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TECHNICAL FIELD
The present specification generally relates to tool protection devices for hand-guided rotating tools.
BACKGROUND
In the manufacturing of automobiles on an assembly line, there are many repetitive process steps. Some of the process steps are performed manually using a variety of tools. When products are manually assembled, it may be somewhat difficult to accurately align the various tools for machining or fastening processes. Incorrect alignment of tools during machining or fastening processes can result in a variety of conditions, such as cross-threading. In many instances, an automobile must be taken off-line and repaired if a cross-threading condition occurs, which causes delay in vehicle production.
SUMMARY
In one embodiment, a hand-held tool protection device includes a handle sized and configured to be grasped by an operator. A neck portion extends outwardly from the handle in a direction of a elongated axis of the handle. A swivel assembly is connected to the neck portion. The swivel assembly includes a body having a top, a bottom and a sidewall. The body is connected to the neck portion at the sidewall of the body. An opening extends through the body and intersects the top and the bottom of the body. A pivotable rod member is slidably and pivotably received in the opening extending through the body to provide a pivot axis. A tool element holding assembly is connected to the pivotable rod member such that the tool element holding assembly pivots therewith about the pivot axis. The tool element holding assembly includes a support assembly configured for receiving a tool such that the tool may be rotated about a tool rotation axis.
In another embodiment, a hand-held tool protection device includes a tubular housing body that is graspable by an operator having a first end bore, a second end bore and an interconnecting bore extending between the first end bore and the second end bore. A tool assembly extends from the first end bore, through the interconnecting bore and into the second end bore. The tool assembly includes a tool comprising a tool holder located at the first end bore, a spring located between the tool holder and the interconnecting bore and a tap portion located at the second end bore. The spring biases the tool toward a retracted position.
In another embodiment, a hand-held tap protection device includes a handle sized and configured to be grasped by an operator. A neck portion extends outwardly from the handle in a direction of an elongated axis of the handle. A swivel assembly is connected to the neck portion. The swivel assembly includes pivot structure having a pivot axis. A tool element holding assembly is connected to the pivot structure such that the tool element holding assembly pivots therewith. The tool element holding assembly includes a support assembly configured for receiving a tap such that the tap may be rotated about a tool rotation axis.
These and additional features provided by the embodiments described herein will be more fully understood in view of the following detailed description, in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The embodiments set forth in the drawings are illustrative and exemplary in nature and not intended to limit the subject matter defined by the claims. The following detailed description of the illustrative embodiments can be understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:
FIG. 1 is a side view of a tool protection device according to one or more embodiments described herein;
FIG. 2 is a section view of a swivel assembly for use with the tool protection device of FIG. 1 according to one or more embodiments described herein;
FIG. 3 is another section view of the swivel assembly of FIG. 2 according to one or more embodiments described herein;
FIG. 4 is a top, partial view of the tool protection device of FIG. 1 according to one or more embodiments described herein;
FIG. 5 is a section view of a support assembly for use with the tool protection device of FIG. 1 ;
FIG. 6 illustrates another embodiment of a tool protection assembly according to one or more embodiments described herein;
FIG. 7 illustrates a section view of the tool protection assembly of FIG. 6 according to one or more embodiments described herein;
FIG. 8 illustrates the tool protection assembly of FIG. 6 in a disengaged configuration according to one or more embodiments described herein; and
FIG. 9 illustrates the tool protection assembly of FIG. 6 in an engaged configuration according to one or more embodiments described herein.
DETAILED DESCRIPTION
Embodiments described herein generally relate to tool protection devices for insulating an operator from a rotating tool element. The tool protection devices may be hand-held and used as the operator manually guides the tool element to a work location while the tool element is not rotating. The tool protection devices may also be used as the tool element rotates during operation, which can inhibit contact between the rotating tool element and the operator.
Referring to FIG. 1 , an exemplary embodiment of a hand-held tool protection device 10 includes a handle portion 12 including a handle 14 , a neck portion 16 , a swivel assembly 18 and a tool element holding assembly 20 . The handle 14 is sized and configured to allow the operator to grasp and hold the tool protection device 10 and is connected to the swivel assembly 18 by the neck portion 16 . In the illustrated embodiment, the neck portion 16 is formed by a relatively straight rod 22 having a threaded portion 24 and a smooth portion 26 . In other embodiments, the rod 22 may have a shape other than straight, such as including one or more bends or curved portions. The neck portion 16 may have a cross-section dimension that is less than the handle 14 , however, other configurations are contemplated.
The swivel assembly 18 is threadably connected to the threaded portion 24 of the rod 22 . In other embodiments, the swivel assembly 18 may be connected to the rod 22 using any other suitable connection, such as by welding, adhesive, etc. Referring also to FIG. 2 , the swivel assembly 18 includes a body 28 including a connector arm 30 for connecting the swivel assembly 18 to the rod 22 and a bore 32 extending vertically through the body 28 and substantially perpendicular to the connector arm 30 that is sized to slidably receive a vertically oriented swivel attachment assembly 34 . The swivel attachment assembly 34 includes a rod member 36 that is slidably and rotatably received in the bore 32 and a vertical arm attachment 38 that is located at an attachment end 40 of the rod member 36 . A latch pin 42 (e.g., a fastener) is located at an upper end 44 of the rod member 36 . The latch pin 42 extends outwardly from and substantially transverse to the rod member 36 . A spring 46 or other suitable biasing member is located about the rod member 36 and between an upper surface 48 of the vertical arm attachment 38 and a bottom surface 50 of the body 28 . The spring 46 is used to bias the swivel attachment assembly 34 toward the illustrated latched position.
Referring to FIGS. 3 and 4 , the swivel attachment assembly 34 can be moved (e.g., manually) in the direction of arrow 52 toward an unlatched position. In the unlatched position, the latch pin 42 is located above adjacent rotation limiting elements 54 and 56 that extend outwardly above a valley surface 58 between the two rotation limiting elements 54 and 56 . In this unlatched position as shown by FIGS. 3 and 4 , the swivel attachment assembly 34 can be rotated (e.g., 25 degrees or more, such as 45 degrees or more, such as 90 degrees or more, such as 180 degrees) to a second latched position above valley surface 60 . In some embodiments, there may be three or more discrete latched positions. For example, FIG. 4 shows three different and discrete latched positions that are located at valley surfaces 58 , 60 and 65 . Operation of the tool protection device will be described in greater detail below.
Referring back to FIG. 1 , the tool element holding assembly 20 includes a vertically oriented rod 62 that extends substantially parallel to the rod member 36 and downwardly below the swivel assembly 18 . A first end of the rod 62 is received within the vertical arm attachment 38 . The rod 62 may be affixed to the swivel assembly 18 using any suitable means, such as adhesive, threads, welding, etc. Connected near an opposite end 70 of the rod 62 is a tool holding assembly 64 . The tool holding assembly 64 includes a support assembly 66 and a horizontally oriented connecting rod 68 that extends substantially perpendicular to the rod 62 and offsets the support structure 66 from the rod 62 in a direction transverse the length of the rod 62 .
Referring to FIG. 5 , the support assembly 66 includes a tubular body 72 defining a sidewall 73 of the support assembly 66 . The support assembly 66 may include a bearing adapter 74 that is sized to rotatably receive a rotating shaft of the tool 76 . In some embodiments, the bearing adapter 74 may include a tubular body 78 having an inner diameter 80 and an outer diameter 82 . The outer diameter 82 may be sized to fit in the tubular body 72 , while the inner diameter 80 may be sized to fit around a shaft 84 of the tool 76 . In some embodiments, the inner diameter 80 may be a dimension that is smaller than a cross-sectional dimension of a tap holder portion 86 and a threaded portion 88 of the tool 76 . This arrangement can prevent unintended removal of the tool 76 from the bearing adapter 74 during use. When the tool protection device 10 is used with a tap as the tool 76 , it may be referred to as a tap protection device. While the inner diameter 80 and the outer diameter 82 are illustrated as being substantially constant, the diameters 80 and 82 may vary along the length of the bearing adapter 74 . Additionally the inner diameter of the support assembly 66 may vary to mate with the outer diameter 82 of the bearing adapter 74 . In some embodiments, the bearing adapter 74 may be split into two or more pieces (e.g., along lines 90 and 92 to facilitate locating the tool 76 within the bearing adapter 74 . Once the tool 76 is located in the bearing adapter 74 , the tool 76 and bearing adapter 74 may be placed within the tubular body 72 . In some embodiments, set screws 94 and 96 may be provided to fasten and fix the bearing adapter 74 within the tubular body 72 such that the tool 76 can rotate relative to the bearing adapter 74 and the tubular body 72 .
Referring back to FIG. 1 , once the tool 76 and bearing adapter 74 are received by the tubular body 72 of the support assembly 66 , the handle 14 may be used to position the tool 76 at a desired location (e.g., at a hole to be tapped, for example, on a vehicle). Once positioned, the handle 14 extends substantially orthogonal to a tapping axis A that is defined by the axis of rotation of the tool 76 . As can be seen, the tapping axis A is also offset laterally from a swivel axis S that is defined by the swivel assembly 18 . In some instances, a manual tapping device may be connected to the tool 76 at the tap holder portion 86 , which is used to rotate the tool 76 . In other instances, a power-operated tapping device may be connected to the tool 76 at the tap holder portion 86 , which is used to rotate the tool 76 .
While the above tool protection device 10 is a somewhat offset configuration (i.e., the gripping location is offset from the tapping axis A), FIG. 6 illustrates another embodiment of a tool protection device 100 having a somewhat in-line configuration where the gripping location is about the tapping axis. Referring to FIG. 6 , the tool protection device 100 generally includes a housing body 102 and a tool assembly 104 slidably and rotatably received in the housing body 102 .
Referring to FIG. 7 , in one exemplary embodiment, the housing body 102 includes a first end bore 106 , a second end bore 108 and an interconnecting bore 110 that connects the first and second end bores 106 and 108 . In the illustrated embodiment, the first end bore 106 has a diameter D 1 that is greater than diameters D 2 and D 3 of the second end bore 106 and the interconnecting bore 110 , respectively. D 3 of the interconnecting bore 110 may have the smallest dimension.
The tool assembly 104 generally includes a tool 112 , a tool holder 114 and a tap portion 116 that is separated from the tool holder 114 by an elongated shaft 118 . The tool holder 114 may be releasably connected to the elongated shaft 118 , for example, using a threaded connection. A spring 120 or other biasing member is located beneath the tool holder 114 and a washer 122 is located above the tap portion 116 .
To assemble the tool protection device 100 , the tool holder 114 may be removed from the elongated shaft 118 . The washer 122 may then be received over the elongated shaft 118 such that the washer 122 rests against the tap portion 116 . The washer 122 may have an inner diameter that is less than a maximum width of the tap portion 116 yet greater than a width of the elongated shaft 118 . The outer diameter of the washer 122 may be larger than D 3 of the interconnecting bore 110 . An end opposite the tap portion 116 may then be received by the second end bore 108 , the interconnecting bore 110 and then into the first end bore 106 . The spring 120 may then be slid over the elongated shaft 118 . The spring 120 may have a maximum width that is greater than D 3 of the interconnecting bore 110 such that the spring can rest against a seating surface 124 of the first end bore 106 . The tool holder 114 may then be connected to the elongated shaft 118 , as illustrated, thereby completing assembly of the tool protection device 100 .
In some embodiments, the tool protection device 100 may be used with an elevated tapping machine 130 that is suspended on a overhead fixture, for example. When the tool protection device 100 is used with a tap, it may be referred to as a tap protection device. As shown in FIG. 8 , the tap portion 116 is retracted within the housing body 102 when the tapping machine 130 is disengaged from the tool 112 . Referring to FIG. 9 , when the tapping machine 130 engages the tool holder 114 , the tap portion 116 may be extended below the housing body 102 for a tapping operation. The bias provided by the spring 120 biases the tool 112 toward the retracted position once the tapping machine 130 is disengaged from the tool 112 .
The above-described tool protection devices can be used in guiding the tapping tool to the area being tapped and can be used to isolate the operator's hands and clothing from the rotating tool during use. The tool protection devices may be formed of any suitable material such as plastics and/or metals and using any suitable process such as molding, machining, etc. Use of the tool protection devices may reduce instances of misalignment during a tapping process, which can reduce instances cross-threading and resulting manufacturing delays.
While particular embodiments have been illustrated and described herein, it should be understood that various other changes and modifications may be made without departing from the spirit and scope of the claimed subject matter. Moreover, although various aspects of the claimed subject matter have been described herein, such aspects need not be utilized in combination. It is therefore intended that the appended claims cover all such changes and modifications that are within the scope of the claimed subject matter.
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A hand-held tool protection device includes a handle sized and configured to be grasped by an operator. A neck portion extends outwardly from the handle in a direction of a elongated axis of the handle. A swivel assembly is connected to the neck portion. The swivel assembly includes a body having a top, a bottom and a sidewall. The body is connected to the neck portion at the sidewall of the body. An opening extends through the body and intersects the top and the bottom of the body. A pivotable rod member is slidably and pivotably received in the opening extending through the body to provide a pivot axis. A tool element holding assembly is connected to the pivotable rod member such that the tool element holding assembly pivots therewith about the pivot axis. The tool element holding assembly includes a support assembly configured for receiving a tool such that the tool may be rotated about a tool rotation axis.
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BACKGROUND OF THE INVENTION
[0001] The instant invention relates to systems for expelling powder materials from mailpieces, and more particularly to a jogger system that compresses mailpieces while performing a jogging function.
[0002] Recent events have led to the realization that unscrupulous individuals may attempt to use the postal delivery system as a vehicle for spreading terrorism. These individuals have, for example, contaminated mailpieces with biological agents (such as anthrax) and distributed such mailpieces to targeted locations via the postal service. While the extent of damage that may occur by using mailpieces as a carrier of biological agents has yet to be determined, the potential for significant health risks is clear. Accordingly, increased efforts have been set forth toward the development of systems and processes that may be effective in detecting contaminated mailpieces within the postal delivery system prior to delivery to their final destination.
[0003] One such proposed system involves snipping the corner off every mailpiece (to create an opening at the corner of the envelope), placing the snipped mailpieces in a jogger system, operating the jogger system for approximately 3 minutes, pulling ambient air through the jogger system, monitoring the pulled air with two systems (one to test particle size and one to capture powder in a filter for subsequent lab testing of the material captured), then banding the mailpieces in a conventional banding machine to squeeze air out of the mailpieces, and finally sampling the air from the banding operation with the above two air-monitoring systems to determine the presence and nature of any powder materials prsent in the airflow. The air pulled through the individual workstations in this process is moved through a HEPA filter and vented outside the work area. Operation of this system is a time consuming process, with manual steps taken between each operation.
[0004] In the proposed system, once the air-monitoring filter has been tested for the presence of a biological agent, the mailpieces are unbanded and moved to a separate area for sorting and final distribution if the results of testing are negative. If a biological agent is detected however, the facility is shut down until decontamination can be performed.
[0005] One of the problems with the proposed system is the time required for the banding/unbanding operation. The value of the banding operation is not in the band that is placed around the mailpieces, but rather in the compression of the mailpieces that occurs during banding. The compression step serves to expel air from the mailpieces. In the event that a biological powder material is present in the mailpieces, it is carried with the expelled air and subsequently detected by the air-monitoring apparatus. Accordingly, if the banding/unbanding operation could be eliminated, the system would have a higher throughput and would benefit from a cost and complexity standpoint. By eliminating the banding/unbanding operation, the banding equipment and the ductwork associated with it can be eliminated. Also, the volume of air that would be required to be pulled through the entire system would be decreased thereby permitting the use of smaller vacuum sources thereby reducing costs.
SUMMARY OF THE INVENTION
[0006] A method for expelling air out of mailpieces includes the steps of creating a stack of the mailpieces; cutting an opening in at least some of the mailpieces; jogging the stack of mailpieces; and subjecting the stack of mailpieces to at least one compression/decompression cycle during the jogging step thereby expelling air out of the at least some of the mailpieces through their corresponding openings. A jogger system incorporates the structure for accomplishing the method.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate a presently preferred embodiment of the invention, and together with the general description given above and the detailed description of the preferred embodiment given below, serve to explain the principles of the invention.
[0008] [0008]FIG. 1 is a schematic diagram of a known warehouse mail processing facility;
[0009] [0009]FIG. 2 is a schematic diagram of the detection system used in the warehouse facility of FIG. 1;
[0010] [0010]FIG. 3 is a flowchart of the processing of mailpieces in the warehouse mail processing facility;
[0011] [0011]FIG. 4 shows a perspective view of an inventive jogger system;
[0012] [0012]FIG. 5 shows a rear view of the jogger system of FIG. 4;
[0013] [0013]FIG. 6 is a flowchart showing the operation of the jogger system of FIG. 4 as used in an inventive detection system;
[0014] [0014]FIG. 7 is a schematic diagram of the inventive detection system;
[0015] [0015]FIG. 8 is a perspective view of the inventive mailpiece opening system;
[0016] [0016]FIG. 9 is a view showing the mailpiece transport and cutter wheel drive system of FIG. 8;
[0017] [0017]FIG. 10 is a top plan view of FIG. 9 showing only the cutter wheels and mailpiece orientation during cutting;
[0018] [0018]FIG. 11 is a schematic drawing showing the cutting of a mailpiece using the cutter wheels of FIG. 10; and
[0019] [0019]FIG. 12 is a schematic drawing showing the cutting of a mailpiece using a second embodiment of cutter wheels.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] [0020]FIG. 1 shows a conventional warehouse facility 1 containing three bio-pods 3 , 5 , and 7 that are used to detect biological agents contained in mailpieces being processed through the warehouse facility 1 . Each of the bio-pods 3 , 5 , and 7 contain one or more of the biological agents detection system 9 shown in FIG. 2. The detection system 9 includes a conventional jogger system 11 , a corner snipper 13 (such as the “Corner Rounder”, model 50P sold by Lassco Products), a vacuum and HEPA filter system 15 , a banding mechanism 17 , first and second air-monitoring systems 19 , 21 and associated ductwork 23 that connects each of the work stations 11 , 13 , 17 , 19 , and 21 to the vacuum and HEPA filter system 15 .
[0021] The operation of the bio-pods 3 , 5 , and 7 will now be described in connection with FIGS. 1, 2, and 3 . First, mailpieces are delivered by a truck 25 to the warehouse facility 1 for processing. The mailpieces may have previously been irradiated with an e-beam in an attempt to destroy any biological agents that may have been present ( 301 ). Upon delivery to the warehouse 1 , the mailpieces are first passed through an X-ray machine 27 in an attempt to detect incendiary or explosive devices and to segregate questionable items accordingly ( 303 ). The mailpieces are then moved into one of the bio-pods 3 , 5 , and 7 ( 305 ). The mailpieces are then placed in the jogger system 11 and jogged (vibrated) in a known manner to register the corners of a batch (typically approximately 1″ thick) of mailpieces ( 307 ). After registration, the batch of mailpieces are placed in the known corner snipper 13 in their registered orientation so that the snipper 13 can snip off one corner of each of the mailpieces in a single cutting motion ( 309 ).
[0022] The small batches of snipped mailpieces are then combined into larger batches of approximately 8-12″ in thickness and reloaded into the jogger system 11 and jogged for approximately 3 minutes ( 311 ). During this jogging period the snipped corners are registered and if any biological agent powder materials are present in the mailpieces it is expected that the powder materials will leave the mailpiece through the opened corners. The jogger system 11 is enclosed and connected to the ducting 23 such that some of the powder material will be pulled from the jogger 11 toward the vacuum system 15 ( 313 ). As the powder material flows toward the vacuum system 15 , portions of it are directed to the first and second air monitoring systems 19 , 21 ( 315 ). The second monitoring system 21 detects the particle size of any powder material that is present and performs a particle size analysis. Based on the particle size analysis, the potential presence of a biological hazard may be indicated ( 317 ).
[0023] The first monitoring system 19 includes a paper filter that collects portions of any powder material that is present in the airflow being deflected therethrough. The paper filter is removed, for example, once per day and sent to a lab to test for the presence of biological agents ( 319 ). If the results of steps 317 and 319 are both negative ( 320 ) the normal processing of the mailpieces 87 continues.
[0024] After the jogging process is completed, the batch of mailpieces is sent to the known banding system 17 where the batch of mailpieces is compressed during banding ( 321 ). The compressing step forces the air inside the mailpieces to be ejected within the enclosed banding system 17 . The vacuum system 15 draws the ejected air from the banding system 17 through the ductwork 23 such that portions of the ejected air will be sampled at the first and second air-monitoring systems 19 , 21 as discussed above ( 322 ). If during the above processing of the mailpieces through the bio-pods 3 , 5 , and 7 no biological agents have been detected, the mail is moved from the bio-pods 3 , 5 , 7 to a mail sorting area 29 ( 323 ). The banded batches of mailpieces are unbanded and sorted for delivery by their destination zipcodes ( 325 ). The batches of mailpieces are then placed on trucks 31 to continue being processed through the normal mailpiece distribution system ( 327 ).
[0025] In practice, the results of the lab tests on the paper filter takes about 24 hours. Accordingly, two of the three bio-pods 3 , 5 , and 7 are used on alternate days for processing mailpieces while the third bio-pod remains unused. If however, a biological agent is detected in one of the bio-pods based on filter testing and particle size analysis, the mailpieces in that bio-pod remains quarantined until authorities complete a forensics investigation and perform any required decontamination of the contaminated bio-pod ( 329 ). In the meantime, the processing of mailpieces continues in the manner described above using the other two bio-pods.
[0026] The instant inventors have eliminated the need for the banding machine 17 by inventing the jogger system 41 shown in FIGS. 4 and 5. The jogger system 41 includes a housing 43 (also referred to herein as a jogger tray) defined by two sidewalls 45 , 47 , a rear wall 49 , a front wall 51 , and a platform 53 . The platform 53 does not extend to the rear wall 49 such that an opening 55 exists, between the rear wall 49 and the platform 53 , that runs the full length of the platform 53 . The jogger tray 43 also includes a cover 57 that is hinged to back wall 49 for movement between the open position shown in FIGS. 4 and 5 and a closed position. In the closed position, the cover 57 together with the side walls 45 , 47 and rear wall 49 define a first enclosed chamber 59 . Further, a second enclosed chamber 60 is defined by the space created between the bottom of the platform 53 , side walls 45 , 47 , rear wall 49 and front wall 51 . Additionally, front wall 51 has an opening 61 therein which is in operative communication with the ductwork 23 to permit air to be pulled through opening 55 into the second chamber 60 and thereafter pulled out from the second chamber by the vacuum and HEPA filter system 15 .
[0027] In addition to the jogging tray 43 , a paddle 62 is mounted for movement between the side walls 47 and 45 . The paddle 61 is mounted on an arm 63 of a bracket 65 . The arm 63 passes through a slot 67 in the back wall 49 . The bracket 65 is mounted on two guide rods 68 , 69 and a lead screw 71 . The lead screw 71 has a pulley 73 attached at one end thereof and is operatively connected to a motor 75 via an endless belt 77 that extends around the pulley 73 and a second pulley 79 connected to a shaft of the motor 75 . Accordingly, as the bidirectional motor 75 is energized, the lead screw 71 is forced into rotation causing a corresponding movement in the bracket 65 along the lead screw 71 and the guide rods 67 , 69 . A controller 81 is operatively connected to the motor 75 to control the supply of power from a power source 82 to the motor 75 . The controller 81 therefore controls the movement of the paddle 62 between the side walls 45 , 47 . The controller 81 and power source 82 are typically mounted on a table (not shown) upon which the jogging system 41 is placed.
