, and a connecting layer 3 of a polymer material weldable by high-frequency welding, said connecting layer being coated on top of said primer layer 2 and connected thereto by means of a second hardening. Fastener braces 6 of the same material as that of the fastener means 1 are welded, in a conventional manner, to the fastener means.
FIGS. 5 through 7 show coupling means in the form of a brace 6 . Obviously, other types of coupling means can be connected to the fastener means 1 .
For instance, the one half of a screw joint can be welded directly onto a fastener element 1 , following which the fastener element can quite simply be arranged by means of the other half of the screw joint in bearing parts. Another example is a fastener ring or the like which is welded directly onto a fastener element.
The electrically conductive fastener means may serve as electrodes in relation to the high-frequency welding. By using fastener elements as electrodes, substantial simplifications can be obtained in the manufacture of end products compared to the assembly methods used so far. For instance, an electrically conductive fastener element of any geometrical shape and suitable to the shape of the end product can be used as electrodes in high-frequency welding, which, in many cases, will considerably simplify the manufacture of the end product.
A considerable advantage obtained by the method according to the invention is that bearing parts of the end products can be connected directly to the fastener elements.
As will appear from the above, a fastener element may serve as the one electrode in high-frequency welding. Alternatively, the fastener element may serve as both electrodes in high-frequency welding.
The above-referenced construction parts may be made of polymer films of polyurethane or polyvinyl chloride. Depending on selected material, film thickness and electrode size and shape, a person skilled in the art is enabled to readily select suitable welding effect and suitable welding times and cooling times for obtaining strong and leak-proof welding seams.
In a corresponding manner, the person skilled in the art selects suitable welding effect and suitable welding times and cooling times for welding together, by high-frequency welding, anchoring parts on construction parts of a polymer material weldable by high-frequency welding.
By the method according to the invention considerable improvements are obtained, compared to prior art methods, in respect of manufacturing time and manufacturing costs for production parts forming part of the end products and also considerable time savings in the context of mounting of the end products.
FIG. 8 schematically shows how anchoring parts according to the invention can be used for building up or assembling structures and components. FIG. 8 shows how two anchoring parts can be connected to each other by the connecting layer being arranged in direct abutment on each other and welded to each other by high-frequency welding. In this manner very strong connections are obtained.
The method is useful eg within the car manufacturing industry or within the building sector for making the assembly of cars or building components, respectively, more efficient. The fastener element 1 on a first anchoring part 5 is connected to a first component, eg by means of a screw joint or conventional welding connection, and a second component which is to be joined with the first component is connected in a corresponding manner to another anchoring part, following which both components can be joined through high-frequency welding as is shown in a schematic view in FIG. 8 . The components that can be interconnected in this manner may obviously be of many different kinds, and in FIG. 8 such components are omitted. One example is interconnection of different window components in a building.
The invention is not limited to the embodiments described above; rather a plurality of other embodiments and modifications are possible within the scope of the appended claims.
For instance, the fastener element can be arranged in other positions on the construction element than those shown in FIG. 4 and FIG. 6 .
In fact, the invention provides a free choice as to where the fastener elements are to be arranged, which, compared to earlier known manufacturing methods, provides a considerably increased amount of options for varying the structure of the end products and the way in which various products and building constructions are to be mounted.
The above examples of electrically conductive material included aluminium, stainless steel, copper, or brass. However, other electrically conductive materials or material combinations will be possible within the scope of the appended claims.
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A method of providing, by high-frequency welding of at least two construction parts ( 4,4 ′) containing polymer material weldable by high-frequency welding to an assembled large unit in which said construction parts are comprised, fastener means ( 1 ) on said unit, said fastener means being intended for anchoring and building up said unit. The fastener means ( 1 ) are made of an electrically conductive material, and a primer layer ( 2 ) is arranged on a surface of the fastener means ( 1 ) and is bonded by means of a first hardening. A material weldable by high-frequency welding is arranged on top of said primer layer and is bonded thereto by means of a second hardening for building up a connecting layer ( 3 ). The invention also relates to anchoring parts ( 5 ) for use for that purpose.
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