[0028] A hinged plate 83 is connected to side wall 47 and biased away from the side wall 47 by a spring 85 . Mailpieces 87 are positioned between the paddle 62 and plate 83 such that the snipped lower corner of each mailpiece is placed near rear wall 49 . Thus, the opening in the mailpieces at the snipped corners are disposed over the opening 55 . Once the mailpieces are placed between the paddle 62 and the plate 83 , the controller 81 controls the motor 75 to move the paddle 62 toward the plate 83 to compress the mailpieces 87 . A switch 91 , mounted on side wall 47 , is activated when plate 83 is forced by the movement of paddle 62 into the mailpieces 87 to contact the switch 91 . The switch 91 , upon activation, sends a signal to the controller 81 . Upon receipt of the switch signal, the controller 81 stops the movement of the paddle 62 into the mailpieces 87 and retracts the paddle 62 a small distance thereby allowing the mailpieces 87 to decompress.
[0029] When the mailpieces 87 are to be removed, the controller 81 will activate the motor 75 to move the paddle 62 toward side wall 45 . A projection 93 on paddle 62 will contact and activate a second switch 95 on rear wall 45 . Upon activation of the second switch 95 , a signal is sent to the controller 81 . Upon receipt of the signal from the second switch 95 , the controller 81 stops the movement of the paddle 62 .
[0030] The entire jogger tray 43 is mounted to a conventional jogging device shown schematically at 97 . The jogging device 97 , when activated, will vibrate the entire jogging tray 43 such that the mailpieces 87 become registered against the rear wall 49 and the platform 53 as shown. To assist in the registration process, the entire jogging tray 43 is mounted to the jogging device 97 such that platform 53 is angled downward toward both the rear wall 49 and the side wall 47 .
[0031] The jogging device 97 can be one of many conventional devices that can vibrate objects attached thereto using mechanical or electromagnetic techniques. Examples of known joggers include the “Quiet Jog” sold by the Omation Division of Opex® Corporation and the “LasscoJog”—model LJ-4 sold by Lassco Products. It is contemplated by the inventors that any known jogging device that can be adapted to have the jogging tray 43 mounted thereto can be used.
[0032] Referring to FIGS. 6 and 7, an inventive detection system 101 is shown incorporating the inventive jogger system 41 . The detection system 101 has eliminated the need for a banding device 17 because the jogger system 41 includes compression apparatus as described above. In operation, the mailpieces 87 are placed in a conventional jogger system 11 in order to register the corners of the mailpieces 87 over the opening 55 as discussed above ( 601 ). The registered mailpieces 87 are then placed in the corner snipper 13 where their corners are cut open ( 603 ). The mailpieces 87 with the cut corners are placed in the jogger tray 41 of the jogger system 41 ( 605 ). Next a start button 99 is depressed by the operator which signals the controller that compression of the mailpieces is required. The controller 81 energizes the motor 75 to move the paddle 62 from the home position at switch 95 into contact with the mailpieces 87 . The paddle 62 is driven until the switch 91 is activated by movement of the plate 83 . At this point in time the mailpieces 87 are in a compressed state ( 607 ). Upon receipt of the signal from activated switch 91 , the controller 81 causes the motor 75 to retract the paddle 62 a small distance such that the mailpieces 87 decompress by filling with air ( 609 ). At this point in time the jogger device 97 is switched on (in a conventional manner) to vibrate the jogger tray 43 for a predetermined period of time, such as one minute ( 611 ). The controller 81 is designed to move the paddle 62 to perform a compression operation as described above once every 20 seconds. Accordingly, during the vibrating of the jogger tray 43 the mailpieces 87 will be compressed and decompressed at the 20 second and 40 second time intervals during the one minute vibration period ( 613 ). Once the vibrating cycle is finished (jogger device) stopped, the paddle 62 returns to the home position and the mailpieces 87 are removed and set aside until the results of the testing at the first and second air-monitoring systems 19 , 21 has been completed ( 615 ). The processing of the mailpieces 87 subsequent to obtaining the air-monitoring tests are the same as shown in FIG. 3 ( 617 ). If the testing is negative steps 323 , 325 , and 327 are performed except that the removal of the band from the mailpieces 87 is not required. If the testing is positive step 329 is performed.
[0033] The compression of the mailpieces 87 during the vibration cycle allows air inside the mailpieces 87 to be expelled through their opened corners. If powdered biological material is present inside the mailpieces 87 , some of the biological powder will be carried with the expelled air. This powder will fall through the opening 55 and into the second chamber 60 . The vacuum and HEPA filter system 15 will draw the powder material through the ductwork 23 such that most of it will be captured by the HEPA filter system 15 while some of it will flow to the air-monitoring systems 19 , 21 . Once the paddle 62 is retracted such that the mailpieces 87 are allowed to decompress, biological powder can still pass through the corner opening of the mailpieces 87 and through the opening 55 during the vibration of the jogging tray 43 .
[0034] The advantage of performing multiple compression/decompression cycles during the vibrating cycle is that during the compression cycle there is a greater probability that any powder residing in the mailpieces 87 will be expelled out of the mailpieces 87 through their opened corners than during the period where the mailpieces 87 are not compressed. Naturally, while a specific number of compression/decompression cycles have been discussed, the instant invention contemplates that any number of compression/decompression cycles can be used during the jogging period and the frequency and duration of such cycles can be adjusted as well. Additionally, the jogging period can be shorter or longer than 1 minute.
[0035] In FIG. 7, two jogger systems 11 and 41 are used to improve the overall efficiency of the detection system 101 . That is, since the initial registration jogging function (step 601 ) and the snipping operation (step 603 ) are likely to take longer than the jogging and compression operation (steps 611 , 613 ), the use of a dedicated registration jogger 11 will improve mailpiece throughput. However, the instant invention could be implemented using only the jogger 41 which would be used in a first instance to register the mailpieces 87 prior to the snipping operation and in a second instant be used for the compression/decompression cycling for expelling powder from the mailpieces 87 .
[0036] By way of reference to FIGS. 8 - 11 , a description of an inventive envelope cutting system that can be used in lieu of the corner snipper 13 shall be described. FIG. 8 shows a Pitney Bowes Inc.® 1250 mail opening system 801 that has been modified to include the inventive cutting system that includes a pair of cutter wheels 803 , 805 . The mail opening system 801 further includes a housing 807 having an envelope infeed platform 809 . An envelope retainer 811 is located on infeed platform 809 and is spring loaded towards an infeed envelope guide wall 813 .
[0037] An envelope outfeed platform 815 is provided with an envelope retainer 817 in the form of a press plate which is spring loaded towards an outfeed envelope support wall 819 to maintain opened (cut) envelopes 87 in a stacked and generally vertical orientation on outfeed platform 815 . The infeed and outfeed platforms 809 , 815 are shown connected by a generally narrow envelope travel path 820 along which mailpieces 87 (such as envelopes) are moved by a belt 821 operating in conjunction with a ski 822 biased toward belt 821 by a spring 823 , as shown in FIG. 9.
[0038] Envelopes 87 retained on the infeed platform 809 are advanced by belt 821 past the generally horizontally oriented cutter wheels 803 , 805 which cut portions of the bottom edges of the envelopes 87 as described in more detail below. As shown in FIG. 9, the cutter wheels 803 , 805 have respective beveled edges 824 , 825 . The cutter wheels 803 , 805 overlap to cut mailpieces 87 that are fed to the cutter wheels 803 , 805 . As the envelopes 87 are moved along travel path 820 they encounter a deflection wall 826 that deflects the envelopes 87 towards retainer 817 and an envelope stacker 827 . The envelope stacker 827 is formed of a plurality of wheels 828 , rotating in the direction of arrow 829 , and having protrusions (not shown) with which each opened envelope 87 is urged by repetitive impacts against a stacking wall 831 . In this manner opened envelopes 87 , as they arrive, are maintained with their leading edges against wall 831 to stack sequentially until all mailpieces 87 at the infeed platform 809 have been opened. The infeed platform 809 is inclined downwardly towards wall 813 and has a slot 833 to enable a bracket (not shown) to support retainer 811 from below platform 809 . Outfeed platform 815 is inclined downwardly away from wall 819 and provided with a slot 835 through which retainer 817 can be movably supported with a bracket 837 . The spring loading of retainers 811 , 817 is obtained with suitable springs mounted below platforms 809 , 815 respectively.
[0039] An envelope jogger 839 is provided to urge the contents of envelopes 87 against one edge or side within the envelopes 87 . The envelopes 87 are placed in a general vertical orientation on a platform 841 which is vibrated in a vertical direction in a conventional manner to bounce envelopes 87 up and down and thus urge their contents to move downwardly towards the bottom edge and to register the bottom edges of the mailpieces 87 .
[0040] After completion of the jogging operation, the jogged and registered envelopes are then are placed on infeed platform 809 with the edges, that are opposite from the edge where the contents were shifted to during jogging, facing down. The mailpieces 87 are fed to the cutter wheels 803 , 805 where they are cut in a manner discussed in more detail below. As the mailpieces 87 are cut, any biological powder material falling off or out of the mailpieces 87 collects below the cutter wheels 803 , 805 and in a chamber (not shown) contained within the housing 807 below the structure shown in FIG. 8. The ductwork 23 is connected through an opening 845 in communication with the chamber so that the biological powder material will be extracted through the ductwork 23 for analysis as previously discussed.
[0041] Referring specifically to FIGS. 9 - 11 , a first embodiment of the cutter wheels 803 , 805 shall be discussed. Belt 821 is driven by a motor 843 via a pulley and belt system 844 and a shaft 845 in order to drive individual mailpieces 87 into a nip 846 defined between the cutting edges 847 and 849 of respective cutter wheels 803 , 805 . As belt 821 is driven, so is the cutting wheel 805 which is also mounted on shaft 845 . The overlap of the beveled edges 847 and 849 also causes a rotation of cutter wheel 803 about a shaft 847 . Accordingly, as the mailpieces 87 are fed along the arrow “A” into nip 846 , the bottom of the mailpieces 87 is cut by the interaction of edges 847 , 849 to produce the slots 851 shown in FIG. 11. The ability to produce the slots 851 is made by providing the cutter wheel 803 with notches 855 that are located around the perimeter of the cutter wheel 803 . The notches 855 provide areas 857 of discontinuity in the cutting edge 847 . It is the discontinuities 857 that produce corresponding uncut areas 853 in the mailpiece 87 while each section of the cutting edge 847 between two discontinuities 857 produces a single slot 851 . It is to be noted that in prior art systems, such as that shown in U.S. Pat. No. 3,828,634 (which is hereby incorporated by reference) two cutting wheels are used that are similar to cutter wheel 805 in that the cutting edges extend around the perimeter in an unbroken manner. Thus, in the prior art the result was that an entire bottom edge of the envelope was completely removed opening the entire bottom of the envelope to permit the extraction of the envelope contents.
[0042] In the instant invention, while the slots 51 provide openings through which powder material can be expelled and tested in the detection system 101 , the solid portions 853 remain intact so that the bottom edge 854 of the mailpiece 87 remains in place. Therefore, the contents inside the mailpiece 87 remain contained therein preserving the privacy of the contents and permitting the mailpiece 87 to be further processed for final delivery through the normal mail processing system if it is not contaminated. The plurality of slots 851 provide a greater amount of open area for the powder material to fall through as compared to the opening created at the corner of the mailpiece 87 by the corner snipper 13 .
[0043] [0043]FIG. 12 shows a second embodiment where the cutter wheel 803 has been replaced by the cutter wheel 859 . The cutter wheel 859 is similar to the cutter wheel 803 but further includes vertically extending cutting edges 861 at each side of the notches 855 . Further, a circular urethane wheel 862 has been mounted on shaft 845 directly below cutter wheel 805 to rotate therewith. Accordingly, as the mailpieces 87 pass between a nip 863 the bottom of the mailpiece 87 is cut in a castellated appearance whereby a plurality of segments 865 of the lower edge 864 have been removed to produce a plurality of edge openings 867 . The openings 867 allow any powder material to pass therethrough during the jogging and compression/decompression cycles while the uncut edge segments 869 retain the contents within the mailpiece 87 . Once again, the opened area of the mailpieces 87 are significantly increased over a cut corner opening to allow more opportunity for powder material to escape during the jogging and compression/decompression cycles.
[0044] Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details, and representative devices, shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims. For example, the following are representative examples of such modifications:
[0045] 1. The functions of the controller 821 and power supply 82 can be integrated in the jogger device 97 so that by pressing a single switch the entire jogging and compression/decompression cycles will automatically be executed. Moreover the jogging cycle can be initiated first with the compression/decompression cycles occurring during the jogging cycle.
[0046] 2. The cutter wheel 803 can be modified to have any number of notches 55 and cutting edges 861 in order to vary the number of slots 851 and openings 867 that are made during cutting. Further, different notches can be of a different size to produce slots 851 and openings 867 of different sizes. Additionally, the notch can be sized to produce only a single larger slot 851 or opening 867 .
[0047] 3. The urethane wheel 862 can be made of other materials that provide a proper backing for cutting and which does not damage the cutting edges 861 . Further, the urethane wheel can be integrated on the cutting wheel 860 .
[0048] 4. The cutter wheels of FIGS. 11 and 12 can be used alone separate from the mail opening device 801 for cutting the envelopes in the inventive manner. However, by using the mail opening system in conjunction therewith the initial jogging and the cutting features are integrated within a single unit.
[0049] 5. While two specific air-monitoring tests are shown, only one may be implemented. Further, the invention contemplates any type of testing that can be performed on the expelled air to detect any type of contamination.
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A method for expelling air out of mailpieces includes the steps of creating a stack of the mailpieces; cutting in at least some of the mailpieces; jogging the stack of mailpieces; and subjecting the stack of mailpieces to at least one compression/decompression cycle during the jogging step thereby expelling air out of the at least some of the mailpieces through their corresponding openings. A jogger system incorporates the structure for accomplishing the method.
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BACKGROUND OF THE INVENTION
In certain conventional type pneumatic punch press feeders control circuits have been used to automatically trigger a feed stroke of the feed slide in response the completion of an index stroke thereof and vice versa; however these control circuits utilize limit switches for sensing for the physical presence of the feed slide when the latter has arrived at the end of one or both of said strokes. One of the difficulties associated with this type of sensing arrangement is that the limit switch means must be positionally adjustable for accommodating different positional limits desired for the end of one or both of said strokes as is required where different feed stroke lengths of the feeder are desired. This condition necessitates not only an adjustable mounting for the limit switch type sensing means but also requires that the circuit connections between said adjustable limit switch sensing means and the remaining portions of the control system be flexible or otherwise adjustable so as to accommodate the said adjustable positionment of one or both of said limit switch means. These requirements can cause practical set-up difficulties, particularly where the sensing means must be installed near an extreme longitudinal end of the feeder and loose and cumbersome circuit tubing and/or other control interconnections must be maintained therewith to accommodate the remote and required adjustable positionment of said sensing means.
The principle object of the present invention is to provide a novel pressure sensing arrangement for controlling the automatic reversal of operative movement of the feed slide in a pneumatically operated punch press feeder.
Another object of the invention is to provide an improved pneumatic feeder having control means for controlling the automatic initiation of the next operative stroke of the feed slide thereof whereby no positional adjustment is required for said control means for different feed stroke lengths of said feeder.
Another object of the invention is to provide a pneumatically operated feeder for punch presses and the like having a reciprocable feed slide and wherein the effective fluid pressure in the fluid motor for actuating the feed slide is sensed in order to determine when one operative stroke of the feed slide has been completed and to initiate a signal in response thereto so as to cause initiation of the next operative stroke of said feed slide.
A further object of the invention is to provide a novel single feed slide type pneumatic feeder having an improved control means which when operated is adapted to cause the feed slide to automatically partake of a plurality of successive feed strokes.
Other objects of the invention will become apparent as the disclosure progresses.
SUMMARY OF THE INVENTION
The present invention affords an improved technique for controlling the automatic reversal of motion of a reciprocable punch press feeder slide. Here the completion of one of the operative strokes of the feed slide is sensed not by determining the physical presence of the slide at a particular location at the end of said one operative stroke but rather by sensing for a particular effective elevated fluid pressure in the main fluid motor cylinder, which elevated pressure is normally generated only when the feed slide completes said one operative stroke.
In the pneumatic system described herein a fluid motor is utilized to move the slide in an index direction against the continuous action of a biasing means, such as a mechanical spring, fluid pressure, etc. The effective fluid pressure in said fluid motor during the index stroke does not rise to full line pressure until after the index stroke has been completed, i.e., until the feed slide engages a fixed stop at the end of said index stroke. Thereafter pressure fluid from the supply line will further fill said fluid motor so as to cause the effective operative pressure therein to finally rise to full line or source pressure. A pressure sensing means that is sensitive to this final pressure rise is provided and may be coupled to an associated valve means which is adapted to cause the initiation of the said next feed stroke of the feed slide. By incorporating a pressure sensing means in this manner in the feeder control no limit switch type sensing means and no adjustable tubing or interconnecting means therefor are required. Thus the present pressure sensitive means and associated valve means may be built into the main body of the feeder and never needs positional adjustment for any changes in the feed stroke length set for the feeder.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of a pneumatically operated feeder and the present improved control means therefor.
FIG. 2 is a side elevational view of the main valve plug in somewhat diagrammatic form. (For ease of illustration the O-ring seals for plug 76 have been omitted from this figure.)
FIG. 3 is an end elevational view of the stationary face of the main control valve plug for the present feeder.
FIG. 4 is a graph illustrating the pressure rise in the present main fluid motor means of the feeder during an index stroke of the feed slide thereof.
FIG. 5 includes an axial sectional view showing the details for the pressure sensing means and related valve means as well as for the plug 33a of the present feeder control arrangement, and further schematically illustrates the interconnections between the said sensing and related valve means and the said plug in said control arrangement.
FIG. 6 is a fragmentary cross sectional view taken in the plane of the valve plug groove 110.
FIG. 7 is a fragmentary plan view illustrating the interconnection between two previously separate feed slides so as to form effectively a single feed slide.
DETAILED DESCRIPTION OF THE INVENTION
The disclosure in my copending U.S. patent application Ser. No. 910,840, filed May 30, 1978, for Stock Feeder for Punch Presses and the Like, now U.S. Pat. No. 4,195,761, is incorporated herein by reference and any and all parts herein described and/or illustrated in connection with the specifications and/or the drawings hereof are, unless otherwise indicated, similar to those parts correspondingly numbered, shown and/or described in said copending application.
Referring to FIG. 1 herein there is shown a schematic sketch that corresponds to FIG. 22 of said copending application. Two essential changes are made herein from the feeder control system illustrated in said FIG. 22 as will now be described. The first change, involving the main valve plug 76, is provided in order to cause the two feed slides 20 and 21 to move together as one and in mutual phase relation, i.e. both feed slides partake of a feed stroke together at the same time in response to the positionment of the main valve means in one operative condition thereof, and both slides partake of an index stroke together at the same time when said main valve means is positioned in another operative condition thereof. Thus the two feed slides 20, 21 are caused to move in unison and these slides are fixedly secured to one another by any suitable structural interconnecting means as is diagrammatically indicated at 795 of FIG. 1. As illustrated in FIG. 7 the feed slides may be secured together by a bar 796 that is fastened to said slides by means of screws 797; there being a plurality of holes 798 provided in the bar to permit the same lateral adjustment of said slides 20, 21. Thus the slides 20, 21 herein effectively constitute a single feed slide and hence they are referred to herein as such. In order to produce this movement in unison of the slides the hole or fluid line arrangement in the valve plug 76 is slightly changed as will now be described in connection with FIGS. 2 and 3. Here the plug 76 is drilled so that the valve port 80, FIG. 3, communicates with the groove 110 through lines 80a and 111 as is illustrated in FIG. 2 and in FIG. 6. In similar fashion valve ports 81, 82 and 83 communicate with grooves 126, 156 and 141 respectively as is diagrammatically illustrated at 81a, 82a and 83a, respectively, of FIG. 2. In this manner fluid pressure may, for one operative position of the rotary valve member 86, be directed into valve ports 80 and 83 simultaneously and thus into the head ends of said main fluid motors 32 and 32a so as to move the feed slide 20, 21 in an index direction 301, FIG. 1; both valve ports 81 and 82 at this time being connected to the valve exhaust line 85, FIG. 3, thereby exhausting gripper motors 31 and 31a so that the stock gripping means 30, 30a are in their stock release positions during said index stroke of feed slide 20, 21. When the said rotary valve member 86 is rotationally stepped to its next operative position the reverse pressure conditions will respectively exist at each of the valve ports 80-83 and hence fluid motors 31 and 31a will be charged with pressure fluid while the head ends of the main fluid motors 32 and 32a will be exhausted so as to thereby produce a feed stroke of said feed slide in the feed direction 300, FIG. 1.
If only the above described change in the control arrangement was made then the feed slide would partake of a feed stroke in response to the actuation of control plunger 94 and would, in response to the completion of this feed stroke, move through an index stroke to an indexed position where it would remain until the next actuation of plunger 94. Here there could not be an automatic initiation of a feed stroke by said slide in response to the completion of an index stroke thereof because there is now no means present to sense the arrival of the feed slide at the said indexed position. Where an automatic initiation of a feed stroke in response to the completion of an index stroke is desired in order to make the single feed slide capable of producing a plurality of feed strokes for each cyclic operation of the control plunger 94, there are provided means to sense when the feed slide completes an index stroke and means operated by the sensing means to control the shifting of the main valve to its next operative condition so as to automatically initiate the next feed stroke of said feed slide. The provision of these means involves the second of said two essential changes to be made in the feeder control system or arrangement as will now be described.
Reference will be made first to FIG. 4 which is a graph that illustrates the varying levels of the effective fluid pressure (P) existing in the head ends of the fluid motors 32 and 32a after pressure fluid is first applied thereto; this graph illustrating a pressure condition which is created in said fluid motors at the completion of an index stroke and which may be used to trigger the next feed stroke of the feed slide. It will be noted that with the feed slide in its left hand position as seen in FIG. 1, when pressure fluid is applied to the head ends of said fluid motors 32, 32a the pressure P will rise rapidly from time t0 to time t1. When said pressure reaches P1 at t1 the feed slide (which is continously biased in feed direction 300 by the continuous presence of pressure fluid in the rod ends of said fluid motors 32 and 32a) will commence to move in an index direction 301, FIG. 1, against the said biasing action, and during the index stroke thereof from t1 to t2 the said effective pressure P will rise relatively slowly to P2. After the index stroke of slide 20, 21 is completed at t2 the pressure P rises rapidly again until at time t4 it reaches P4 which is the full supply line pressure that is applied to the feeder. The rapid rise in pressure from P2 to P4 thus indicates the completion of an index stroke and this higher pressure level may be sensed and used to control initiation of the next feed stroke by the feed slide. Accordingly a pressure sensitive valve means is provided which is sensitive to a fluid pressure higher than P2 and near P4, for example P3 shown in FIG. 4. Such a pressure sensitive valve means, schematically illustrated at 800, of FIG. 1, is connected by an input line 801 so as to be controlled by the control line to the head end of the main cylinder 32a. The output line 802 of the pressure sensitive valve means 800 is effectively connected to one input end of the shuttle valve 250; the reverse valve 225a of said FIG. 22 of said copending application and its associated parts and passages being eliminated from the plug 33a for the motor 32a.
With the control arrangement illustrated in FIG. 1 it will be seen that an index stroke of the feed slide may be initiated under the control of the reverse 225 and in response to the completion of a feed stroke thereof in the manner described in said copending application, while a feed stroke thereof may be initiated under the control of the pressure sensitive valve means 800 and in response to the completion of an index stroke by said feed slide. With this bidirectional type of control the feed slide may now be controlled so as to automatically partake of a plurality of feed strokes in response to each cyclic actuation of the control plunger 94 by the press with which the present feeder is to be used.
The details of the construction and arrangement for the pressure sensitive valve means 800 are illustrated in FIG. 5 and will now be described. The plug 33a as previously mentioned has eliminated therefrom the former reverse valve (225a) and the fluid conduit lines immediately associated therewith. Thus the control lines 166 and 150 communicating between the main valve and the plug grooves 47a and 53a control as before the operation of said fluid motors 31a and 32a respectively as is more fully described in said copending application. The output groove 59a of plug 33a communicates not only through lines 245a, 251a, shuttle valve 250 etc. with the power pawl motor 207 as before, but also with the said output line 802, FIGS. 1 and 5, of the pressure sensitive valve means 800. The input control line 801 to the valve means 800 is connected to the said control line 150 for the head end of the fluid motor 32a as is indicated in FIG. 5.
The pressure sensitive valve means 800 includes a normally exhausting three way valve 804 that includes a valve chamber 805 that is adapted to be continuously supplied with pressure fluid from a source 806 through a line 807; the source 806 having a pressure level of P4, i.e. equal to the line pressure that is operatively applied to the feeder. The upper end of the valve chamber 805 is adapted to be closed by a valve disc 810 that is slidably carried on the lower end of a valve stem 811; the disc being provided with a suitable internal O-ring and being retained on the lower end of said stem by any suitable means such as an "E-clip" fastener ring 812 secured to the lower end of said stem 811. The disc 810 is adapted to normally valvingly seat against the shoulder 813 of the valve body 23 so as to prevent pressure fluid from passing from supply chamber 805 into the valve output line 802; the line 802 normally communicating with the valve exhaust line 814 through an intermediate chamber 815 that is coextensive with said chamber 805. When the valve stem 811 is moved downward from its normal FIG. 5 position and relative to disc 810 the shoulder portion 811a thereof will first move past and block the inner end of the exhaust line 814 and thereafter stem shoulder 816 will engage the disc 810 and displace the latter downward so as to allow pressure fluid from chamber 805 to flow into said output line 802. When the valve stem 811 moves upwardly disc 810 will first seat again in its said normal FIG. 5 position and thereafter further upward movement of stem 811 will cause stem shoulder 811a to uncover the inner end of said exhaust line 814 so that pressure fluid may again exhaust from output line 802 to said exhaust line 814. The pressure fluid in chamber 805 with bias stem 811 to its normal upper or FIG. 5 position as determined by engagement of the fastener ring 812 with the lower surface of disc 810.
The above described operation of the three way valve 804 is adapted to be produced by a fluid motor 820, FIG. 5, that is arranged so as to in effect constitute a pressure sensing means. Here the upper end of valve stem 811 is connected to a piston 821 that is axially movably disposed in a cylinder 822; the upper or head end of said cylinder communication with said input control line 801 while the lower or rod end thereof is vented through a line 823. The effective diameter of piston 821 is made only slightly greater than the effective diameter for the valve disc 810 so that the fluid pressure in the upper end of cylinder 822 (which pressure through input line 801 reflects the pressure in the head ends of the fluid motors 32 and 32a) will have to reach a value of at least P3, FIG. 4, before the piston 821 will downwardly unseat the valve disc 810 from its said normal FIG. 5 position. In that the three way valve 804 is thus operated only after an effective fluid pressure of at least P3 has been reached and this pressure as stated in connection with FIG. 4 occurs only after completion of an index stroke, then when said index stroke is completed the valve 804 will be opened as just described so as to initiate an output pressure fluid flow in line 802 which through shuttle valve 250 etc. will operate the power pawl motor 207 so that the main rotary valve member 86 will be stepped to its next operative rotary position and a feed stroke of said feed slide will thus be automatically initiated.
The above described control arrangement can be used to cause the feed slide 20, 21 to repeatedly move through a continuing succession of feed and index strokes, the desired number thereof being determined by the number of effective teeth on the ratchet wheel 92, etc. as explained in said copending application. In this way the present feeder which has effectively only one feed slide, instead of two as provided in the feeder of said copending application, is adapted to automatically execute two or more stock feed strokes in response to each cyclic operation of the control plunger 94 as produced by the motion of the press ram.
The above described arrangement affords a simple, compact and relatively inexpensive pressure sensitive control system for automatically producing a plurality of successive operative strokes by a simple feed slide in response to each cycle of operation of the press.
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A pneumatically operated feeder for punch presses and the like and having a feed slide that is adapted to be moved automatically through successive feed and index strokes. Instead of using a limit switch type device for sensing for the physical presence of the feed slide when the latter has reached the end of an operative stroke thereof, an improved control means is provided to identify the completion of such an operative stroke and to thereby cause said feed slide automatically to initiate its next operative stroke. When pressure fluid is applied to the main fluid motor of the feeder in order to produce say an index stroke of the feed slide the effective fluid pressure in said motor will not normally reach line pressure until after completion of said index stroke. Recognizing this operating condition exists in the feeder pressure sensitive means are provided for so identifying the completion of said index stroke, and valve means responsive to the operation of said pressure sensitive means are provided for causing said feed slide automatically to initiate a feed stroke after completion of said index stroke.
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CROSS REFERENCES TO RELATED APPLICATIONS
[0001] The application claims the benefit of priority of U.S. provisional patent App. No. 62/100,469, filed Jan. 6, 2015, the disclosure of which is incorporated by reference herein.
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
[0002] Not applicable.
BACKGROUND OF THE INVENTION
[0003] The present disclosure generally pertains to exercise and medical rehabilitation apparatus, and more particularly, to resistance tubes used for fitness, exercise, and medical rehabilitation. Some examples of resistance tubes according to the present disclosure may be used for fitness training to tone muscle and increase strength, while others may be used for physical rehabilitation following injury or medical procedures.
[0004] Resistance bands or tubing comes in multiple elasticities to provide a selection of varying weights and sizes. Oftentimes, a handle is permanently affixed on each end of the tubing, and each weight and size of resistance tube has its own set of handles. Additionally, straps or alternative attachment means may be used instead of handles to attach to appendages such as ankles and arms.
[0005] Some handles allow for interchanging of fitness resistance tubing. Some handles include a cutout for resistance tubing and resistance tubing stretched to fit the tubing in place within the handle. Other handles include sliding mechanisms to slide one side of the handle up and down to place the tubing within the housing. However, these systems may not securely and safely hold resistance tubing in place, and may be time consuming and difficult to exchange tubing.
[0006] It is therefore advantageous to have an apparatus, device, and system that enables secure and safe hold of resistance tubing while having a configuration for quick and easy exchange, insertion and removal of resistance tubing. The apparatus, device, and system of the disclosure can be used in multiple fields, including fitness, exercise, and therapy. Other fields include, but are not limited to the medical, construction, and industrial fields.
SUMMARY OF THE INVENTION
[0007] The exercise apparatus of this invention has a handle assembly which releasably engages a resistance tube. The handle assembly has a base with a central tube opening. A first flap or block and a second flap or block are pivotably mounted to the base on opposite sides of the central tube opening. When pivoted towards each other, the blocks compress a resistance tube which is passed through the central opening and secure it in place. The base has two opposed ears which extend upwardly of the central tube opening. A flexible strap is secured to the ears, and extends through a cylindrical tube to which a flexible handle cushion is mounted.
[0008] An alternative embodiment handle assembly has a base with three pairs of blocks pivotably mounted thereto. Each pair of blocks is positioned on opposite sides of a separate tube opening, and is adjustable to secure an end of a resistance tube in place.
[0009] An exercise regimen process is provided by selecting a resistance tube handle having a handle assembly, a base, and a first block and a second block pivotably mounted to the base. At least one resistance tube is selected, followed by positioning the first and second block in an open position. The resistance tube is then inserted through the base and the blocks are closed, followed by pulling the resistance tube into a seated position. A user may then increase and decrease the resistance on the resistance tube handle for a selected exercise regimen.
[0010] Additionally, a user may then increase and decrease the resistance on the resistance tube handle for a selected exercise regimen by interchanging the resistance tube with one of another resistance level, and/or by adding or subtracting resistance tubes where there is a multiple pocket handle base.
[0011] It is an object of the present invention to provide a handle for securely gripping a resistance tube end which is readily released to permit changing of one resistance tube for another.
[0012] Further objects, features and advantages of the invention will be apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The foregoing and other features of the present disclosure will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. Understanding that these drawings depict only several embodiments in accordance with the disclosure and are, therefore, not to be considered limiting of its scope. The disclosure will be described with additional specificity and detail through use of the accompanying drawings.
[0014] FIG. 1 is an exploded isometric view of a single tube apparatus of the present invention.
[0015] FIG. 2 is a cross sectional view of the apparatus of FIG. 1 .
[0016] FIG. 3 is a top plan view of a triple tube apparatus of the present invention, with one set of blocks shown in an open position, one in a partially closed position, and one in a locked position.
[0017] FIG. 4 is a side elevational view of the triple tube apparatus of FIG. 3 .
[0018] FIG. 5 is a side elevational view of two triple tube apparatus of FIG. 3 in use, with resistance tubes extending therebetween.
[0019] FIG. 6 is a cross-sectional view of the apparatus of FIG. 4 showing the resistance tube engaged therein.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be used, and other changes may be made, without departing from the spirit or scope of the subject matter presented here. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the Figures, may be arranged, substituted, combined, and designed in a wide variety of different configurations, all of which are explicitly contemplated and make part of this disclosure.
[0021] Referring to FIGS. 1 and 2 , an apparatus 2 is shown with a handle assembly 4 and tube assembly 6 , which engages a resistance tube 8 in the locked position. The handle assembly 4 includes a grip member or strap 10 , handle tube 12 , and handle cushion 14 . The tube assembly includes a base 16 with protruding ears 17 with openings 18 , 20 which define a pair of strap connectors 18 , 20 . Two pivoting blocks or flaps 22 , 24 are mounted by rods 26 , 28 to the base 16 on opposite sides of a central opening 48 formed in a bottom wall 19 of the base 16 .
[0022] As best shown in FIG. 6 , the resistance tube 8 is of a conventional type having an elastic cylindrical tube 9 having a uniform exterior diameter. The ends of the tubes 8 are made larger in diameter by rigid conical end inserts 11 which are received within the tube 9 and which form the tubes to have an expanded end diameter.
[0023] The base central opening 48 allows the resistance tube 8 to pass through the base 16 . The blocks 22 , 24 are movable by the user's fingers between an open position, in which the wider end of a tube 8 can be passed through the central opening 48 , and a closed position, in which the blocks define an opening which is smaller than the central opening and in which the wider end of the tube is retained on the handle.
[0024] As shown in FIG. 2 the blocks 22 , 24 may be identical, and each block has an inside wall 23 which has a concave inner surface 50 which may define a portion of a cone. Each block inside wall 23 extends between two end walls 25 which are perpendicular to the axis of the rod 26 , 28 about which the block rotates. The base bottom wall 19 has a planar upper surface 29 . Each block end wall 25 has a curved inner cam surface 31 which is spaced from the bottom wall upper surface 29 in the open position, and which engages the bottom wall upper surface in the closed position. This engagement provides some resistance to moving the block to the open position, and thereby assists in retaining the first block in the closed position.
[0025] The base 16 includes a connection means for the rods 26 , 28 comprising shaft openings 21 in the sides of the base 16 and which engage and tightly maintain the position of the rods 26 , 28 . The shaft openings 21 are spaced above and parallel to the base bottom wall upper surface 29 . The rods 26 , 28 pass through openings 27 formed in the end walls 25 of the blocks 22 , 24 . With the rods press fit in the openings 21 of the base, and the blocks mounted on the rods, the blocks 22 , 24 are free to hinge or rotate about the axes defined by the rods 26 , 28 . Each block 22 , 24 has two locking tabs 32 , 34 , shown in FIG. 2 , which project below the block inside walls. The tabs 32 , 34 fit into respective locking recesses 36 , 38 which extend below the upper surface of the base 16 bottom wall. The rotation of the blocks into the closed position extends the locking tabs 32 , 34 into the recesses 36 , 38 , thereby maintaining the blocks 22 , 24 in the closed position. The locking tabs 32 , 34 meet the locking recesses 36 , 38 with a friction or snap fit, and the engagement preferably gives an audible or tactile signal to the user that the block has fully seated in the closed position to assure the user that the handle is now prepared to engage an attached resistance tube 8 .
[0026] The strap 10 is connected to the base 16 at the strap connectors 18 , 22 and passes through the handle tube 12 . The strap 10 is constructed of durable materials suitable for strength, tension and resistance, which are known in the art. The handle tube 12 is constructed of suitable lightweight materials, such as high strength plastics or metals, for durability and strength suitable for high resistance and tension. The handle cushion 14 is constructed of a durable lightweight material with comfort and grip friction, suitable materials are known in the art, including various foams and rubber materials. Antibacterial resistance materials may also be utilized.
[0027] The handle apparatus 2 provides a system for exercising with linear components, such as resistance tubing, while providing efficient options for interchangeability. Such linear accessories may be interchangeable so that only one set of handles is required. The user can change between different sizes and weights of resistance tubing to perform multiple exercises.
[0028] The tube 8 has a semi-conical end 40 for placement between the closed blocks 22 , 24 . The blocks 22 , 24 form an inner semi-conical shaped orifice 42 when in the closed position, with a first edge 44 and second edge 46 , the second edge 46 forming a larger orifice than that formed by the first edge 44 . The handle 2 securely holds the tube 8 . During use, as axial force increases on the tube 8 , the tube 8 is drawn tighter within the handle 2 , to provide for a safe exercise apparatus.
[0029] The base 16 and blocks 22 , 24 may be made of a variety of materials known in the art for lightweight, strong, and high impact performance, such as various extruded plastics and metal alloys. Each set of blocks 22 , 24 may also be referred to as a “pocket” when the blocks 22 , 24 are in the closed position. A multiple “pocket” base 16 having three pockets is shown in FIGS. 3-6 . It is contemplated that a multiple pocket base has two or more pockets.
[0030] As shown on the right of FIG. 3 , the blocks 22 , 24 in an open position allow the semiconical end of a resistance tube to pass through the tube central opening 48 . To give maximum clearance around the central opening 48 in the base 16 , the blocks 22 , 24 , may be provided with a semicircular relief 15 formed in an outside wall 13 which extends between the end walls 25 , as shown in FIG. 1 . The user may select the resistance tube 8 of preference, or a combination of more than one resistance tubes 8 . In the embodiment of FIGS. 3-6 , three sets of blocks 22 , 24 are configured to receive resistance tubes 8 . However, it is contemplated that a single assembly (such as shown in FIG. 1 ), a double assembly (not shown), or an apparatus configured to receive more than three tubes may be constructed. After selecting single or multiple resistance tubes 8 , the user inserts each tube 8 through a central opening 48 in the bottom of the base 16 such that the semi-conical end 40 extends beyond the open blocks 22 , 24 .
[0031] The user then rotates or hinges the blocks 22 , 24 about the rods 26 , 28 to a closed position as shown on the left of FIG. 3 , the locking tabs 32 , 34 meeting the locking recesses 36 , 38 . The tube 8 is then partially pulled through the orifice 42 formed by the closed blocks 22 , 24 to a position wherein the inner semi-conical surfaces 50 of the inside walls of the blocks 22 , 24 meet the semi-conical end of the tube 8 . The tube 8 is then safely seated within the block orifice 42 , at which point the user may choose to add another resistance tube 8 , or begin an exercise regimen using the apparatus 2 . During use, as axial force increases on the tube 8 , the tube 8 is drawn tighter within the handles 2 , to provide for a safe exercise system.
[0032] When the blocks 22 , 24 are in the closed position, the handle assembly 4 can be alternatively viewed as having a semi-circular and semi-conical groove for seating a similarly shaped outer surface of a resistance tube. Alternatively, the closed block pair formation can be viewed as a u-shaped or v-shaped bracket for seating a similarly shaped outer surface of a resistance tube (not shown).
[0033] In an alternative embodiment, the tube end may be semi-pyramidically shaped with three or four edges (not shown) with the block orifice having the corresponding semi-pyramidical shape for receiving the semi-pyramidically shaped resistance tube. Alternatively, the resistance tube end may be a semi wedge-shaped having two or more edges, and the block orifice having a corresponding semi wedge shape for receiving the semi wedge-shaped resistance tube.
[0034] In an alternative embodiment (not shown), more than one block 22 and more than one block 24 are connected in series. By example, an apparatus 2 is configured to receive three exercise tubes in which three blocks 22 hinge together and three blocks 24 hinge together. Alternatively, two sets of blocks 22 can operate together and a third block 22 operates independent of the pair, and two sets of blocks 24 can operate together and a third block 22 operates independent of the pair. Alternatively, any combination of independent and in-series block operation is contemplated for apparatus 2 having two or more block pairings 22 , 24 .
[0035] The triple tube apparatus 2 of FIGS. 3-6 has three sets of blocks 22 , 24 . The blocks in FIG. 3 are shown in open, semi-open, and closed positions. Each of the blocks 22 rotates independent of the other blocks 24 , and each set of blocks 22 , 24 operates independent of the other sets. The user may select resistance tubes of the same or varying resistance. For example, Smart fitness cables available from Prism Fitness Group have a multitude of resistance levels ranging from 10-100 pound resistance levels. A user may select a light, medium, and heavy resistance tube to have a customized exercise regimen. The user may then open the blocks 22 , 24 holding the light resistance tube, remove it, and replace it with a medium resistance tube to increase the overall amount of resistance for the user's particular exercise regimen. Removal and replacement is performed quickly and safely, allowing the user to avoid injury and perform efficient exercise routines.
[0036] The relationship between the resistance tube and the apparatus 2 is indicated in FIG. 6 . The first block 22 pivots about a first axis defined by a first rod 26 , and the second block 24 pivots about a second axis defined by the second rod 28 . The first axis is parallel to the second axis, with the central opening 48 positioned between the first axis and the second axis. The central opening 48 has a maximum dimension R 1 , which in the illustrated embodiment corresponds to the diameter of a circular through hole. This maximum dimension is measured in a plane parallel to a plane extending through the first axis and the second axis, i.e., in the plane of the upper surface 29 of the base.
[0037] The first block 22 and the second block 24 are pivotable between an open position and a closed position. In the closed position, the inside walls 23 of the first block 22 and the second block 24 face each other to define a through hole 42 extending between the first block and the second block and communicating with the base central opening 48 . The through hole 42 defined between the first block inside wall and the second block inside wall has a second minimum dimension R 2 measured in a plane parallel to the plane extending through the first axis and the second axis, i.e, in a plane directly above the upper surface 29 of the base. In the illustrated embodiment, the through opening approximates a converging frustoconical surface, which converges to its narrowest point directly above the upper surface of the base. This second minimum dimension is less than the first maximum dimension, such that a resistance tube having a main diameter R 3 and a larger expanded end diameter R 4 can extend through the base central opening 48 when the first block 22 and second block 24 are in the open position, and the resistance tube 8 expanded end diameter is retained against passing through the central opening when the first block and the second block are in the closed position. In other words, the main diameter R 3 is less than R 1 , and the expanded end diameter R 4 of the resistance tube is greater than R 2 .
[0038] Various alternatives are contemplated as being within the scope of the following claims, particularly pointing out and distinctly claiming a subject matter regarded as the invention.
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A handle assembly base has a central tube opening for receiving an elastic resistance tube with an expanded end diameter. A first block and a second block are pivotably mounted to the base on opposite sides of the central tube opening. When pivoted towards each other, the blocks define a reduced area opening through which the expanded end diameter of the resistance tube cannot pass, thereby retaining the resistance tube to the base. The base has two opposed ears which extend upwardly of the central tube opening. A flexible strap is secured to the ears, and extends through a cylindrical tube to which a flexible handle cushion is mounted to provide a grip for the user to engage the handle.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a fiber suitable for components for automotive interior manufactured by thermoforming etc.
[0003] 2. Description of the Related Art
[0004] Conventionally, components for car interior made of a fabric are attached to steel plates in a car body such as ceiling, floor, seats and part of doors. Since the installation sites of the components for interior has various asperities, it is necessary to form the components for interior into a shape conforming to the asperities of the installation sites by thermoforming etc.
[0005] Moreover, for example, polyethylene terephthalate having a melting point of 200 degrees C. is used for the fiber forming the component for a car interior, such that the fiber does not melt at a temperature (e.g., approx. 180 degrees C.) upon the thermoforming.
RELATED ART DOCUMENTS
[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. H11-48221
SUMMARY OF THE INVENTION
Problems that the Invention Tries to Solve
[0007] Since the polyethylene terephthalate has relatively high specific gravity of 1.3 to 1.4, a component for interior made of polyethylene having low specific gravity of 0.9 is examined. However, the melting point of the polyethylene is 120 degrees C., and it melts in the heat treatment at approx. 180 degrees C. upon the thermoforming. Therefore, it is an objective of the present invention to provide a fiber suitable for forming a component for automotive interior, and a component for automotive interior formed by the fiber. The fiber having a lower specific gravity in comparison with the conventional fiber, and maintaining a structure thereof even in the heat treatment upon the thermoforming without changing its texture.
Means for Solving the Problems
[0008] In order to solve the above deficiencies, the present invention provides a film-protected fiber for automotive interior, comprising a core fiber, comprising a material having a relatively low melting point, and a protective film, comprising a material having a relatively high melting point, and surrounding a periphery of the core fiber, wherein when thermoforming the film-protected fiber into a shape conforming to an inner part of an automotive body at a temperature sufficient for melting the core fiber, the original structure of the fiber can be maintained due to the protective film.
[0009] Moreover, the present invention provides the film-protected fiber for automotive interior, wherein specific gravity of the core fiber is relatively small in comparison with specific gravity of the protective film, and wherein the material of the core fiber is polyethylene or polypropylene.
[0010] Moreover, the present invention provides the film-protected fiber for automotive interior, wherein the above polyethylene or polypropylene is a plant-based material. Moreover, the present invention provides the film-protected fiber for automotive interior, wherein the material of the protective film is polyethylene terephthalate or nylon. Moreover, the present invention provides the film-protected fiber for automotive interior, wherein a weight proportion of the core fiber to an entirety of the fiber is 30% to 70%.
[0011] Furthermore, the present invention provides an automotive interior component that is formed by overlapping a fabric, comprising the film-protected fiber for automotive interior, and a shape-maintaining material, comprising a material having a comparable melting point to that of the material of the core fiber of the film-protected fiber for automotive interior.
Effects of the Invention
[0012] According to the present invention having the above configuration, it is possible to obtain a fiber for components of automotive interior, having a smaller specific gravity in comparison with the conventional fiber, and when thermoforming the fiber into a shape conforming to an inner part of an automotive body at a temperature sufficient for melting the core fiber, the original structure of the fiber can be maintained due to a protective film.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a cross-sectional diagram showing an example of a structure of a film-protected fiber for automotive interior of a first embodiment.
[0014] FIG. 2 is a conceptual diagram explaining an example of protection of a core fiber in thermoforming regarding the film-protected fiber for automotive interior of the first embodiment.
[0015] FIG. 3 is a diagram showing an example of a structure of a component for automotive interior of a second embodiment.
[0016] FIG. 4 is a conceptual diagram explaining an example of thermoforming regarding the film-protected fiber for automotive interior of the second embodiment.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Embodiments of the present invention will be described hereinbelow with reference to the drawings. The present invention is not to be limited to the above embodiments and able to be embodied in various forms without departing from the scope thereof.
[0018] Note that the first embodiment will mainly describe Claims 1 to 6 . Moreover, the second embodiment will mainly describe Claim 7 .
First Embodiment
[0019] <Concept of First Embodiment>
[0020] A film-protected fiber for automotive interior of a first embodiment of the present invention has a structure having the specific gravity approx. 1.0, where a core fiber is polyethylene, and polyethylene terephthalate as a protective fiber is arranged outside the core.
[0021] When thermoforming non-woven fabric or woven fabric made of the above fiber of the present invention into a shape conforming to an inner part of an automotive body, even if the polyethylene, which has a relatively low melting point and is arranged in the core of the fiber, melts, it is protected by the polyethylene terephthalate, which has a relatively high melting point and is arranged outside the core fiber, thereby preventing from flowing out. After that, the melted core fiber is cooled and sets to the same shape as that before the thermoforming, thereby maintaining the structure of the fiber.
[0022] <Configuration of First Embodiment>
[0023] FIG. 1 is a cross-sectional diagram showing an example of a structure of a film-protected fiber for automotive interior of the first embodiment. As shown in FIG. 1 , a ‘film-protected fiber for automotive interior’ ( 0100 ) of the first embodiment comprises a ‘core fiber’ ( 0101 ) made of a material having a relatively low melting point in comparison with the protective film, and a ‘protective film’ ( 0102 ) made of a material having a relatively high melting point in comparison with the core fiber.
[0024] Moreover, the ‘core fiber’ ( 0101 ) has a relatively small specific gravity in comparison with that of the protective film. Specifically, examples of the materials of the ‘core fiber’ include various polyethylene or polypropylene. Moreover, the polyethylene or polypropylene may be a plant-based material. This enables reduction of environmental load caused by fiber manufacturing etc.
[0025] Moreover, the weight proportion of the core fiber to an entirety of the fiber may be 30% to 70%. Here, when the proportion of the core fiber to the entirety of the fiber is 30%, it is possible to reduce the specific gravity of the fiber with maximum effect of maintaining the structure of the fiber in the thermoforming. Meanwhile, when the proportion of the core fiber to the entirety of the fiber is 70%, it is possible to maximally reduce the specific gravity of the fiber with the effect of maintaining the structure of the fiber in the thermoforming.
[0026] Examples of materials of the ‘protective film’ include polyethylene terephthalate or nylon. Moreover, in addition to the above, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate may be used.
[0027] Moreover, as to a diameter of the film-protected fiber for automotive interior of the first embodiment with the above configuration, for example, a fiber, whose diameter is 2 to 30 micrometers, may be used.
[0028] Moreover, as to methods for manufacturing the above fiber, having the core fiber and protective film surrounding the core fiber, the following methods may be used. For example, a first spinning solution is generated by thermal melting of fiber component of the core fiber, and a second spinning solution is generated by thermal melting of fiber component of the protective film. Then, the first and second spinning solutions are delivered from a spinneret having a double concentric ring structure, thereby carrying out spinning.
[0029] Moreover, the fiber component of the core fiber is dissolved by solvent, thereby generating the first spinning solution, and the first spinning solution is delivered from the spinneret, thereby carrying out spinning. After that, the second spinning solution generated from the fiber component of the protective film is used for coating.
[0030] When carrying out molding press of the fabric made of the film-protected fiber for automotive interior of the first embodiment having the above configuration by heat and pressure treatment at approx. 180 degrees C. as shown in FIG. 2( a ), although the core fiber made of, for example, plant polyethylene, having a melting point of 120 degrees C., melts, the protective film made of, for example, polyethylene terephthalate, having a melting point of 200 degrees C., does not melt. Therefore, the melted core fiber never flows out due to the protective film. Then, as shown in FIG. 2( b ), the melted core fiber is cooled and sets again in the protective film, thereby enabling thermoforming without changing the structure of the fiber.
[0031] Hereinafter, descriptions of forming and thermoforming process of the fabric for automotive interior utilizing the fiber of the first embodiment are provided. Specifically, for example, as to a fabric for flooring of a car, cotton having the protective film made of polyethylene terephthalate and the core fiber made of plant polyethylene of the first embodiment are blended, and carding and punching are carried out to the cotton. Then, the fabric is latex coated and dried at 150 to 160 degrees C., and simultaneous treatment of polyethylene lamination and cooling is carried out, thereby manufacturing the fabric (non-woven fabric) for automotive interior.
[0032] Subsequently, the non-woven fabric thus manufactured is heated at 150 to 180 degrees C. to form the fiber into a shape conforming to an inner part of the automotive body, and then, cooling and press-forming are carried out. Even after these treatments, since the plant polyethylene as the core fiber does not flow out due to the protective film, the non-woven fabric made of the fiber of the first embodiment can be firmly formed without changing its texture.
[0033] Moreover, as to a fabric for the ceiling of a car, similarly, cotton of the first embodiment is blended, and carding and punching are carried out to the cotton. Then, the fabric is latex coated and dried at 150 to 160 degrees C., thereby manufacturing the fabric (non-woven fabric). After that, as after-mentioned in a second embodiment, the fabric is stuck to the shape-maintaining material after-mentioned in the second embodiment with an adhesive, and for example, heated at 130 to 180 degrees C., thereby carrying out the forming treatment of this fabric and the shape-maintaining material. Even after these treatments, since the plant polyethylene as the core fiber does not flow out due to the protective film, the fabric can be firmly formed without changing its texture.
[0034] As described above, by utilizing the fiber of the first embodiment, it is possible to maintain the structure of the fiber in the forming of the non-woven fabric and in the thermoforming so that the fiber can be firmly formed into the shape conforming to the inner part of the automotive body.
[0035] <Brief Description of Effects of First Embodiment>
[0036] As described above, by utilizing the fiber of the first embodiment, it is possible to reduce the specific gravity in comparison with the conventional fiber, and even when thermoforming the fiber into a shape conforming to an inner part of an automotive body at a temperature sufficient for melting the core fiber, the original structure of the fiber can be maintained due to the protective film without changing its texture.
Second Embodiment
[0037] <Concept of Second Embodiment>
[0038] The second embodiment is an automotive interior component formed by overlapping the fabric made of the film-protected fiber for automotive interior of the first embodiment and the shape-maintaining material, and the material has a comparable melting point to the material of the core fiber. By hot pressing from the fabric side upon the thermoforming, as described above, it is possible to keep the texture of the fabric, and to prevent the shape-maintaining material from flowing out, thereby maintaining its shape.
[0039] <Configuration of Second Embodiment>
[0040] FIG. 3 is a diagram showing an example of a structure of a component for automotive interior of a second embodiment. As shown in FIG. 3 , a ‘component for automotive interior’ ( 0300 ) of the second embodiment comprises a ‘fabric’ ( 0301 ) made of the film-protected fiber for automotive interior of the first embodiment, and a ‘shape-maintaining material’ ( 0302 ) overlapped with the fabric.
[0041] Moreover, the ‘fabric’ ( 0301 ) may be a non-woven fabric or a tufted carpet as long as it is made of the film-protected fiber for automotive interior of the first embodiment.
[0042] The ‘shape-maintaining material’ ( 0302 ) has a lower melting point than the material of the protective film of the film-protected fiber for automotive interior. Examples of the material include a component formed by glass fiber impregnated with polypropylene resin or a component formed by mixture of rigid urethane and non-woven glass fabric.
[0043] Moreover, the fabric and the shape-maintaining material may be overlapped, for example, by sticking with an adhesive.
[0044] FIG. 4 is a conceptual diagram explaining an example of thermoforming regarding the film-protected fiber for automotive interior of the second embodiment. As shown in FIG. 4 , the component for automotive interior ( 0400 ) is formed by overlapping a fabric ( 0401 ) made of the film-protected fiber for automotive interior of the first embodiment, formed by the protective film of polyethylene terephthalate (melting point of 200 degrees C.) and the core fiber of polyethylene (melting point of 120 degrees C.), and a shape-maintaining material ( 0402 ) made of the polyethylene same as the core fiber.
[0045] Moreover, when thermoforming the component for automotive interior by heating the fabric side, for example, at 180 degrees C., the fabric in the upper side deforms without melting nor without changing its texture as described above. Moreover, by the component for automotive interior of the second embodiment, it is possible to suitably heat the shape-maintaining material through the fabric. Therefore, the shape-maintaining material can deform without melting and maintain the shape thereof.
[0046] <Brief Description of Effects of Second Embodiment>
[0047] As described above, according to the second embodiment, it is possible to provide the automotive interior component that can keep its surficial texture even in the thermoforming, and that can firmly maintain its shape by the shape-maintaining material.
DESCRIPTION OF REFERENCE NUMERALS
[0048] 0100 . Film-protected fiber for automotive interior
[0049] 0101 . Core fiber
[0050] 0102 . Protective film
[0051] 0300 . Component for automotive interior
[0052] 0301 . Fabric
[0053] 0302 . Shape-maintaining material
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Provided is a fiber which is equal to conventional fibers in heat resistance and which, even when heated during thermoforming, maintains the shape thereof and suffers no change in texture. This fiber is suitable for forming an interior automotive member. Also provided is an interior automotive member formed from the fiber. The film-protected fiber comprises: a core fiber constituted of a material having a relatively low melting point; and a protective film which is constituted of a material having a relatively high melting point and with which the periphery of the core fiber is surrounded. Even when the film-protected fiber is thermoformed, at a temperature sufficient for melting the core fiber, into a shape conforming to, e.g., an inner part of an automotive body, the original structure of the fiber can be maintained due to the protective film.
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BACKGROUND OF THE INVENTION
The present invention relates to double-hung window assemblies and particularly to such windows having pivotally mounted sashes.
Pivoting sashes have become quite common in double-hung window assemblies as they have the usual advantage of being able to be raised and lowered as well as the special advantage of being tiltable to make cleaning of the window pane easier. Attention is directed to U.S. Pat. No. 4,581,850 which illustrates a double hung pivotal window assembly. While the structure of this patent and other similar commercial double hung pivoting assemblies have overcome many of the disadvantages of the prior window assemblies, several disadvantages still exist.
For example, a problem still arises where, during manufacturing and installation of the conventional assemblies, a "belly band" or similar elastic constriction must be used to maintain the assembly together so that the assembly remains truly square when installed in the window opening. Such "belly bands" while necessary, are a particular nuisance during transport and storage, since they must be kept in place during and after installation.
Another disadvantage occurs as a result of the inability to mount the sash to the sash frame, so that binding and warping of the sash frame are prevented. Still another problem arises out of the inability of locking the pivot sash in an open position so as to remove any stress on the pivot joint caused by its weight.
It is the object of the present invention to provide an improved pivotal sash assembly to overcome the aforementioned disadvantages as well to provide numerous other advantages will be obvious to persons skilled in the art from contemplation of the following disclosure.
SUMMARY OF THE INVENTION
According to the present invention, a sash retaining and pivot assembly is provided which engages cooperatively with the sash weight slide. The pivot assembly is provided with a connecting T-Bar having wings which fit together with the slide, within the jamb frame channel so as to hold the jamb frame and sashes in a unitary manner. Further, the pivot assembly and the weight slide cooperate to effect locking of the sash in pivoted position.
The sash retaining pivot assembly of the present invention, when used within a window constructed with a "tilt in to clean" feature, will provide integral locking of the window sash within the window frame at the pivot location. While still allowing removal of the sash at a 90 degree tilt, the self aligning locking mechanism will engage and secure the sash within the frame at approximately a 60 degree tilt.
A window incorporating the sash retaining pivot assembly will provide advantages during window installation, as well as after window installation. During window installation, the sash retaining pivot assembly will retain alignment of the sash with the frame without the use of a "belly band". This will allow for easier shimming and squaring of the window within the opening.
After the window is installed within the opening, the sash retaining pivot assembly will continue to benefit the window construction by maintaining the alignment of frame to sash, which will provide the window with a constant and proper spacing between frame and sash.
BRIEF DESCRIPTION OF THE DRAWINGS
In The Drawings:
FIG. 1 is a fragmentary front elevational view of a double hung window assembly of a type to which the present invention is applied;
FIG. 2 is a sectional view along lines 2--2 of FIG. 1 showing the sash retaining assembly and weight slide assembly connecting the sash and jamb frame;
FIG. 3 is a fragmentary perspective view of the bottom corner of the window sash of FIG. 1 showing the sash retaining assembly extending from the sash;
FIG. 4 is an enlarged view of the sash retaining assembly removed from the sash and the mounting bracket for securing the same to the sash;
FIG. 5A is a bottom plan view of the unitary embodiment of the T-Bar and guide of the sash retaining assembly;
FIG. 5B is an end view of the T-Bar guide of FIG. 5.
FIG. 6A is a detailed view of the T-Bar looking at its end;
FIG. 6B is a side elevational detail of the T-Bar;
FIG. 6C is a top plan view in detail of the T-Bar;
FIG. 7 is a perspective view of the pivot shoe showing the T-Bar inserted therein;
FIG. 8A is a plan view of the pivot shoe;
FIG. 8B is a sectional view along line 8--8 of FIG. 8A;
FIG. 9A is an elevational view of the rotary cam used in the slide; and
FIG. 9B is a plan view of the rotary cam.
DESCRIPTION OF THE INVENTION
The present invention is depicted in connection with double-hung windows of the type illustrated in FIG. 1, by the numeral 10. Such windows include a rectangular main jamb frame 12, forced of elongated channel sections, and a pair of sashes 14 and 16. The sashes have opposing vertical stiles 18, a top and bottom header 20 and a glass pane 22. The frame 12 and sashes 14 and 16 can be formed of metal although strong rigid plastic is currently preferred because of its thermal properties, ease of fabrication, strength and decorative durability. In general, the form of the sashes and jamb will follow conventional structure and form. Those features not of a conventional nature will be described herein and reference can be made to the aforementioned patent and others as well as commercial windows for the conventional features.
According to the present invention, the frame 12 as seen in FIG. 2 comprises an elongated continuous extrusion having in cross-section a inner sash channel 24 and an outer sash channel 26, each of which is cross sectionally C-shaped to provide an inwardly directed flange 28 defining a continuous slot 30. The exterior surfaces of the flanges 28 provide straight, smooth guides 32 against which the stiles 18 of the associated sash slide. If desired, as seen in FIG. 3 a pad of fabric, rubber or the like forming a slidable seal member 34 is adhered to the stile 18 to seal the space between the sash and the frame.
The sashes 14 and 16 are not only independently movable up and down within the frame, but are pivotal with respect to the frame to facilitate cleaning, maintenance and replacement of parts. To this end, the opposite sides of each sash is provided with a sash retaining assembly 36, fixed to the sash, and a slidable pivot-shoe assembly 38 located in the associated frame channel. Although only one such pair of retaining assemblies 36 and pivot shoe assemblies 38 are shown, it will be understood that each sash has two pairs, one pair on each of the right and left sides of the sash.
As seen in FIGS. 3 and 4, the sash retaining assembly 36 comprises an enlarged box-like body 40 from the forward end of Which extends a T-Bar 42. The body 40 and T-Bar 42 may be unitarily molded or cast as depicted in FIGS. 5A-5B or may be formed of two parts that frictionally fit together using the T-Bar of FIGS. 6A-6C. Preferably, as seen in detail, the T-Bar is separate so that it may be adjusted longitudinally. T-Bar 42 has a generally rectangular cross-section with a longitudinally directed groove 44 on its upper side forming a keyed front end 46. Set back from the forward end of the T-Bar and extending perpendicular to its axis are a pair of oppositely extending lateral wings 48 having arcuate extreme edges 50 and a back surface 52 which has beveled ramps 53 on at least one edge. At least one hole 54 is formed in bottom of the body 40 between the two larger sides.
Returning to FIGS. 3 and 4 the body 40 of the assembly 36 is inserted within a receiving hole 56 formed in the stile or header of the sash (14, 16) and held fixedly in place by a bolt 58 so the arms 48 are spaced predeterminately from the surface of the stile 18 or the associated header 20. The body 40 may be shaped and provided with enlarged embossment to such walls 60, etc. so that when so inserted, will not twist within the receiving hole 56.
The slidable pivot shoe assembly 38, as shown in FIG. 7 consists of a flat molded plastic slide 64 of substantially rectangular shape and of width and thickness so as to be closely and slidably received in channels 24, 26. The upper approximately two thirds of the slide 64 is provided with an enlarged window 66 bounded at its upper edge with a number of slots and fingers 68. The slots 68 and window 66 cooperate to receive and hold the ends of any sash balance and weighted cords (not shown).
Turning now to FIGS. 8A and 8B, the remaining portion of the slide 64 is formed with a web 70 and both front and back faces 72 and 74 respectively. Front face 72 is cut back to form a recessed area. Passing through the slide 64 is a central bearing hole 76. Extending from the web 70 are a pair of brake shoes or flaps 78 located on either side of the central bearing hole 76. Each retaining flap 78 is integrally attached at its interior ends 80 to the web 70 at the front of slide 64, while the open end of each flap 78 is freely extending and enlarged to form a depending stop 82 so that the flap is resiliently liftable when an object is inserted between the flap and the recessed front face. In the preferred embodiment of the instant invention, the back face 74 is formed with a recessed portion 86, so that the wings 48 of T-Bar 42 can be fitted and rotated within the dimensional envelope of pivot shoe assembly 38, allowing the wings 48 of T-Bar 42 to be positioned within the same channel 24, 26 with the pivot shoe.
Set within the bearing hole 76 from the front recessed face 72 is a rotary cam 88 (FIGS. 9A and 9B) having a cylindrical hub 90 in which is formed a rectangular bore 92, of sufficient size to permit entry of the extending forward end 46 of the T-Bar 42. An elongated key 94 extends the length of the bore 92 so as to mate with the keyway 46 in the T-Bar 42 insuring only proper entry of the T-Bar into the cam. A semi-circular flange 96, extends radially from the front end of cylinder hub 90. The flange having beveled lateral wings 100 are being integrally formed at one side of the front end of cylindrical hub 90 while the opposite side has a straight edge 98.
The cam 88 is set within the central bearing hole 76 so that the arcuate flange 96 lies interiorly in the recessed area of front face 72 and the wings 100 lie between recessed front face 72 and the flaps 78. In this manner the straight edge 98 lies between the flaps 78 against the stops 82 in a resiliently locked position. Upon exertion of rotary force on the cam 88, the beveled wings 100 of the flange 96 wedge beneath the stops 82 of flaps 78 forcing the flaps 78 away from front face 72 allowing the cam to rotate until the opposing square corners of the straight edge 98 abut against stops 82. The locked position and the rotated position define the extreme positions in which the sash is pivoted.
Mounting of the sash within the frame should now be clear. The pivot shoe assembly 38 is prepared i.e., the slide 64 and the cam 88 is assembled. Thereafter, the forward keyway 46 of the T-Bar 42 is inserted in the rectangular bore 92 of the cam 88 and the window sash with the entire retaining assembly placed between the opposed jamb frame 12. In making this placement, the pivot shoe assembly 38 and the lateral wings 48 of the T-Bar 40 are placed within the appropriate slot 30 in the jamb frame 12, as seen in FIG. 2, so that the pivot shoe assembly is slidable therein. Since the back face 74 of the slide 64 is cut back to form a recess, both the slide 64 and the lateral wings 48 of the T-Bar sit between the inner surface of the flange 28 and the bottom wall of the channel 30, holding the sashes and the jamb frame 12 square with each other. Attachment of the bolt 58 in this condition joins the retaining assembly 36, including the T-Bar 42 to the sash and attaches the entire unit to the jamb frame in a unitary manner for transport and storage. As a result, the entire window assembly becomes a single unit obviating the need for the conventional "belly band" or other strapping.
Because the flaps 78 pivot only in response to the turning of the cam from the back side of the slide 64, the slide may move freely along the length of the channel until the beveled edge 98 is forced beneath the flaps 78. When this occurs, the flaps frictionally engage the bottom wall of the channel and acts like a shoe brake arresting movement of the slide and thus of the window. Because the T-Bars are firmly fixed to the sash and the wings 48 fit behind the flanges 28 of the channels, the frames are captivated to the sash, and cannot belly out i.e., bow or warp, during or after installation, nor during storage and transportation when there is no jambs support for them.
In operation, the installed double hung window assembly of the present invention functions in the generally conventional manner, in that the sashes are freely movable upward and downward against their balance weights. When desired, either one of the sashes may be pivoted inwardly causing the retaining assembly 36 to be rotated resulting in rotation of T-Bar 42, and thus, the cam 88. As cam 88 rotates, its flange 96 causes the flaps 78 to pivot outwardly, forcing them to press with great frictional force against the inside wall of the channel 30 until this force overcomes any desire for the sash to move upwardly or downwardly or to further pivot. Thus, in this tilted position, the pivot window is held fast and securely against inadvertent movement. It may be washed or repaired etc., without fear of change.
It will be clear that the slide and T-Bar can be assembled with either the upper or lower sash, and merely by adjusting the extension of the T-Bar from the stile will fit into either the front or rear channel of the jamb frame 12. In either situation the pivot assembly will function in the same way. Likewise, the pivot assembly is obviously applicable to windows with horizontally slidable/rotatable sashes.
Various modifications, changes and embodiments have been disclosed herein. Others will be obvious to those skilled in the art. Accordingly, it is to be understood that the foregoing disclosure is illustrative only and not limiting of the invention.
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A tiltable window sash mounted in a channelled window frame having a T-shaped bar projecting from the sash into the window frame channel, with the wings of the T-Bar engaging the inside of the window frame channel so that sash to frame alignment is maintained. The bar simultaneously provides a pivotal axis about which the sash is tilted. The bar engages a sliding pivot shoe located in the window frame channel to provide a guide for sliding of the sash. The pivot shoe has a cam operated dial acting brake; the cam is coupled to the T-shaped bar, so that the sash is tilted; the cam operates a first brake preventing sliding of the tilted sash, and when a predetermined angle of sash tilt is reached, a second brake is operated by the cam preventing further tilting of the sash, thus supporting the sash in a tilted position.
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REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of U.S. Provisional Patent Application No. 60/441,759, filed Jan. 23, 2003, whose disclosure is hereby incorporated by reference in its entirety into the present disclosure.
STATEMENT OF GOVERNMENT INTEREST
[[0002]] This work was supported in part by NSF grants CCR-9701915, CCR-9702466, CCR-9705594, CCR-9811929, EIA-9972881, CCR-9988361, and EIA-0080124; by DARPA/ITO under AFRL contract F29601-00-K-0182. The government has certain rights in the invention.
FIELD OF THE INVENTION
[0003] The present invention is directed to microprocessors and more particularly to microprocessors having multiple clock domains.
DESCRIPTION OF RELATED ART
[0004] The continuing push for higher microprocessor performance has led to unprecedented increases in clock frequencies in recent years. While the Pentium III microprocessor broke the 1 GHz barrier in 2000, the Pentium IV is currently shipping at 2 GHz. At the same time, due to issues of reliability and performance, wire dimensions have been scaled in successive process generations more conservatively than transistor dimensions. The result of these frequency and dimensional trends is that microprocessor clock speeds have become increasingly limited by wire delays, so much so that some of the more recent microprocessors, e.g., the Pentium IV [14], have pipeline stages solely dedicated to moving signals across the chip. Furthermore, a growing challenge in future systems will be to distribute the clock across a progressively larger die to increasing numbers of latches while meeting a decreasing clock skew budget. The inevitable conclusion reached by industrial researchers is that in order to continue the current pace of clock frequency increases, microprocessor designers will eventually be forced to abandon singly-clocked globally synchronous systems in favor of some form of asynchrony [8, 24].
[0005] Although purely asynchronous systems have the potential for higher performance and lower power compared to their synchronous counterparts, major corporations have been reluctant to fully migrate to asynchronous design methodologies. Two major reasons for this reluctance are the immaturity of asynchronous design tools relative to those in the synchronous domain, and the cost and risk of moving away from the mature design infrastructures that have been successfully used to create many generations of microprocessor products. Yet many existing synchronous designs do incorporate a limited amount of asynchrony. For example, several multiprocessor systems run the memory bus off of a different clock than the processor core in order to allow a single system to accommodate processors of different frequencies. In such dual clock domain systems, the logic in each of the two clock domains is designed using conventional synchronous design methodologies. Well-known and highly-reliable techniques are used to synchronize communication between the two domains, albeit at the cost of extra delay.
[0006] An additional trend due to the wire scaling dilemma is to replace microarchitectural techniques requiring long global wires with alternatives requiring only local wiring. This approach improves both clock frequency and the scalability of the design in future process generations. For example, in several microprocessors including the Alpha 21164 and 21264 [11, 20] and the UltraSPARC III [17], the use of global wires to stall early pipeline stages has been replaced by the use of replay traps that cancel instructions and restart the pipeline. Although flushing the pipeline in this manner requires additional cycles for reloading, it results in a higher clock frequency and more scalable implementation due to the elimination of global wires. The designers of the UltraSPARC III fully embraced this approach by creating six functional blocks that run relatively independently of one another, with most long wires eliminated between units [17].
[0007] Reference numerals in brackets refer to the following references:
[1] D. H. Albonesi. Dynamic IPC/Clock Rate Optimization. Proceedings of the 25 th International Symposium on Computer Architecture, pages 282-292, June 1998. [2] F. Bellosa. OS-Directed Throttling of Processor Activity for Dynamic Power Management. Technical Report TR-14-3-99, C.S. Dept., University of Erlangen, Germany, June 1999. [3] F. Bellosa. The Benefits of Event-Driven Energy Accounting in Power-Sensitive Systems. In Proceedings of the 9 th ACM SIGOPS European Workshop, September 2000. [4] L. Benini, A. Bogliolo, S. Cavallucci, and B. Ricco. Monitoring System Activity for OS-directed Dynamic Power Management. In Proceedings of the International Symposium on Low - Power Electronics and Design, August 1998. [5] D. Brooks, V. Tiwari, and M. Martonosi. Wattch: A Frame-work for Architectural-Level Power Analysis and Optimizations. In Proceedings of the 27 th International Symposium on Computer Architecture, June 2000. [6] D. Burger and T. Austin. The Simplescalar Tool Set, Version 2.0. Technical Report CS-TR-97-1342, University of Wisconsin, Madison, Wis., June 1997. [7] J. Casmira and D. Grunwald. Dynamic Instruction Scheduling Slack. In Proceedings of the Kool Chips Workshop, in conjunction with the 33 rd International Symposium on Microarchitecture ( MICRO -33), December 2000. [8] B. Chappell. The fine art of IC design. IEEE Spectrum, 36(7):30-34, July 1999. [9] B. R. Childers, H. Tang, and R. Melhem. Adapting Processor Supply Voltage to Instruction-Level Parallelism. In Proceedings of the Kool Chips Workshop, in conjunction with the 33 rd International Symposium on Microarchitecture ( MICRO -33), December 2000. [10] L. T. Clark. Circuit Design of XScale™ Microprocessors. In 2001 Symposium on VLSI Circuits, Short Course on Physical Design for Low - Power and High - Performance Microprocessor Circuits. IEEE Solid-State Circuits Society, June 2001. [11] J. H. Edmondson et al. Internal Organization of the Alpha 21164, a 300-MHz 64-bit Quad-issue CMOS RISC Microprocessor. Digital Technical Journal, 7(1):119-135, 1995. Special Edition. [12] B. Fields, S. Rubin, and R. Bodik. Focusing Processor Policies via Critical-Path Prediction. In Proceedings of the 28 th International Symposium on Computer Architecture, July 2001. [13] M. Fleischmann. Longrun™ power management. Technical report, Transmeta Corporation, January, 2001. [14] P. N. Glaskowsky. Pentium 4 (Partially) Previewed. Microprocessor Report, 14(8):1,11-13, August 2000. [15] K. Govil, E. Chang, and H. Wasserman. Comparing Algorithms for Dynamic Speed-Setting of a Low-Power CPU. In Proceedings of the 1 st ACM/IEEE International Conference on Mobile Computing and Networking, pages 13-25, November 1995. [16] T. R. Halfhill. Transmeta breaks x86 low-power barrier. Microprocessor Report, 14(2), February 2000. [17] T. Horel and G. Lauterbach. UltraSPARC III: Designing Third-Generation 64-Bit Performance. IEEE Micro, 19(3):73-85, May/June 1999. [18] C.-H. Hsu, U. Kremer, and M. Hsiao. Compiler-Directed Dynamic Frequency and Voltage Scaling. In Proceedings of the Workshop on Power - Aware Computer Systems, in conjunction with the 9 th International Conference on Architectural Support for Programming Languages and Operating Systems (ASPLOS-IX), November 2000. [19] C. J. Hughes, J. Srinivasan, and S. V. Adve. Saving Energy with Architectural and Frequency Adaptations for Multimedia Applications. In Proceedings of the 34 th Annual International Symposium on Microarchitecture (MICRO-34), December 2001.
[0027] [20] R. E. Kessler, E. J. McLellan, and D. A. Webb. The Alpha 21264 Microprocessor Architecture. In Proceedings of the International Conference on Computer Design, pages 90-95, Austin, Tex., October 1998. IEEE Computer Society.
[21] S. Leibson. XScale (StrongArm-2) Muscles In. Microprocessor Report, 14(9):7-12, September 2000. [22] T. Li and C. Ding. Instruction Balance, Energy Consumption and Program Performance. Technical Report UR-CS-TR-739, Computer Science Dept., University of Rochester, December 2000. Revised February 2001. [23] D. Marculescu. On the Use of Microarchitecture-Driven Dynamic Voltage Scaling. In Proceedings of the Workshop on Complexity - Effective Design, in conjunction with the 27 th International Symposium on Computer Architecture, June 2000. [24] D. Matzke. Will Physical Scalability Sabotage Performance Gains? IEEE Computer, 30(9):37-39, September 1997. [25] T. Pering, T. Burd, and R. W. Brodersen. The Simulation and Evaluation of Dynamic Voltage Scaling Algorithms. In Proceedings of the International Symposium on Low - Power Electronics and Design, August 1998. [26] R. Pyreddy and G. Tyson. Evaluating Design Tradeoffs in Dual Speed Pipelines. In Proceedings of the Workshop on Complexity - Effective Design, in conjunction with the 28 th International Symposium on Computer Architecture, June 2001. [27] L. F. G. Sarmenta, G. A. Pratt, and S. A. Ward. Rational Clocking. In Proceedings of the International Conference on Computer Design, Austin, Tex., October 1995. [28] A. E. Sjogren and C. J. Myers. Interfacing Synchronous and Asynchronous Modules Within A High-Speed Pipeline. In Proceedings of the 17 th Conference on Advanced Research in VLSI, pages 47-61, Ann Arbor, Mich., September 1997. [29] G. Sohi. Instruction Issue Logic for High-Performance Interruptible, Multiple Functional Unit, Pipelined Computers. ACM Transactions on Computer Systems, 39(3):349-359, March 1990. [30] TSMC Corp. TSMC Technology Roadmap, July 2001. [31] M. Weiser, A. Demers, B. Welch, and S. Shenker. Scheduling for Reduced CPU Energy. In Proceedings of the 1 st USENIX Symposium on Operating Systems Design and Implementation, November 1994.
SUMMARY OF THE INVENTION
[0039] It is an object of the invention to overcome the above-noted deficiencies of the prior art. It is another object of the invention to provide an approach that allows for aggressive future frequency increases, maintains a synchronous design methodology, and exploits the trend towards making functional blocks more autonomous.
[0040] To achieve the above and other objects, the present invention is directed to a multiple clock domain (MCD) microarchitecture, which uses a globally-asynchronous, locally-synchronous (GALS) clocking style. In an MCD microprocessor each functional block operates with a separately generated clock, and synchronizing circuits ensure reliable inter-domain communication. Thus, fully synchronous design practices are used in the design of each domain. Although the inter-domain synchronization increases the number of clock cycles required to run a given application, an MCD microprocessor affords a number of potential advantages over a singly clocked design:
The global clock distribution network is greatly simplified, requiring only the distribution of the externally generated clock to the local Phase Lock Loop (PLL) in each domain.
[0042] The independence of each local domain clock implies no global clock skew requirement, permitting potentially higher frequencies within each domain and greater scalability in future process generations.
The designers of each domain are no longer constrained by the speeds of critical paths in other domains, affording them greater freedom in each domain to optimize the tradeoffs among clock speed, latency, and the exploitation of application parallelism via complex hardware structures. Using separate voltage inputs, external voltage regulators, and controllable clock frequency circuits in each clock domain allows for finer grained dynamic voltage and frequency scaling, and thus lower energy, than can be achieved with single clock, single-core-voltage systems. With the ability to dynamically resize structures and alter the clock speed in each domain, the IPC/clock rate tradeoff can be tailored to application characteristics within each individual domain [1], thereby improving both performance and energy efficiency.
[0046] In the present application, we describe an initial implementation of an MCD microprocessor that is a straightforward extension of a singly-clocked synchronous dynamic superscalar design. By accurately modeling inter-domain synchronization, we characterize the performance and energy costs of the required synchronization circuitry. We then explore the potential benefits of per-domain dynamic voltage and frequency scaling. Our results demonstrate a 20% average improvement in energy-delay product for a set of benchmarks that includes both compute and memory-bound applications. Unlike rate-based multimedia applications, these benchmarks have not traditionally been candidates for voltage and frequency scaling.
[0047] We disclose a multiple clock domain (MCD) microarchitecture, which uses a globally-asynchronous, locally-synchronous (GALS) clocking style along with dynamic voltage and frequency scaling in order to maximize performance and energy efficiency for a given application. Our design uses existing queue structures in a superscalar processor core to isolate the different clock domains in a way that minimizes the need for inter-domain synchronization.
[0048] Performance results for applications drawn from standard benchmark suites suggest that the division of the processor into multiple domains incurs an average baseline performance cost of less than 4%. At the same time, by scaling frequency and voltage in different domains dynamically and independently, we can achieve an average improvement in energy-delay product of nearly 20%. By contrast, global voltage scaling to achieve comparable performance degradation in a singly clocked microprocessor achieves an average energy-delay improvement of only 3%.
[0049] Our current analysis uses an off-line algorithm to determine the points in the program at which different domains should change frequency and voltage. Variations within the scope of the invention include effective on-line algorithms, including approaches for effective scaling of the front end, as well as the ability to deliver tunable on-chip voltage and frequency with low latency.
[0050] The following paper describes the invention and is hereby incorporated by reference in its entirety into the present disclosure: Semeraro et al, “Energy-Efficient Processor Design Using Multiple Clock Domains with Dynamic Voltage and Frequency Scaling,” High Performance Computer Architecture (HPCA), Feb. 2, 2002.
BRIEF DESCRIPTION OF THE DRAWINGS
[0051] A preferred embodiment of the present invention will be disclosed in detail with reference to the drawings, in which:
[0052] FIG. 1 shows a multiple clock domain processor block diagram;
[0053] FIG. 2 shows a queue structure;
[0054] FIG. 3 shows a full flag;
[0055] FIG. 4 shows synchronization timing;
[0056] FIG. 5 shows performance degradation results;
[0057] FIG. 6 shows energy saving results;
[0058] FIG. 7 shows energy-delay improvement results;
[0059] FIGS. 8A and 8B show frequency changes for art generated by our off-line algorithm for the dynamic 1% configuration for Transmeta and XScale, respectively; and
[0060] FIGS. 9A and 9B show summary statistics for intervals chosen by the off-line tool for the dynamic 5% configuration for Transmeta and XScale reconfiguration data, respectively.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0061] Matzke has estimated that as technology scales down to a 0.1 μm feature size, only 16% of the die will be reachable within a single clock cycle [24]. Assuming a chip multiprocessor with two processors per die, each processor would need to have a minimum of three equal-size clock domains. The preferred embodiment uses four domains, one of which includes the L 2 cache, so that domains may vary somewhat in size and still be covered by a single clock. In effect, we treat the main memory interface as a fifth clock domain, external to the MCD processor, and always running at full speed.
[0062] In choosing the boundaries between domains, we attempted to identify points where (a) there already existed a queue structure that served to decouple different pipeline functions, or (b) there was relatively little inter-function communication. Our four chosen domains, shown in the architecture 100 of FIG. 1 , comprise the front end 110 (including instruction cache 112 , fetch unit 114 , and branch prediction, rename, and dispatch 116 ); integer issue/execute 120 (including integer issue queue 122 and integer arithmetic logic units and register file 124 ); floating point issue/execute 130 (including floating point issue queue 132 and floating point arithmetic logic units and register file 134 ); and load/store issue/execute 140 (including load/store unit 142 , L 1 D-cache 144 , and L 2 cache 146 in communication with the main memory interface 150 as well as with the cache 112 of the front end 110 ). Although we were initially concerned about the performance impact of implementing separate load/store and integer domains, we discovered that the additional synchronization penalty did not significantly degrade performance. Furthermore, because we discovered no energy savings from decoupling instruction fetch from rename/dispatch, we combined these regions into a single fetch/rename/dispatch domain to eliminate their inter-domain synchronization overhead. Finally, execution units of the same type (e.g., integer units) were combined into a single domain to avoid the high cost of synchronizing the bypass and register file datapaths among these units. As a result of these divisions, there were no explicit changes to the pipeline organization of the machine. We also believe that these divisions would result in a physically realizable floorplan for an MCD processor.
[0063] The primary disadvantage of an MCD processor is the performance overhead due to inter-domain synchronization. In this section, we discuss the circuitry required to perform this synchronization. We discuss how to model its performance cost below.
[0064] Some synchronization schemes restrict the phase relationship and relative frequencies of the clocks, thereby eliminating the need for hardware arbitration [27]. Unfortunately, these schemes impose significant restrictions on the possible choices of frequencies. In addition, the need to control the phase relationships of the clocks means that global clock synchronization is required. Our design specifically recognizes the overhead associated with independent clocks with no known phase relationship. We believe this overhead to be unavoidable in an MCD processor: one of the motivating factors for the design is the recognition that traditional global clock distribution will become increasingly difficult in the future.
[0065] The issue queues in the integer, floating point, and load/store domains (the Load/Store Queue within the Load/Store Unit), together with the Reorder Buffer (ROB) in the front end domain, serve to decouple the front and back ends of a conventional processor. Choosing these queues as inter-domain synchronization points has the advantage of hiding the synchronization cost whenever the queue is neither full nor empty (as described below).
[0066] The general queue structure that we use for inter-domain communication is shown in FIG. 2 . The assertion of the Full flag indicates to the producer that it can no longer write to the queue until the flag is deasserted ({overscore (Full)}), while the Empty flag when asserted indicates that there is no valid data for the consumer to read from the queue. The consumer waits until Empty is deasserted before reading again.
[0067] The use of a full handshake protocol for this interface requires that the producer/consumer check the Full/Empty flag after every operation in order to avoid queue overruns on writes or reads from an empty queue. This requirement significantly slows down the interface, thereby degrading performance. Rather, we assume that the Full and Empty flags are generated far enough in advance such that writes and reads can occur every clock cycle without over- or underflowing the queue. In other words, the Full flag is generated early enough such that a burst of writes every cycle will terminate (due to recognition by the producer of the assertion of the Full flag) just as the last remaining queue entry has been written. An analogous situation exists for the consumer side of the queue, although our particular queues are different in this regard as we discuss later. Note that this scheme may result in underutilization of the queue under particular conditions. For example, if the write that initiates assertion of the Full flag is at the end of a burst, then there will be empty but unusable entries in the queue (because the Full flag will have been asserted) the next time the producer has data to write into the queue.
[0068] In order to avoid underutilization of the queues, we assume extra queue entries to buffer writes under worst-case conditions so that the original number of queue entries can be fully utilized. In the MCD design, the worst-case situation occurs when the producer is operating at the maximum frequency (max_freq) and the consumer at the minimum frequency (min_req). An additional complication occurs due to the need to compare queue head and tail pointers from different clock domains in order to generate the Full and Empty flags. Under these conditions, and assuming an additional cycle for the producer to recognize the Full signal, (max_freq/min_freq)+1 additional entries are required. Our results do not account for the performance advantage nor the energy cost of these additional entries.
[0069] Even with completely independent clocks for each interface, the queue structure is able to operate at full speed for both reading and writing under certain conditions. This concurrency requires a dual-ported SRAM structure where simultaneous read and write cycles are allowed to different SRAM cells. As long as the interfaces are designed to adhere to the protocol associated with the Full and Empty flags, the queue structure does not need to support simultaneous read and write access to the same SRAM cell. As long as the queue is not full (as described above) the producer can continue to write data on every rising edge of Clock w ( FIG. 3 ). Similarly, so long as the queue is not empty, the consumer can continue reading on every rising edge of Clock r . Therefore, both interfaces operate at full speed so long as the queue is partially full, although newly written entries may not be recognized by the consumer until after a synchronization period. Once the queue becomes full, the queue state of {overscore (Full)} can only result from data being read out of the queue on the read interface. When this event occurs, the queue pointer in the read domain must get synchronized with the write domain clock (Clock w ) in order to dessert Full. A similar desynchronization delay occurs with the generation of the {overscore (Empty)} condition due to a write to an empty queue.
[0070] Many of the queues that we use as synchronization points have a different interface than that described above. For the issue queue for example, each entry has Valid and Ready flags that the scheduler uses to determine whether an entry should be read (issued). The scheduler by design will never issue more than the number of valid and ready entries in the queue. Note, however, that due to synchronization, there is a delay before the scheduler sees newly written queue data. The delay associated with crossing a clock domain interface is a function of the following:
The synchronization time of the clock arbitration circuit, T S , which represents the minimum time required between the source and destination clocks in order for the signal to be successfully latched at the destination. We assume the arbitration and synchronization circuits developed by Sjogren and Myers [28] that detect whether the source and destination clock edges are sufficiently far apart (at minimum, T S ) such that a source-generated signal can be successfully clocked at the destination. The destination clock is enabled only under these conditions. We assume a T S of 30% of the period of the highest frequency. The ratio of the frequencies of the interface clocks. The relative phases of the interface clocks.
[0074] This delay can best be understood by examining a timing diagram ( FIG. 4 ), which shows source clock F 1 and destination clock F 2 . Consider the case when the queue is initially empty. Data is written into the queue on the rising edge of F 1 (edge 1 ). Data can be read out of the queue as early as the next rising edge of F 2 . If T≦T S , the earliest that the data can be read is one F 2 period later (edge 3 ). This extra delay represents one source of performance degradation due to synchronization. The value of T is determined by the relative frequency and phases of F 1 and F 2 , as well as the relative jitter of the clock sources, and may well change over time. The cost of synchronization is controlled by the relationship between T and T S , and to a lesser degree by the magnitude of T S . The analogous situation exists when the queue is Full, replacing Empty with Full, edge 1 with edge 2 , and edge 3 with edge 4 in the above discussion.
[0075] Our simulator, described below, accurately accounts for the inter-domain overhead.
[0076] Our simulation testbed is based on the SimpleScalar toolset [6] with the Wattch [5] power estimation extensions. The original SimpleScalar model supports out of order execution using a centralized Register Update Unit (RUU) [29]. We have modified this structure to more closely model the microarchitecture of the Alpha 21264 microprocessor [20]. Specifically, we split the RUU into separate reorder buffer (ROB), issue queue, and physical register file structures. A summary of our simulation parameters appears in Table 1.
TABLE I Architectural parameters for simulated processor Branch predictor: comb. of bimodal and 2-level PAg Level1 1024 entries, history 10: Level2 1024 entries; Bimodal predictor size 1024; Combining predictor size 4096; BTB 4096 sets, 2-way Branch Mispredict Penalty 7 Decode Width 4 Issue Width 6 Retire Width 11 L1 Data Cache 64 KB, 2-way set associative L1 Instruction Cache 64 KB, 2-way set associative L2 Unified Cache 1MB, direct mapped L1 cache latency 2 cycles L2 cache latency 12 cycles Integer ALUs 4 + 1 mult/div unit Floating-Point ALUs 2 + 1 mult/div/sqrt unit Integer Issue Queue Size 20 entries Floating-Point Issue Queue Size 15 entries Load/Store Queue Size 64 Physical Register File Size 72 integer, 72 floating-point Reorder Buffer Size 80
[0077] We selected a mix of compute-bound, memory-bound, and multimedia applications from the MediaBench, Olden, and SPEC2000 benchmark suites. Table 2 specifies the benchmarks used along with the window of instructions simulated. We show combined statistics for the encode and decode phases of adpcm, epic, and g721, and for the mipmap, osdemo, and texgen phases of mesa.
TABLE 2 Benchmarks Bench- Simulation window mark Suite Datasets (instructions) adpcm Media- ref entire program epic Bench ref entire program g721 ref 0-200 M mesa ref entire program em3d Olden 4 K nodes, arity 10 70 M-119 M health 4 levels, 1 K iters 80 M-127 M mst 1 K nodes entire program 199 M power ref 0-200 M treeadd 20 levels, 1 iter entire program 189 M tsp ref 0-200 M bzip2 SPEC input.source 1000 M-1100 M gcc 2000 Int 166.i 1000 M-1100 M mcf ref 1000 M-1100 M parser ref 1000 M-1100 M art SPEC ref 300 M-400 M swim 2000 FP ref 1000 M-1100 M
[0078] For the baseline processor, we assume a 1 GHz clock and 1.2 V supply voltage, based on that projected for the forth-coming CL010LP TSMC low-power 0.1 μm process [30]. For configurations with dynamic voltage and frequency scaling, we assume 32 frequency points spanning a linear range from 1 GHz down to 250 MHz. Corresponding to these frequency points is a linear voltage range from 1.2 V down to 0.65 V. In Wattch, we simulate the effect of a 1.2-0.65 V voltage range by using a range of 2.0-1.0833 V because Wattch assumes a supply voltage of 2.0 V. Our voltage range is tighter than that of XScale (1.65-0.75 V), reflecting the compression of voltage ranges in future generations as supply voltages continue to be scaled aggressively relative to threshold voltages. In addition, the full frequency range is twice that of the full voltage range. As we demonstrate below, these factors limit the amount of power savings that can be achieved with conventional dynamic voltage and frequency scaling.
[0079] We assume two models for dynamic voltage and frequency scaling: an XScale model and a Transmeta model, both of which are based on published information from the respective companies [10, 13]. For both of these models, we assume that the frequency change can be initiated immediately when transitioning to a lower frequency and voltage, while the desired voltage must be reached first before increasing frequency. For the Transmeta model, we assume a total of 32 separate voltage steps, at 28.6 mV intervals, with a voltage adjustment time of 20 μs per step. Frequency changes require the PLL to re-lock. Until it does the domain remains idle. We model the PLL as a normally distributed locking circuit with a mean time of 15 μs and a range of 10-20 μs. For the XScale model, we assume that frequency changes occur as soon as the voltage changes, i.e., as the voltage is changed, the frequency is changed accordingly. There is no penalty due to a domain being idle waiting for the PLL: circuits execute through the change. To approximate a smooth transition, we use 320 steps of 2.86 mV each, with 0.1718 μs required to transition from one step to the next. Traversing the entire voltage range requires 640 μs under the Transmeta model and 55 μs under the XScale model.
[0080] Processor reconfiguration decisions (choices of times, frequencies, and voltages) could in principle be made in hardware, software, or some combination of the two, using information gathered from static analysis, on-line statistics, or feedback-based profiling. For the purposes of the current study we have attempted to identify the energy savings that might be achieved with good quality control algorithms, without necessarily determining what those algorithms should look like. More concretely, we employ an off-line tool that analyzes a trace collected during a full-speed run of an application in an attempt to determine the minimum frequencies and voltages that could have been used by various domains during various parts of the run without significantly increasing execution time. A list of these frequencies and voltages—and the times they should be applied—is then fed back into our processor simulator in the course of a second, dynamic scaling run, to obtain accurate estimates of energy and performance.
[0081] It is unclear whether this experimental methodology will overestimate or underestimate the benefits that might be achieved by realistic on-line control algorithms: our feedback-based system can in principle use future knowledge, but it is not provably optimal: a good on-line strategy might conceivably do better. What the methodology does provide is an existence proof: with the frequencies and voltages chosen by our analysis tool one could expect to realize the energy savings described below.
[0082] The two subsections that follow describe, respectively, our multiple clock domain simulator and the analysis tool used to choose reconfiguration points.
[0083] The disadvantage of multiple clock domains is that data generated in one domain and needed in another must cross a domain boundary, potentially incurring synchronization costs as described in Section 2. In order to accurately model these costs, we account for the fact that the clocks driving each domain are independent by modeling independent jitter, the variation in the clock, on a cycle-by-cycle basis. Our model assumes a normal distribution of jitter with a mean of zero. The standard deviation is 1110 ps, consisting of an external Phase Lock Loop (PLL) jitter of 100 ps (based on a survey of available ICs) and lops due to the internal PLL. These values assume a 1 GHz on-chip clock generated from a common external 100 MHz clock source. Despite the common use of the external clock, because the local clock sources are independent, the clock skew within individual domains is not a factor when calculating inter-domain penalties.
[0084] Our simulator tracks the relationships among all of the domain clocks on a cycle-by-cycle basis based on their scaling factors and jitter values. Initially, all the clocks are randomized in terms of their starting times. To determine the time of the next clock pulse in a domain, the domain cycle time is added to the starting time, and the jitter for that cycle (which may be a positive or negative value) is obtained from the distribution and added to this sum. By performing this calculation for all domains on a cycle by cycle basis, the relationship between all clock edges is tracked. In this way, we can accurately account for synchronization costs due to violations of the T>T S relationship or to inter-domain clock rate differences.
[0085] For all configurations, we assume that all circuits are clock gated when not in use. We do not currently estimate the power savings or clock frequency advantage (due to reduced skew) from the absence of a conventional global clock distribution tree that supplies a low-skew clock to all chip latches.
[0086] To select the times and values for dynamic scaling in a given application, our reconfiguration tool begins by running the application on the simulator, at maximum speed. During this initial run we collect a trace of all primitive events (temporally contiguous operations performed on behalf of a single instruction by hardware in a single clock domain), and of the functional and data dependences among these events. For example, a memory instruction (load/store) is broken down into five events: fetch, dispatch, address calculation, memory access, and commit. Data dependences link these events in temporal order. Functional dependences link each event to previous and subsequent events (in different instructions) that use the same hardware units. Additional functional dependences capture the limited size of structures such as the fetch queue, issue queues, and reorder buffer. In the fetch queue, for example, event n depends on event n-k, where k is the size of the queue.
[0087] We use our trace information to construct a dependence directed acyclic graph (DAG) for each 50K cycle interval. (The length of this interval is chosen to be the maximum for which the DAG will fit in cache on our simulation servers.) Once the DAG has been constructed, we proceed through two additional analysis phases. The first phase uses the DAG as input, and confines its work to a single interval. Its purpose is to “stretch” (scale) individual events that are not on the application's critical execution path, as if they could, on an instruction-by-instruction basis, be run at a lower frequency. The final phase uses summary statistics from the first phase in order to cluster intervals into larger contiguous periods of time, with a uniform clock rate for each.
[0088] Whenever an event in the dependence DAG has two or more incoming arcs, it is possible—in fact likely—that one arc will constitute the critical path and that the others will have “slack”. This slack indicates that the previous operation completed earlier than necessary. If all of the outgoing arcs of an event have slack, then we have an opportunity (assuming zero-cost scaling) to save energy by performing the event at a lower frequency and voltage. With each event in the DAG we associate a power factor whose initial value is based on the relative power consumption of the corresponding clock domain, as determined by parameters in Wattch. When we stretch an event we scale its power factor accordingly. Calculations are made on a relative basis, on the assumption that energy is proportional to the square of the clock frequency. The stretching phase of our reconfiguration tool uses a “shaker” algorithm to distribute slack and scale edges as uniformly as possible. Since SimpleScalar, like any real processor, executes events as soon as possible subject to dependences and hazards, slack always appears at the ends of non-critical paths in the original execution trace. The shaker algorithm thus begins at the end of its 50K cycle interval and works backwards through the DAG. When it encounters an event whose outgoing edges all have slack, the shaker checks to see whether the power factor of the event exceeds a certain threshold, originally set to be slightly below the maximum power of any event in the graph. If so (this is a high-power event), the shaker scales the event until either it consumes all the available slack or its power factor drops below the current threshold. If any slack remains, the event is moved later in time, so that as much slack as possible is moved to its incoming edges. When it reaches the beginning of the DAG, the shaker reverses direction, reduces its power threshold by a small amount, and makes a new pass forward through the DAG, scaling high-power events and moving slack to outgoing edges. It repeats this process, alternately passing forward and backward over the DAG, reducing its power threshold each time, until all available slack has been consumed, or until all events adjacent to slack edges have been scaled down to one quarter of their original frequency. When it completes its work for a given 50K cycle interval, the shaker constructs a summary histogram for each clock domain. Each histogram indicates, for each of the 320 frequency steps in the XScale model (being the maximum of the number of steps for the two models), the total number of cycles for the events in the domain and interval that have been scaled to run at or near that frequency.
[0089] Unfortunately, it turns out to be difficult to capture the behavior of the front end in terms of dependences among events. Unlike the time between, say, the beginning and the end of an add in the floating-point domain, the time between fetch and dispatch is not a constant number of cycles. In addition, experiments with manually selected reconfiguration points suggested that scaling of the front was seldom as beneficial as scaling of other domains. As a result, we have chosen to run the front at a steady 1 GHz, and to apply the shaker algorithm to events in the other 3 domains only. Since the front end typically accounts for 20% of the total chip energy, this choice implies that any energy improvements we may obtain must come from the remaining 80%. Future attempts to address the front end may yield greater savings than are reported here.
[0090] The final, clustering phase of our off-line analysis tool recognizes that frequencies cannot change on an instantaneous, instruction-by-instruction basis. It also allows for a certain amount of performance degradation. Using the histograms generated by the shaker, we calculate, for each clock domain and interval, the minimum frequency f that would permit the domain to complete its work with no more than d percent time dilation, where d is a parameter to the analysis. More specifically, we choose a frequency (from among 32 possible values for Transmeta and from among 320 possible values for XScale) such that the sum, over all events in higher bins of the histogram, of the extra time required to execute those events at the chosen frequency is less than or equal to d percent of the length of the interval. This calculation is by necessity approximate. It ignores ILP within domains: it assumes that the dilations of separate events in the same domain will have a cumulative effect. At the same time it ignores most dependences across domains: it assumes that the dilations of events in different domains will be independent. As an exception to this rule, we add the events of the load/store domain into the histogram of the integer domain. This special case ensures that effective address computations occur quickly when memory activity is high. For most applications the overall time dilation estimate turns out to be reasonably accurate: FIGS. 5-7 and 8 A- 9 B show performance degradation (with respect to the MCD baseline) that is roughly in keeping with d.
[0091] Whereas the shaker algorithm assumes that reconfiguration is instantaneous and free, the clustering algorithm must model reconfiguration times and costs. For each adjacent pair of intervals for a given domain, it merges histograms on a bin-by-bin basis and calculates the minimum frequency that would allow us to run the larger, combined interval at a single frequency. For the Transmeta power model we require that the time dilation of too-slow events together with the time required to reconfigure at interval boundaries not exceed d percent of total execution time. Since it eliminates one reconfiguration, merging intervals under the Transmeta model often allows us to run the combined interval at a lower frequency and voltage, thereby saving energy. Most mergers under the XScale model occur when adjacent intervals have identical or nearly identical target frequencies. The clustering algorithm continues to perform mergers, recursively, so long as it is profitable from an energy standpoint to do so.
[0092] When it is done performing mergers, the clustering algorithm calculates the times at which reconfiguration must begin in order to reach target frequencies and voltages at target times. If reconfiguration is not possible, for example, because of a large swing in frequency that would take longer (because of the time to reduce or increase voltage) than the available interval, it is avoided. Since transitions in the Transmeta model take 20 μs per voltage level, this results in the inability to accommodate short intervals with a large frequency variance. The algorithm completes its work by writing a log file that specifies times at which the application could profitably have requested changes in the frequencies and voltages of various domains. This file is then read by the processor simulator during a second, dynamic configuration run.
[0093] In this section, we compare the performance, energy, and energy-delay product of the MCD microarchitecture to that of a conventional singly clocked system. The base-line configuration is a single clock 1 GHz Alpha 21264-like system with no dynamic voltage or frequency scaling. The baseline MCD configuration is split into four clock domains as described in Section 2 but with the frequency of all clocks statically set at 1 GHz. This configuration serves to quantify the performance and energy cost of inter-domain synchronization. The dynamic 1% and dynamic 5% configurations are identical to baseline MCD except that they support dynamic voltage and frequency scaling within each clock domain. For the dynamic 1% case the clustering phase of our off-line reconfiguration tool uses a target of 1% performance degradation (beyond that of baseline MCD); for the dynamic 5% case it uses a target of 5%. Finally, the global configuration models the baseline configuration with the addition of dynamic scaling of its single voltage and frequency, and serves to quantify the benefits of multiple clock domains.
[0094] The frequency for the global case is set so as to incur an overall performance degradation equal to that of the dynamic 5% configuration, and its voltage is correspondingly reduced. The energy savings of global is calculated by running each application under SimpleScalar and Wattch using the reduced frequency and voltage values. This approach permits the energy savings of the MCD approach to be compared to that of conventional voltage and frequency scaling for the same level of performance degradation. We performed a sanity check of the energy results of the global configuration by comparing the Wattch results against a simple calculation of the energy of the baseline configuration scaled relative to the square of the voltage ratios and found the results to agree to within 2%.
[0095] FIGS. 5, 6 , and 7 display the performance degradation, energy savings, and change in energy×delay of the base-base-line MCD, dynamic 1%, dynamic 5%, and global configurations with respect to the baseline configuration, under the XScale model of voltage and frequency scaling. The Transmeta model produced far less promising results than the XScale model. Because of the roughly 15 μs required to re-lock the PLL under the Transmeta model, reconfigurations are profitable much more rarely than they are under the XScale model, and energy improvements are much less. We will return to a comparison of the Transmeta and XScale models after discussing the XScale results in more detail.
[0096] The baseline MCD design, which simply uses multiple clock domains with no voltage or frequency scaling, shows an average performance degradation of less than 4%, with average energy cost of 1.5%. The resulting impact on energy-delay product approaches −10% for adpcm and −5% overall. Note that any overheads introduced by the algorithms add directly to this baseline MCD overhead. For instance, the average dynamic 5% performance overhead is almost 10% or roughly what might be expected given the target degradation of 5% above the base-line MCD.
[0097] Our second observation is that the overall energy savings of the global approach is similar to its performance degradation, and averages less than 12% across the sixteen benchmarks. This result is somewhat counterintuitive, since when both frequency and voltage are reduced linearly by the same percentage, performance drops linearly with frequency, yet energy drops quadratically with voltage. Recall, however, that in our model a four-fold change in frequency (from 1 GHz down to 250 MHz) results in a less than two-fold change in voltage (from 1.2 V down to 0.65 V, modeled as 2.0 V to 1.0833 V in Wattch). As discussed above, this difference is due to the compression of voltage ranges relative to frequency ranges in successive process generations, as voltages are scaled down relative to threshold voltage, and frequencies are scaled up. The slope of the voltage curve has become much less steep than that of the frequency curve, greatly diminishing the quadratic effect on energy of a voltage reduction.
[0098] The MCD approaches, by contrast, achieve significant energy and energy×delay improvements with respect to the baseline configuration, with a comparatively minor overall performance degradation. For example, the dynamic 5% configuration achieves an average overall energy reduction of 27% and an energy×delay improvement of almost 20% relative to the baseline configuration, while incurring a performance degradation of less than 10% across the sixteen benchmarks under the XScale model. The dynamic 1% algorithm, which tries to more strictly cap the performance degradation at the expense of energy savings, trades off a significant energy savings to achieve this goal, resulting in an energy×delay improvement of roughly 13%. Even so, this still far exceeds the 3% energy×delay improvement obtained with the global approach.
[0099] In several cases the opportunity to hide latency behind cache misses allows actual performance degradation to be significantly less than what one might expect from the frequencies chosen by the dynamic algorithm. In particular, the slack associated with L 1 data cache misses often allows our reconfiguration tool to scale the integer and floating-point domains without significantly impacting overall performance (due to the fact that the available ILP is not sufficient to completely hide the miss latency), even when the utilization for these domains is high. The load/store domain, of course, must continue to operate at a high frequency in order to service the misses as quickly as possible, since the second level cache is in the same domain (unless we have a lot of level-two cache misses as well). The impact of misses can be seen in gcc (dynamic 1%), where the cache miss rate is high (12.5%) and the average frequency of the integer domain drops to approximately 920 MHz, but total performance degradation is less than 1%.
[0100] By contrast, branch mispredictions do not provide an opportunity for dynamic scaling: the dependence chain developed to resolve a branch precludes significant frequency reductions in the integer domain, and sometimes in the load/store domain as well. Applications that experience a high branch mispredict rate are likely to show performance degradation in accordance with frequency slowdown. This effect can be seen in swim, where the energy savings barely exceeds the performance degradation. (Here the floating point domain must also remain at a high frequency because of high utilization.)
[0101] The dynamic algorithm performs poorest with respect to global voltage scaling in g721. This is an integer benchmark with a well balanced instruction mix, high utilization of the integer and load/store domains, a low cache miss rate, a low branch misprediction rate, and high baseline MCD overheads. Its IPC is relatively high (above 2), and the integer and load/store domains must run near maximum speed in order to sustain this. The floating point domain can of course be scaled back to 250 MHz, but because of the high activity levels in the other domains, the resulting energy savings is a smaller fraction of total processor energy than it is in most of the other integer applications.
[0102] Comparing FIGS. 5-7 with corresponding results (not shown here) under the Transmeta scaling model, we found that the XScale model enables us to achieve significantly higher energy savings for a given level of performance degradation. The reasons for this result are illustrated in FIGS. 8A and 8B , which display the frequency settings chosen by our reconfiguration tool for a 30 ms interval of the art benchmark, with a target performance degradation of 1%. In comparing FIGS. 8A and 8B , note that under the XScale model ( FIG. 8B ) we are able both to make a larger number of frequency changes and to make those changes over a wider range of frequencies. In particular, while art is a floating-point intensive application, there are many instruction intervals during which we can safely scale back the floating-point domain. Because of its 10-20 μs PLL relock penalty, the Transmeta model does not allow us to capture this comparatively short-term behavior.
[0103] FIGS. 9A and 9B present summary statistics for the intervals chosen by our off-line reconfiguration tool in all 16 applications, under both the Transmeta and XScale models. Those figures show summary statistics for intervals chosen by the off-line tool for the dynamic 5% configuration for Transmeta and XScale reconfiguration data, respectively. Solid bars indicate, for the integer, load-store, and floating-point domains, the number of reconfigurations requested per 1 million instructions. Points above the bars indicate the average frequencies chosen for those domains. “Error bars”, where shown, indicate the range of dynamic frequencies for the domain. While the average frequencies chosen for the integer, load-store, and floating-point domains are similar in the two graphs, the total number of reconfigurations is much lower under the Transmeta model, and the frequency ranges are narrower.
[0104] FIGS. 8A through 9B all illustrate the value of using different frequencies in different clock domains: by controlling these frequencies independently we can maintain the required frequency in domains that are critical to performance, while aggressively scaling those domains that are less performance-critical. The floating-point domain in particular can be scaled back to the lowest available frequency in many applications, including some that include non-trivial numbers of floating-point operations. Note, however, that due to clock gating, the floating point domain is often not the largest source of energy dissipation for integer programs: the integer domain often is the largest source and thus even modest adjustments of its domain voltage yield significant energy savings. Furthermore, although one would expect dynamic scaling to reduce static power as well, we have not quantified the corresponding contribution to the energy savings. Dynamic voltage gating might achieve additional savings (given appropriate support for saving/restoring critical processor state), and would seem to be a promising avenue for future research.
[0105] Several manufacturers, notably Intel [21] and Transmeta [16], have developed processors capable of global dynamic frequency and voltage scaling. Since minimum operational voltage is roughly proportional to frequency, and power is roughly proportional to the voltage squared, this dynamic scaling can be of major benefit in applications with real-time constraints for which the processor as a whole is over-designed: for example, video rendering. Marculescu [23] and Hsu et al. [18] evaluated the use of whole-chip dynamic voltage scaling with minimal loss of performance using cache misses as the trigger [23]. Other work [7, 26] has also begun to look at steering instructions to pipelines or functional units running statically at different speeds so as to exploit scheduling slack in the program to save energy. Our contribution is to demonstrate that a microprocessor with multiple clock domains provides the opportunity to reduce power consumption on a variety of different applications without a significant performance impact by reducing frequency and voltage in domains that do not contribute significantly to the critical path of the current application phase.
[0106] Govil et al. [15] and Weiser et al. [31] describe interval-based strategies to adjust the CPU speed based on processor utilization. The goal is to reduce energy consumption by attempting to keep the processor 100% utilized without significantly delaying task completion times. A history based on the utilization in previous intervals is used to predict the amount of work and thereby adjust speed for maximum utilization without work backlog. Pering et al. [25] apply a similar principle to real-time and multimedia applications. Similarly, Hughes et al. [19] use instruction count predictions for frame based multimedia applications to dynamically change the global voltage and frequency of the processor while tolerating a low percentage of missed frame deadlines. Bellosa [2, 3] describes a scheme to associate energy usage patterns with every process in order to control energy consumption for the purposes of both cooling and battery life. Cache and memory behavior as well as process priorities are used as input in order to drive the energy control heuristics. Benini et al. [4] present a system that monitors system activity and provides information to an OS module that manages system power. They use this monitoring system in order to demonstrate how to set the threshold idle time used to place a disk in low-power mode. Our work differs in that we attempt to slow down only those parts of the processor that are not on an application's critical path.
[0107] Fields et al. [12] use a dependence graph similar to ours, but constructed on the fly, to identify the critical path of an application. Their goal is to improve instruction steering in clustered architectures and to improve value prediction by selectively applying it to critical instructions only. We use our graph off-line in order to slow down non-critical program paths. Li et al. [22] explore the theoretical lower bound of energy consumption assuming that both the program and the machine are fully adjustable. Assuming equal energy dissipation in all hardware components, they show that a program with balanced load on all components consumes less energy than one with significant variance.
[0108] Childers et al. [9] propose to trade IPC for clock frequency. The user requests a particular quality of service from the system (expressed in MIPS) and the processor uses an interval-based method to monitor the IPC and adjust the frequency and voltage accordingly. In their work, a process with high IPC will run at a low clock frequency while a process with low IPC will run at a high clock frequency, which is contrary to what is required for some applications (e.g., when low IPC is due to high miss rates). Our techniques work to achieve the exact opposite in order to provide maximum performance with minimum energy.
[0109] While a preferred embodiment of the present invention has been set forth above, those skilled in the art who have reviewed the present disclosure will readily appreciate that other embodiments can re realized within the scope of the invention. For example, numerical values and fabrication techniques are illustrative rather than limiting. Also, while four domains have been disclosed, it is possible to implement a processor with more or fewer domains and with different boundaries among the domains. Other possible variations of the invention have been noted above. Therefore, the present invention should be construed as limited only by the appended claims.
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A multiple clock domain (MCD) microarchitecture uses a globally-asynchronous, locally-synchronous (GALS) clocking style. In an MCD microprocessor each functional block operates with a separately generated clock, and synchronizing circuits ensure reliable inter-domain communication. Thus, fully synchronous design practices are used in the design of each domain.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to camptothecin analogs having an E-ring ketone which inhibit the enzyme topoisomerase I and have anticancer activity. This invention is also related to the treatment of tumors in animals with camptothecin analogs.
[0003] 2. Background of the Invention
[0004] Camptothecin (CPT) is a naturally occurring cytotoxic alkaloid which is known to inhibit the enzyme topoisomerase I and is a potent anti tumor agent. Camptothecin compounds have the general ring structure shown below.
[0005] Camptothecin was isolated from the wood and bark of Camptotheca acuminata by Wall et al. (Wall et al., 1966, J. Am. Chem. Soc., 88: 3888). It has been shown that if the E-ring α-hydroxy lactone functions are altered or removed, that the resulting compounds have no activity regarding topoisomerase I inhibition or inhibition of cancer cells. (Wall, Plant Antitumor Agents. V. Alkaloids with Antitumor Activity Symposiumsberichtes, pp. 77 87, 4. Internationales Symposium, Biochemie und Physiologie der Alkaloide, Halle (Saale) 25. Bis 28. Jun., 1969, edited by K. Mothes, K. Schreiber, and H. R. Schutte, Akademie Verlag, Berlin, 1969; and Nicholas et al, J. Med. Chem., 33, 972 (1990).)
[0006] Another process that affects all camptothecin compounds is that at an alkaline pH, as low as 7.5 or higher, the lacton E-ring is readily hydrolyzed to give an E-ring opened carboxylate product. This compound is much less active in the above mentioned activities.
[0007] The cytotoxic activity of camptothecin compounds is believed to arise from the ability of these compounds to inhibit both DNA and RNA synthesis and to cause reversible fragmentation of DNA in mammalian cells. Topoisomerase I relaxes both positively and negatively supercoiled DNA and has been implicated in various DNA transactions such as replication, transcription and recombination. The enzyme mechanism is believed to involve a transient breakage of one of the two DNA strands and the formation of a reversible covalent topoisomerase I enzyme DNA complex. Camptothecin interferes with the DNA breakage reunion reaction by reversibly trapping the enzyme DNA intermediate termed the “cleavable complex”. The cleavable complex assay is a standard test for determining the cytotoxic activity of camptothecin compounds. The high levels of topoisomerase I in several types of human cancer and the low levels in correspondingly normal tissue provide the basis for tumor treatment with biologically active camptothecin analogs.
[0008] U.S. Pat. No. 4,894,456 describes methods of synthesizing camptothecin compounds which act as inhibitors of topoisomerase I and are effective in the treatment of leukemia (L 1210). U.S. Pat. No. 5,225,404 discloses methods of treating colon tumors with camptothecin compounds.
[0009] Numerous camptothecin compounds and their use as inhibitors of topoisomerase I are reported by U.S. Pat. No. 5,053,512; U.S. Pat. No. 4,981,968; U.S. Pat. No. 5,049,668; U.S. Pat. No. 5,106,742; U.S. Pat. No. 5,180,722; U.S. Pat. No. 5,244,903; U.S. Pat. No. 5,227,380; U.S. Pat. No. 5,122,606; U.S. Pat. No. 5,122,526; and U.S. Pat. No. 5,340,817.
[0010] U.S. Pat. No. 4,943,579 discloses the esterification of the hydroxyl group at the 20 position of camptothecin to form several prodrugs. This patent further discloses that the prodrugs are water soluble and are converted into the parent camptothecin compounds by hydrolysis.
[0011] Brangi et al., Cancer Research, 59, 5938 5946 Dec. 1, 1999, reports an investigation of Camptothecin resistance in cancer cells and reports the compound difluoro 10, 11 methylenedioxy 20(S) camptothecin.
[0012] A need continues to exist, however, for camptothecin analogs having improved stability under physiological conditions.
SUMMARY OF THE INVENTION
[0013] Accordingly, one object of the present invention is to provide a camptothecin analog having improved stability under physiological conditions.
[0014] Another object of the present invention is to provide a method of treating leukemia or solid tumors in a mammal in need thereof by administration of a camptothecin analogs.
[0015] Another object of the present invention is to provide a method of inhibiting the enzyme topoisomerase I and/or alkylating DNA of associated DNA topoisomerase I by contacting a DNA topoisomerase I complex with a camptothecin analog.
[0016] These and other objects of the present invention are made possible by a camptothecin analog having the structure:
where X and Y are each independently NO 2 , NH 2 , H, F, Cl, Br, I, COOH, OH, O—C 1-6 alkyl, SH, S—C 1-6 alkyl, CN, NH—C 1-6 alkyl, N(C 1-6 alkyl) 2 , CHO, C 1-8 alkyl, N 3 , -Z-(CH 2 ) a —N—((CH 2 ) b OH) 2 , wherein Z is selected from the group consisting of O, NH and S, and a and b are each independently an integer of 2 or 3, -Z-(CH 2 ) 2 —N—(C 1-6 alkyl) 2 wherein Z is selected from the group consisting of O, NH and S, and a is an integer of 2 or 3, —CH 2 -L, where L is halogen (F, Cl, Br, I), + N 2 , + (OR 1 ) 2 , + S(R 1 ) 2 , + N(R 1 ) 3 , OC(O)R 1 , OSO 2 R 1 , OSO 2 CF 3 , OSO 2 C 4 F 9 , C 1-6 alkyl-C(═O)—, C 4-18 aryl-C(═O)—, C- 1-6 alkyl SO-2-, perfluoro C 1-6 alkyl-SO 2 — or C 4-18 aryl-SO 2 —, (where each R 1 independently is C 1-6 alkyl, C 4-18 aryl or C 4-18 ArC 1-6 alkyl); or —CH 2 NR 2 R 3 , where (a) R 2 and R 3 are, independently, hydrogen, C 1-6 alkyl, C 3-7 cycloalkyl, C 3-7 cycloalkyl-C 1-6 alkyl, C 2-6 alkenyl, hydroxyl-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 COR 4 where R 4 is hydrogen, C 1-6 alkyl, perhalo-C 1-6 alkyl, C 3-7 cycloalkyl, C 3-7 cycloalkyl-C 1-6 alkyl, C 2-6 alkenyl, hydroxyl-C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxy-C 1-6 alkyl, or (b) R 2 and R 3 taken together with the nitrogen atom to which they are attached form a saturated 3-7 membered heterocyclic ring which may contain a O, S or NR 5 group, where R 5 is hydrogen, C 1-6 alkyl, perhalo-C 1-6 alkyl, aryl, aryl substituted with one or more groups selected from the group consisting of C 1-6 alkyl, halogen, nitro, amino, C 1-6 alkylamino, perhalo-C 1-6 alkyl, hydroxyl-C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and —COR 6 where R 6 is hydrogen, C 1-6 alkyl perhalo-C 1-6 alkyl, C 1-6 alkoxy, aryl, and aryl substituted with one or more C 1-6 alkyl, perhalo-C 1-6 alkyl, hydroxyl-C 1-6 alkyl, or C 1-6 alkoxy-C 1-6 alkyl groups; R 7 is H, or C(O)—(CH 2 ) m —NR 8 R 9 , where m is an integer of 1-6 or —C(O)CHR 10 NR 8 R 9 , where R 10 is the side chain of one of the naturally occurring α-amino acids, R 8 and R 9 are, independently, hydrogen, C 1-8 alkyl or —C(O)CHR 11 NR 12 R 3 , where R 11 is the side chain of one of the naturally occurring α-amino acids and R 12 and R 13 are each independently hydrogen or C 1-8 alkyl; W is independently H or F, R 13 and R 14 are each H or combine to form a double bond; and n is an integer of 1 or 2, and salts thereof.
[0027] These compounds have the necessary α-hydroxy-ethyl substitutents at C 20 and a ketone in place of the lactone structure. Such a compound has a spatial orientation virtually identical with that of camptothecin, however it is much more stable than CPT under alkaline conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
[0029] FIG. 1 illustrates the synthesis of a tricyclic ketone used to form the compound of the present invention;
[0030] FIG. 2 illustrates a synthetic reaction scheme for preparing compounds according to the present invention; and
[0031] FIG. 3 illustrates a synthetic reaction scheme for preparing compounds according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] Unless indicated to the contrary, the term “alkyl” as used herein means a straight chain or branched chain alkyl group with 1-30, preferably 1-18 carbon atoms, more preferably 1-8 carbon atoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, undecyl, dodecyl, myristyl, heptadecyl and octadecyl groups. The term “alkyl” also includes C 3-30 cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
[0033] Unless indicated to the contrary, the term “aryl” as used herein means a carbocyclic aromatic ring having 6-18 carbon atoms, preferably 6 10 carbon atoms in the aromatic ring structure. The aromatic rings may be substituted by one or more alkyl group, preferably alkyl groups having 1-10 carbon atoms. A particularly preferred aryl group is phenyl.
[0034] Unless indicated to the contrary, the term “aralkyl” as used herein means a straight chain or branched chain alkyl group as defined above for the term “alkyl” bonded to an aryl group as defined above for the term “aryl”. Preferred aralkyl groups are benzyl, phenethyl, etc.
[0035] As used herein, the term “acyl” means formyloxy and acyl moieties derived from aromatic carboxylic acids, heterocyclic carboxylic acids, aralkyl carboxylic acids, as well as alkyl and aromatic sulfonic acids. The alkyl groups of these acyloxy moieties may be a straight chain or branched chain alkyl group with 1-7 carbon atoms. Additionally, the acyl moiety may contain one or more unsaturated carbon carbon bonds and may also carry one or more substituents such as halogen, amino and hydroxyl groups.
[0036] The camptothecin analogs of the present invention may bear a leaving group at one or more of the positions C 7 or Cg of the camptothecin ring structure. More specifically, the leaving group is a group of the formula —CH 2 -L, where L is a functional group which can be easily displaced, i.e. L is a good leaving group in nucleophilic substitution reactions. Suitable groups L include halogen (F, Cl, Br, I), + N 2 , + O(R 1 ) 2 , + S(R 1 ) 2 , + N(R 1 ) 3 , OC(O)R 1 , OSO 2 R 1 , OSO 2 CF 3 , and OSO 2 C 4 F 9 , C 1-6 alkyl-C(═O)—, C 4-18 aryl-C(═O)—, C 1-6 alkyl-SO 2 —, perfluoroC 1-6 alkyl-SO 2 — and C 4-18 aryl-SO 2 —, (where each R 1 independently is C 1-6 alkyl, C 4-18 aryl or C 4-18 ArC 1-6 alkyl).
[0037] While not being bound by any particular theory, it is believed that nucleophilic groups on DNA displace leaving group L from the camptothecin analogs of the present invention resulting in alkylation of the DNA by the alkylating group of the camptothecin ring structure. Suitable nucleophilic groups present in DNA include the nucleophilic groups found in DNA bases adenine, guanine, thymine, and cytosine, such as NH 2 , —NH— and ═N— groups. When a camptothecin analog of the invention having a —CH 2 -L group is contacted with DNA, nucleophilic displacement of leaving group L results in alkylation of the nucleic acid. The compounds of the present invention exhibit a novel anti tumor activity by alkylating DNA.
[0038] Camptothecin analogs have an asymmetric carbon atom at the 20-position making two enantiomeric forms, i.e., the (R) and the (S) configurations, possible. This invention includes each enantiomeric form individually, as well as combinations or mixtures of these forms. The invention also includes other forms of the camptothecin analogs including solvates, hydrates, polymorphs, salts, etc. Particularly preferred compounds are camptothecin derivatives having the (S) configuration at the 20-position.
[0039] In a preferred embodiment, X is NO 2 , NH 2 , H, F, Cl, Br, I, COOH, OH, O—C 1-6 alkyl, SH, S—C 1-6 alkyl, CN, CH 2 NH 2 , NH—C 1-6 alkyl, CH 2 NH—C 1-6 alkyl, N(C 1-6 alkyl) 2 , CH 2 N(C 1-6 alkyl) 2 , O—CH 2 CH 2 N(CH 2 CH 2 OH) 2 , NH—CH 2 CH 2 N(CH 2 CH 2 OH) 2 , S—CH 2 CH 2 N(CH 2 CH 2 OH) 2 , O—CH 2 CH 2 CH 2 N(CH 2 CH 2 OH) 2 , NH—CH 2 CH 2 CH 2 N(CH 2 CH 2 OH) 2 , S—CH 2 CH 2 CH 2 N(CH 2 CH 2 OH) 2 , O—CH 2 CH 2 N(CH 2 CH 2 CH 2 OH) 2 , NH—CH 2 CH 2 N(CH 2 CH 2 CH 2 OH) 2 , S—CH 2 CH 2 N(CH 2 CH 2 CH 2 OH) 2 , O—CH 2 CH 2 CH 2 N(CH 2 CH 2 CH 2 OH 2 ) 2 , NH—CH 2 CH 2 CH 2 N(CH 2 CH 2 CH 2 OH 2 ) 2 , S—CH 2 CH 2 CH 2 N(CH 2 CH 2 CH 2 OH 2 ) 2 , O—CH 2 CH 2 N(C 1-6 alkyl) 2 , NH—CH 2 CH 2 N(C 1-6 alkyl) 2 , S—CH 2 CH 2 N(C 1-6 alkyl) 2 , O—CH 2 CH 2 CH 2 N(C 1-6 alkyl) 2 , NH—CH 2 CH 2 CH 2 N(C 1-6 alkyl) 2 , S—CH 2 CH 2 CH 2 N(C 1-6 alkyl) 2 , CHO, N 2 , C 1-8 alkyl, CH 2 -L where L is halogen (F, Cl, Br, I), + N 2 , + O(R 1 ) 2 (where each R 1 independently is alkyl, aryl or aralkyl as defined above), + S(R 1 ) 2 , + N(R 1 ) 3 , OC(O)R 1 , OSO 2 R 1 , OSO 2 CF 3 , OSO 2 C 4 F 9 , C 1-6 alkyl-C(═O)—, C 4-8 aryl-C(═O)—, C 1-6 alkyl-SO 2 —, perfluoro C 1-6 alkyl-SO 2 — and C 4-18 aryl-SO 2 —.
[0040] In a preferred embodiment Y is H, C 1-8 alkyl, or CH 2 NR 2 R 3 where (a) R 2 and R 3 are, independently, hydrogen, C 1-6 alkyl, C 3-7 cycloalkyl, C 3-7 cycloalkyl-C 1-6 alkyl, C 2-6 alkenyl, hydroxyl-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 COR 4 where R 4 is hydrogen, C 1-6 alkyl, perhalo C 1 -alkyl, C 3-7 cycloalkyl, C 3-7 cycloalkyl-C 1-6 alkyl, C 2-6 alkenyl, hydroxyl-C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, or (b) R 2 and R 3 taken together with the nitrogen atom to which they are attached form a saturated 3-7 membered heterocyclic ring which may contain a O, S or NR 5 group, where R 5 is hydrogen, C 1-6 alkyl, perhalo C 1-6 alkyl, aryl, aryl substituted with one or more groups selected from the group consisting of C 1-6 alkyl, halogen, nitro, amino, C-6 alkylamino, perhalo-C 1-6 alkyl, hydroxyl-C 1-6 alkyl, C 1-6 alkoxy, C 1-6 -alkoxy-C 1-6 alkyl and —COR 6 where R 6 is hydrogen, C 1-6 alkyl perhalo-C 1-6 alkyl, C 1-6 alkoxy, aryl, and aryl substituted with one or more C 1-6 alkyl, perhalo-C 1-6 alkyl, hydroxyl-C 1-6 alkyl, or C 1-6 alkoxy-C 1-6 alkyl groups.
[0041] The group R 7 may be an ester of a naturally occurring or non naturally occurring amino acid such as an ester of glycine or β-alanine. In particular, the present invention is directed to camptothecin analogs where the group R 7 is C(O)—(CH 2 ) m —NR 8 R 9 , where m is the integer 1, 2, 3, 4, 5 and 6 and R 8 and R 9 are each H.
[0042] Suitable side chains R 10 and R 1 appearing on the group R 7 are the side chains of the amino acids glycine, α-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, aspartate, glutamate, asparagine, glutamine, cysteine and methionine. Moreover, the group R 7 , may comprise two amino acid units linked by a peptide linkage. In particular the group R 7 may comprise a β-alanine group linked to a lysine of the structure
[0043] Moreover, the group R 7 may provide basis for the formation of a mono or di salts, via the free amine groups, such as a hydrochloride or dihydrochloride.
[0044] A synthon for attaching such a group to a terminal hydroxyl group is described by Hudkins et al. Bioorg. Med. Chem. Lett, 8 (1998) 1873 1876).
[0045] Particularly preferred esters are glycinate esters and the peptide ester based on β-alanine lysine. These esters are pro drugs which are converted to the camptothecin analog compound by hydrolysis of the ester bond. The esters may be prepared by the method described in U.S. Pat. No. 4,943,579 which is incorporated herein by reference for a more complete description of the process of preparing the esters and for a description of suitable esters formed by the process. The esterification synthon may need to introduced in a protected form, such that the reaction of amine groups is inhibited, followed by removal of the protecting group. Such protecting groups are well known to those of ordinary skill in the art and are described by Hudkins et al. Bioorg. Med. Chem. Lett, 8 (1998) 1873 1876).
[0046] Specific examples of non limiting compounds include 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone; 7-ethyl 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone; 7-chloromethyl 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone; 7-bromomethyl 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone; 7-hydroxymethyl 10,11-difluromethylenedioxy-20-(S)-camptothecin E-ring ketone, 9-nitro 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone, 9-amino 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-nitro 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone and 7-ethyl-9-amino 10,11-difluoromethylenedioxy-20-(S)-camptothecin E-ring ketone.
[0047] Specific non limiting examples further include the C 20 amino acid ester of the above identified compounds 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone; 7-ethyl 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone; 7-chloromethyl 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone; 7-bromomethyl 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone; 7-hydroxymethyl 10,11-difluromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone, 9-nitro 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone, 9-amino 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-nitro 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-amino 10,11-difluoromethylenedioxy-20-O-glycinyl-20-(S)-camptothecin E-ring ketone, 10,11-difluoromethylenedioxy-20-O—N-methylglycinyl-20-(S)-camptothecin E-ring ketone; 7-ethyl 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone; 7-chloromethyl 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone; 7-bromomethyl 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone; 7-hydroxymethyl 10, 11 difluromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone, 9-nitro 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone, 9-amino 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-nitro 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-amino 10,11-difluoromethylenedioxy 20-O—N methylglycinyl-20-(S)-camptothecin E-ring ketone, 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone; 7-ethyl 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone; 7-chloromethyl 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone; 7-bromomethyl 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone; 7-hydroxymethyl 10,11-difluromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone, 9-nitro 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone, 9-amino 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-nitro 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone and 7-ethyl-9-amino 10,11-difluoromethylenedioxy 20-O—N,N dimethylglycinyl-20-(S)-camptothecin E-ring ketone.
[0048] Additional specific non limiting examples further include 10,11-difluoromethylenedioxy-20-O—O-ala-lys-20-(S)-camptothecin E-ring ketone; 7-ethyl 10,11-difluoromethylenedioxy-20-O—O-ala-lys-20-(S)-camptothecin E-ring ketone; 7-chloromethyl 10,11-difluoromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone; 7-bromomethyl 10,11-difluoromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone; 7-hydroxymethyl 10,11-difluromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone, 9-nitro 10,11-difluoromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone, 9-amino 10,11-difluoromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-nitro 10,11-difluoromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone and 7-ethyl-9-amino 10,11-difluoromethylenedioxy-20-O-β-ala-lys-20-(S)-camptothecin E-ring ketone.
[0049] Additional specific non limiting examples further include 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone; 7-ethyl 10,11-difluoromethylenedioxy-20-O-B-ala-20-(S)-camptothecin E-ring ketone; 7-chloromethyl 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone; 7-bromomethyl 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone; 7-hydroxymethyl 10,11-difluromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone, 9-nitro 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone, 9-amino 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone, 7-ethyl-9-nitro 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone and 7-ethyl-9-amino 10,11-difluoromethylenedioxy-20-O-β-ala-20-(S)-camptothecin E-ring ketone.
[0050] The compounds of the present invention may be prepared by conventional methods known to those of ordinary skill in the art, without undue experimentation.
[0051] For example, the claimed compounds may be prepared by condensation of a aminophenylcarbonyl of formula IV or V
where X, Y, W and n are as defined for formula I with a tricyclic ketone of formula III
where R 13 and R 14 are defined as for formula I.
[0055] The condensation reaction is analogous to the condensation reaction described by Wall et al. U.S. Pat. No. 5,122,526, the relevant portions of which are hereby incorporated by reference.
[0056] The synthetic sequence is described with reference to FIG. 1 . The 20-desoxy tricyclic analog (1) is treated with an appropriate amine as shown in the example. It is a cyclopentyl amine and the corresponding amide (2) is obtained. On acetylation, 2 is converted to the acetate 3. The next step is a homologolation reaction. Other homologolation reactions may be carried out by converting 2 to a bromide, etc. The compound 4 is converted to a hydroxy derivative containing one more carbon atom, compound 5. Compound 5 may be brominated to the bromo analog 6. Compound 6 in turn is converted as shown to the tricyclic 20-desoxy ketone 7. Compound 7 may be hydroxylated to the (RS)-20-hydroxy compound 8. Finally, acidic cleavage of the ketal yields the 20(RS)-hydroxy ketone 9 which is the reactant that can be converted now to many camptothecin analogs (as shown in the attached example).
[0057] Additional, non limiting examples of condensation reactions are illustrated in FIG. 2 .
[0058] Alternatively, suitable E-ring ketone compounds may also be prepared from the corresponding compothecin compound bearing an E-ring lactone, illustrated in FIG. 3 , by the following reaction sequence:
i) reaction of the E-ring lactone with a primary alkylamine to form an α-hydroxy alkylamide; ii) activation of a pendant D ring hydroxymethylene group to form a leaving group, such as by formation of an acetate, followed by a displacement reaction with a dialkyl malonate, such as diethylmalonate; iii) esterification of the alkylamide to an alkyl ester; iv) cyclization of a D-ring methylene malonate onto the alkyl ester to form the E-ring ketone followed by decarboxylation of an ester group; and v) decarboxylation of the remaining ester group.
[0064] In a further embodiment, an α-β E-ring unsaturation may be introduced by conventional methods known to those of ordinary skill in the art, such as by reacion with DDQ.
[0065] An alternative procedure for preparing the E-ring ketone from camptothecin is attached and involves a procedure as shown. If the E-ring ketone can be prepared at the very end, a conjugated B ring can be prepared as shown in the very last step. Such a compound might have very interesting properties. It might possibly intercalate with DNA whereas camptothecin does not.
[0066] Substitution at the C 7 position may be conducted by condensation with the corresponding aldehyde of the C 7 substituent. Esterification with an amino acid at C 20 is possible by conventional methods known to those of ordinary skill in the art. Substitution at C 9 with groups such a nitro and amino is also possible in a manner analogous to that described in the literature.
[0067] The compounds of the invention having the group —CH 2 -L at C 9 are prepared from known 20(S)—CPT compounds bearing a halogen, for example, a bromine atom, at the C 9 position. The halogen atom can be readily converted into the corresponding cyano analog by reaction with CuCN, followed by hydrolysis to form the corresponding carboxy analog. The carboxy analog is reduced to the corresponding hydroxy methyl analog which can be reacted with Ph 3 P—CCl 4 to provide the corresponding chloromethyl analog. The chloromethyl analog can be readily converted to the bromomethyl and iodomethyl analogs using LiBr or LiI. The remaining compounds of the invention are prepared from these compounds by reaction with the corresponding acid chloride, sulfonyl chloride, etc. These reactions are well known to one having ordinary skill in this art.
[0068] Compounds in which L is Br or I are readily prepared from the compound in which L is Cl by simple halide exchange employing LiBr or LiI in dimethylformamide (DMF) solution (Larock, R. C., Comprehensive Organic Transformations, VCH Publishers, Inc., p. 337, N.Y. 1989).
[0069] Alternatively, the 7-methyl compounds (L is H) can be prepared either by a Friedlander reaction employing the corresponding acetophenone, or by a free radical alkylation reaction (Sawada et al., 1991, Chem. Pharm. Bull., 39: 2574). Free radical bromination of 7-methyl substrates can be accomplished by employing N-bromosuccinimide (NBS) in acetic acid (HOAc) under catalysis by benzoyl peroxide to give compounds in which L is Br.
[0070] 9-Nitro-difluoro-10,11-methylenedioxy-20-(S)-camptothecin may be prepared from difluoro-10,11-methylenedioxy-20-(S)-camptothecin by treatment with HNO 3 . 9-Amino difluoro-10,11-methylenedioxy-20-(S)-camptothecin may be prepared from 9-nitro difluoro-10,11-methylenedioxy-20-(S)-camptothecin via reduction with SnCl 2 .
[0071] Other compounds which possess oxygen derived leaving groups, such as triflate or tosylate, are prepared from the 7-hydroxymethyl and/or 7-halomethyl compounds. The 7-hydroxymethyl compounds are prepared from the corresponding parent compounds by the hydroxymethylation reaction. (e.g. Sawada et al., 1991, Chem. Pharm. Bull., 39: 2574) Treatment of these compounds with readily available sulfonic acid chlorides or anhydrides using known procedures (Stang et al., 1982, Synthesis, 85) provides the highly electrophilic substrates noted above. Alternatively, the compounds described above can be generated from any of the substrates where L is Cl, Br or I by reaction with the silver salt of the corresponding acid (e.g., silver trifluoromethanesulfonate, silver tosylate, etc.) as described generally by Stang et al. and more specifically by Gramstad and Haszeldine (T. Gramstad and R. N. Haszeldine, 1956, J. Chem. Soc., 173).
[0072] C 20 esters may be prepared by esterifying the 20-position hydroxyl group of a camptothecin analog to form an ester containing a water soluble moiety. Generally, the camptothecin analog is initially suspended in methylene chloride or other inert solvent, stirred and cooled. To the cooled mixture is added one equivalent of an acid having the formula HOOC—CHR 10 —NR 8 R 9 or HOOC—(CH 2 ) m —NR 8 R 9 , where m is an integer from 1-6, preferably 2-6, and R 10 is the side chain of one of the naturally occurring α-amino acids. R 8 and R 9 are, independently, hydrogen or C 1-8 alkyl. Suitable side chains R 10 are the side chains of the amino acids glycine, α-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, leucine, arginine, histidine, aspartate, glutamate, asparagine, glutamine, cysteine and methionine. Particularly preferred esters are glycinate esters. One equivalent of dicyclohexylcarbodiimide (DCC) and a catalytic amount of an amine base, preferably a secondary or tertiary amine, are also added to the mixture, which is then stirred to complete the reaction. Any precipitate which forms is removed by filtration and the product is isolated after removal of the solvent.
[0073] The free amine(s) may be converted to an acid addition salt by the addition of a pharmaceutically acceptable acid. Suitable acids include both inorganic and organic acids. Suitable addition salts include, but are not limited to hydrochloride, sulfate, phosphate, diphosphate, hydrobromide, nitrate, acetate, malate, maleate, fumarate, tartrate, succinate, citrate, lactate, methanesulfonate, p-toluenesulfonate, palmoate, salicylate and stearate salts. The salts may be purified by crystallization from a suitable solvent.
[0074] The water soluble 20-hydroxyl esters of the present invention are substantially less toxic than the parent compounds from which the esters are prepared.
[0075] The camptothecin analogs are administered in a dose which is effective to inhibit the growth of tumors. As used herein, an effective amount of the camptothecin analog is intended to mean an amount of the compound that will inhibit the growth of tumors, that is, reduce the site of growing tumors relative to a control in which the tumor is not treated with the camptothecin analog. These effective amounts are generally from about 1-60 mg/kg of body weight per week, preferably about 2-20 mg/kg per week.
[0076] The compounds of the present invention may be administered as a pharmaceutical composition containing the camptothecin analog and a pharmaceutically acceptable carrier or diluent. The active materials can also be mixed with other active materials which do not impair the desired action and/or supplement the desired action. The active materials according to the present invention can be administered by any route, for example, orally, parenterally, intravenously, intradermally, subcutaneously, or topically, in liquid or solid form.
[0077] For the purposes of parenteral therapeutic administration, the active ingredient may be incorporated into a solution or suspension. The solutions or suspensions may also include the following components: a sterile diluent such as water for injection, saline solution, fixed oils, polyethylene glycols, glycerine, propylene glycol or other synthetic solvents; antibacterial agents such as benzyl alcohol or methyl parabens; antioxidants such as ascorbic acid or sodium bisulfite; chelating agents such as ethylenediaminetetraacetic acid; buffers such as acetates, citrates or phosphates and agents for the adjustment of tonicity such as sodium chloride or dextrose. The parenteral preparation can be enclosed in ampoules, disposable syringes or multiple dose vials made of glass or plastic.
[0078] Another mode of administration of the compounds of this invention is oral. Oral compositions will generally include an inert diluent or an edible carrier. For the purpose of oral therapeutic administration, the aforesaid compounds may be incorporated with excipients and used in the form of tablets, gelatine capsules, troches, capsules, elixirs, suspensions, syrups, wafers, chewing gums and the like. Compositions may be prepared according to any method known to the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of sweetening agents, flavoring agents, coloring agents and preserving agents. Tablets containing the active ingredient in admixture with nontoxic pharmaceutically acceptable excipients which are suitable for manufacture of tablets are acceptable. These excipients may be, for example, inert diluents, such as calcium carbonate, sodium carbonate, lactose, calcium phosphate or sodium phosphate granulating and disintegrating agents, such as maize starch, or alginic acid; binding agents, such as starch, gelatin or acacia; and lubricating agents, such as magnesium stearate, stearic acid or talc. Tablets may be uncoated or may be coated by known techniques to delay disintegration and adsorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monostearate or glyceryl distearate alone or with a wax may be employed. Formulations for oral use may also be presented as hard gelatin capsules wherein the active ingredient is mixed with an inert solid diluent, for example calcium carbonate, calcium phosphate or kaolin, or as soft gelatin capsules wherein the active ingredient is mixed with water or an oil medium, such as peanut oil, liquid paraffin or olive oil.
[0079] The tablets, pills, capsules, troches and the like may contain the following ingredients: a binder such as microcrystalline cellulose, gum tragacanth or gelatin; an excipient such as starch or lactose, a disintegrating agent such as alginic acid, Primogel, corn starch and the like; a lubricant such as magnesium stearate or Sterotes; a glidant such as colloidal silicon dioxide; and a sweetening agent such as sucrose or saccharin or flavoring agent such as peppermint, methyl salicylate, or orange flavoring may be added. When the dosage unit form is a capsule, it may contain, in addition to material of the above type, a liquid carrier such as a fatty oil. Other dosage unit forms may contain other various materials which modify the physical form of the dosage unit, for example, as coatings. Thus tablets or pills may be coated with sugar, shellac, or other enteric coating agents. A syrup may contain, in addition to the active compounds, sucrose as a sweetening agent and certain preservatives, dyes and colorings and flavors. Materials used in preparing these various compositions should be pharmaceutically or veterinarially pure and non-toxic in the amounts used.
[0080] Aqueous suspensions of the invention contain the active materials in admixture with excipients suitable for the manufacture of aqueous suspensions. Such excipients include a suspending agent, such as sodium carboxymethylcellulose, methylcellulose, hydroxypropylethyl cellulose, sodium alginate, polyvinylpyrrolidone, gum tragacanth and gum acacia, and dispersing or wetting agents such as a naturally occurring phosphatide (e.g., lecithin), a condensation product of an alkylene oxide with a fatty acid (e.g., polyoxyethylene stearate), a condensation product of ethylene oxide with a long chain aliphatic alcohol (e.g., heptadecaethylene oxycetanol), a condensation product of ethylene oxide with a partial ester derived from a fatty acid and a hexitol (e.g., polyoxyethylene sorbitol mono-oleate), or a condensation product of ethylene oxide with a partial ester derived from fatty acid and a hexitol anhydride (e.g., polyoxyethylene sorbitan mono oleate). The aqueous suspension may also contain one or more preservatives such as ethyl or n-propyl p-hydroxybenzoate, one or more coloring agents, one or more flavoring agents and one or more sweetening agents, such as sucrose, aspartame, saccharin, or sucralose.
[0081] Oil suspensions may be formulated by suspending the active ingredient in a vegetable oil, such as arachis oil, olive oil, sesame oil or coconut oil, or in a mineral oil such as liquid paraffin. The oil suspensions may contain a thickening agent, such as beeswax, hard paraffin or cetyl alcohol. Sweetening agents may be added to provide a palatable oral preparation. These compositions may be preserved by the addition of an antioxidant such as ascorbic acid.
[0082] Dispersible powders and granules of the invention suitable for preparation of an aqueous suspension by the addition of water may be formulated from the active ingredients in admixture with a dispersing, suspending and/or wetting agent, and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those disclosed above. Additional excipients, for example sweetening, flavoring and coloring agents, may also be present.
[0083] The pharmaceutical composition of the invention may also be in the form of oil in water emulsions. The oily phase may be a vegetable oil, such as olive oil or arachis oil, a mineral oil, such as liquid paraffin, or a mixture of these. Suitable emulsifying agents include naturally occurring gums, such as gum acacia and gum tragacanth, naturally occurring phosphatides, such as soybean lecithin, esters or partial esters derived from fatty acids and hexitol anhydrides, such as sorbitan mono-oleate, and condensation products of these partial esters with ethylene oxide, such as polyoxyethylene sorbitan mono oleate. The emulsion may also contain sweetening and flavoring agents.
[0084] Syrups and elixirs may be formulated with sweetening agents, such as glycerol, sorbitol or sucrose. Such formulations may also contain a demulcent, a preservative, a flavoring or a coloring agent.
[0085] The pharmaceutical compositions of the invention may be in the form of a sterile injectable preparation, such as a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to the known art using those suitable dispersing or wetting agents and suspending agents which have been mentioned above. The sterile injectable preparation may also be a sterile injectable solution or suspension in a nontoxic parenterally acceptable diluent or solvent, such as a solution of 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are water and Ringer's solution, an isotonic sodium chloride. In addition, sterile fixed oils may conventionally be employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono or diglycerides. In addition, fatty acids such as oleic acid may likewise be used in the preparation of injectables. Sterilization may be performed by conventional methods known to those of ordinary skill in the art such as by aseptic filtration, irradiation or terminal sterilization (e.g. autoclaving).
[0086] Aqueous formulations (i.e oil in water emulsions, syrups, elixers and injectable preparations) may be formulated to achieve the pH of optimum stability. The determination of the optimum pH may be performed by conventional methods known to those of ordinary skill in the art. Suitable buffers may also be used to maintain the pH of the formulation.
[0087] The compounds of this invention may also be administered in the form of suppositories for rectal administration of the drug. These compositions can be prepared by mixing the drug with a suitable nonirritating excipient which is solid at ordinary temperatures but liquid at the rectal temperatures and will therefore melt in the rectum to release the drug. Non limiting examples of such materials are cocoa butter and polyethylene glycols.
[0088] They may also be administered by intranasal, intraocular, intravaginal, and intrarectal routes including suppositories, insufflation, powders and aerosol formulations.
[0089] The compounds of the present invention may also be administered in the form of liposome or microvesicle preparations. Liposomes are microvesicles which encapsulate a liquid within lipid or polymeric membranes. Liposomes and methods of preparing liposomes are known and are described, for example, in U.S. Pat. No. 4,452,747, U.S. Pat. No. 4,448,765, U.S. Pat. No. 4,837,028, U.S. Pat. No. 4,721,612, U.S. Pat. No. 4,594,241, U.S. Pat. No. 4,302,459 and U.S. Pat. No. 4,186,183. The disclosures of these U.S. patents are incorporated herein by reference. Suitable liposome preparations for use in the present invention are also described in WO-9318749-A1, J-02056431-A and EP-276783-A.
[0090] The camptothecin analogs may be used individually to inhibit the growth of tumors. Alternatively, combinations of two or more camptothecin analogs may be used or combinations of one or more camptothecin analogs with one or more known anti tumor compounds. When a camptothecin analog is combined with a conventional anti tumor compound, the camptothecin analog will generally be present in an amount ranging from about 1-99 wt. %, preferably, 5-95 wt. % of the combined amount of camptothecin and conventional anti tumor compound. The pharmaceutical compositions noted above may contain these combinations of compounds together with an acceptable carrier or diluent.
[0091] The ester compounds of the invention may be administered to treat leukemia and solid tumors in mammals, including humans. The esters of the present invention are prodrugs which are hydrolyzed to camptothecin analogs demonstrating inhibitory activity on topoisomerase I. The camptothecin analogs formed by hydrolysis of the esters of the invention are also effective in treating leukemia and solid tumors in mammals. Numerous camptothecin analogs have been shown to be effective against leukemia using the standard L1210 leukemia assay (Wall et al. (1993), Journal of Medicinal Chemistry, 36: 2689-2700). High activity of camptothecin and camptothecin analogs has also been shown in the P388 leukemia assay (Wall (1983), Medical and Pediatric Oncology, 11: 480A-489A). The later reference also provides a correlation between anti leukemia activity as determined by the L1210 and the P388 leukemia assays with efficacy of camptothecin analogs against solid tumors. Compounds reported as active in the leukemia assays also have demonstrated activity in a number of solid tumors including a colon xenograft, a lung xenograft, a Walker sarcoma and a breast xenograft (Wall (1983), Table IV, page 484 A). Recent studies have confirmed the correlation between topoisomerase I inhibitory activity and anti leukemia/anti tumor activity of camptothecin analogs (Giovanella et al. (1989), Science, 246: 1046-1048). The compounds of the present invention are particularly effective in the treatment of colon, lung, breast and ovary solid tumors, brain glioma and leukemia. These compounds may also be used to treat malaria.
[0092] Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
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Camptothecin analogs having an E-ring ketone are effective anti tumor compounds. These compounds inhibit the enzyme topoisomerase I and may alkylate DNA of the associated topoisomerase I DNA cleavable complex.
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BACKGROUND OF THE INVENTION
This invention relates to a yarn finish. More specifically, this invention relates to a spin finish for polyamide feeder yarn to be processed at high temperature into carpet yarn such as by steam jet texturing.
Various finishes for synthetic filaments are disclosed in the prior art for high temperature processing. However, none of the prior art teach a specific combination of ingredients to achieve the specific beneficial results of the composition of this invention. The critical amounts and ingredients are shown in the discussion below. Many of the prior art finishes flash off in high temperature processing such as steam jet texturing for yarn. Others fail to have emulsion stability or have insufficient yarn lubrication. Still others require numerous, costly components, and do not provide good package formation during take-up of the yarn, or good package unwinding properties.
The yarn finish of this invention is an improvement over the finish disclosed in U.S. Pat. No. 3,781,202 which is hereby specifically incorporated by reference in toto. The esters resulting from the reaction of a long chain fatty acid with a monohydric long chain aliphatic alcohol are known as textile yarn lubricants in U.S. Pat. No. 3,306,850 and U.S. Pat. No. 3,649,535. However, for high temperatures, diesters are taught, or other lubricants must be added.
SUMMARY OF THE INVENTION
The composition of the oil portion of yarn spin finish of this invention is
I______________________________________Component Percent by Weight______________________________________a) tridecyl stearate 40 to 60b) corn oil glyceride 20 to 30 ethoxylated with 10 mols ethylene oxidec) sulfated glycerol trioleate 20 to 30orII______________________________________a) tridecyl stearate 40 to 60b) polyethylene glycol (10) 20 to 30 oleatec) sulfonated petroleum product 20 to 30______________________________________
The compound labeled b) is an emulsifier. The compound labeled c) is an antistatic compound.
The yarn finish composition has all the advantages of the finish disclosed in U.S. Pat. No. 3,781,202 in addition to the following advantages over the prior (including that in U.S. Pat. No. 3,781,202) high temperature spin finishes for textile yarn.
Lower yarn to metal friction
Higher yarn to yarn friction
Low number of components
Low cost
Better yarn package formation
Better yarn package unwind properties The combination of low yarn to metal and high yarn to yarn friction is particularly important and can be achieved only by the particular combination and ratio of components listed above, without losing other equally important benefits. The better yarn package formation during take-up of the yarn from spinning is also important. Of course, the low number of components and cost is always important. Higher yarn to yarn friction is conducive to better cohesion in the package as it is taken up and in the yarn as it is processed. For example, this improved cohesion improves tuftability when the yarn is tufted into a carpet.
The friction characteristics are also influenced by the emulsifier. Other compounds than those listed adversely affect the unique lubrication properties of this finish.
The amount of finish used on the yarn is set forth in U.S. Pat. No. 3,781,202.
By tridecyl stearate is meant the pure compound or the compound prepared by reacting tridecyl alcohol with commercial stearic acid, which may also contain some palmitic acid.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The oil portion of the oil in water emulsion, 4 to 20 percent by weight oil, of this improved spin finish for textured carpet yarn is preferably
I______________________________________Component Percent by Weight______________________________________tridecyl stearate 55corn oil ethoxylated with 10 mols 22ethyleneoxidesulfated glycerol trioleate 23orII______________________________________tridecyl stearate 50polyethylene glycol (10) oleate 23sulfonated petroleum product 27______________________________________
By polyethylene glycol (10) oleate is meant 10 mols of polyethylene glycol was reacted with 1 mol oleic acid.
TABLE A
Comparison of Friction and Package Formation
Yarn finish I is labeled I above.
Yarn finish II is labeled II above.
Yarn finish III is shown in Table I of U.S. Pat. No. 3,781,202 and represents the prior art finish and control for these runs.
______________________________________Run Yarn Package Yarn to Yarn toNo. Finish Formation Rating Metal Yarn Slip Stick______________________________________1 I 2.2 390 370 5501 II 1.5 340 380 8001 III 0.5 410 380 4902 I 75 440 6102 II 65 530 11302 III 90 430 6403 I 48 540 7903 II 49 520 10103 III 60 480 690______________________________________
Run No. 1 was spinning of a 2600 denier, continuous filament yarn which was draw wound and then textured.
Run 2 was spinning of a 1300 denier, continuous filament yarn which was draw-textured in one operation.
Run No. 3 was spinning of a 2600 denier continuous filament yarn, also draw-textured in one operation.
The yarn to metal friction test is described in ASTMD 3108-72T, with results reported here in grams rather than coefficient of friction. The yarn to yarn friction tests were made by simply modifying the yarn to metal test by removing the metal pin and twisting the yarn upon itself 360° in the same location. While running this test, friction builds up as the yarn "sticks" then breaks loose as the yarn "slips." The values reported herein as "stick" and "slip" are the maximum and minimum values obtained for the "stick" and "slip" portions of the test.
The package formation rating is an objective visual rating by experts of the package formed - higher number means better package.
Each rating is an average from 20 packages. The ratings are as follows:
0 -- sluffing off end
1 -- severe bulge on sides
2 -- slight bulge on sides
3 -- straight sides, no bulge
These results clearly show the highly improved package formation and friction properties of the improved finish of this invention.
The following table shows the criticality of the particular emulsifier-antistatic agent combinations of this invention to the improved friction, static and other properties of the finish of this invention.
TABLE B______________________________________ Finish Finish Finish Finish A II B CIngredient Percent by Weight______________________________________tridecyl stearate 50 50 50 50sulfonated petroleum 30 27 30 35productcorn oil glyceride 20ethoxylated with 10 molsethylene oxidepolyethylene glycol (10) 23oleateoleic acid ethoxylated 20 15with 5 mols e. o.static, millivolts 55 25 48 70yarn to metal friction, 420 390 360 390gramsyarn to yarn friction,gramsslip 643 635 705 785stick 953 1133 1195 1310oil on yarn, % by 1.0 0.9 0.9 0.9weight, based on yarnweight______________________________________
The static property of the yarn finishes is measured by using a Valchem Friction Analyzer which is similar to the apparatus of the yarn to metal test described in ASTM 3108-72T. In place of the strain gages an eye through a pair of copper electrodes utilizes the Farraday cage principle to detect the amount of static generated across a metal pin. The Farraday "eye" is located just downstream from the pin over which the yarn coated with finish passes traveling at 200 feet per minute. The static is measured with an electrometer, amplified and recorded in millivolts.
As can be seen above, tridecyl stearate with the emulsifier and antistatic agents switched from Finish I and Finish II, i.e., Finish A above, has high yarn to metal friction and poorer static property. Using other emulsifiers gave poorer static properties, also.
Table C, below, shows the processing results of the finishes of this invention, I and II, compared with other finishes; note, that only finishes I and II combine retention of finish after jet texturing, low yarn to metal friction, good package formation, good tufting (into carpet) performance and excellent texturing performance. Each of the other finishes is deficient in one or more of these properties, even though the componenets are similar.
Sulfonated petroleum product is define in U.S. Pat. No. 3,781,202.
TABLE C__________________________________________________________________________ Finish Compositions I II D E F III.sup.1__________________________________________________________________________Refined coconut oil 63 59 Lubricanttridecyl stearate 55 50 Lubricantisodecyl stearate 63 Lubricantbutyl stearate 50 Lubricantpolyethylene glycol (10) oleate 23 Emulsifierpolyethylene glycol (10) corn oil 20 Emulsifiersulfated petroleum product 27 12 12 10 Antistatsulfated glycerol triolate 25 Antistatsorbitol oleate + 40 ethylene oxide 25 Emulsifierpolyethylene glycol oleate 25 Emulsifiersorbitan oleate 25 Emulsifiertallow amine + 20 ethylene oxide 25 Antistat__________________________________________________________________________ Finish CompositionsFiber ProcessingData I II D E F III__________________________________________________________________________% finish on .80 .85 .85 .80 .95 .78undrawn yarn% finish after .75 .81 .85 .50 .44 .77jet draw-texturePackage formation.sup.4 2.2 2.0 1.5 1.3 2.4 .5Yarn to Metal 75 65 90 50 60 90friction texturedyarn in gramsTexturizing E E F P P Gperformance.sup.2Tufting G G F F P Gperformance.sup.3__________________________________________________________________________ .sup.1 III is spin finish described in U.S. Pat. No. 3,781,202, Table I. .sup.2 draw-steam jet textured at 5000 fpm 3tufting performance per 50 yards carpet, 180 ends on 30" slat type tufting machine 5/32" gauge G = good -- less than 25 pull backs & 15 snags F = fair -- less than 50 pull backs & 30 snags P = poor -- more than 50 pull backs & 30 snags .sup.4 package formation -- average rating 20 packages 0 = sluffing off end 1 = severe bulge on sides 2 = slight bulge on sides 3 = straight sides -- no bulge
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A spin finish composition for nylon feeder yarn to be processed at high temperature into carpet yarn, such as by steam jet texturing, comprising tridecyl stearate with a specific emulsifier and an antistatic agent results in improved processing and better quality yarn, and yarn packages.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention generally relates to a dispenser for small objects, such as candy, pills, tablets, and other objects of similar size. In particular, the present invention relates to a dispenser having a housing and a cover that can be opened to multiple different stable opened positions, including a stowed position in which the cover is substantially flush with the housing and does not extend substantially beyond the boundaries of the housing.
[0003] 2. Related Background Art
[0004] Dispensers for small objects, such as candy, pills, tablets, and other objects of similar size are well known in the art. Such dispensers take a variety of forms. For example, they may be formed of a hollow body and a separately formed top portion, the top portion comprising a flat surface having an aperture and a closure element that allows access to objects within the hollow body of the dispenser through the aperture when open, while securing objects within the hollow body when closed. Such dispensers may require lifting or pressing the closure element in order to open the aperture. Examples of dispensers of these types can be found in U.S. Pat. Nos. 4,538,731, 5,636,732, 4,144,985, 5,273,177 and 4,095,712.
[0005] Other dispensers comprise box-like containers with lids that slide open, e.g., U.S. Design Pat. No. 407,972, lids that rotate open, e.g., U.S. Pat. Nos. 2,979,223, 5,709,305 and 5,718,347, or lids that slide and rotate open, e.g., U.S. Pat. No. 3,741,430. Still other dispensers comprise box-like containers with drawers that slide out of the containers, e.g., U.S. Design Pat. No. 400,006 and U.S. Pat. Nos. 3,833,143, 3,888,350, 4,113,098 and 4,126,224. A number of these dispensers include locking mechanisms to keep the dispenser securely closed, for example, to prevent young children from having access to pills stored in the dispenser.
[0006] One problem of conventional dispensers such as those mentioned above is that, while such dispensers are generally designed to be compact, they tend to lose their compact size when they are placed in a fully opened position in order to dispense the contents. Thus, for example, in dispensers having a drawer, the drawer may be virtually the same size as the container, so that opening the drawer causes the dispenser to increase in size to up to twice its closed size. In dispensers having a lid, when the lid is opened the lid generally protrudes to a great extent, since the lid is often as wide or as long as one of the dimensions of the container.
[0007] While U.S. Pat. No. 5,203,469 discloses a tool box having a lid that can be stored flat against the bottom of the box, in order to store the lid in this fashion the lid must be disengaged from the box, inverted, and then reattached to the box. This is a cumbersome and inconvenient way of storing the lid and retaining the compact size of the opened box.
[0008] Another problem occurring in conventional dispensers is the inability to be opened into a plurality of different stable opened states, which are stably open to different degrees so as to allow different rates of dispensing. Thus some dispensers have only a single opened state, e.g., a state designed for dispensing a small amount of the contents or a state designed for dispensing the entire contents, but do not have both of these states or additional states which would allow for multiple dispensing rates.
[0009] Another problem occurring in conventional dispensers is accidental spillage. For example, some dispensers permit being opened only to a wide open state, in which accidental spillage can easily occur. Relatedly, other dispensers allow for a plurality of opened states whereby the dispenser can be opened to different degrees, but do not permit an opened state designed for dispensing only a small amount of the contents. Again, in some dispensers that allow for such a plurality of opened states, these states are not stable. That is, the user may not be able to rely on the dispenser's remaining in a particular (partly) opened state. Rather, the dispenser may easily, and without the user so intending, open itself to a wider opened state, which may cause the contents to spill out against the user's wishes. In addition, some conventional dispensers, especially those with locking mechanisms, such as childproof dispensers, require a significant amount of force to open them. When using such a dispenser, the user can easily unintentionally cause the dispenser to suddenly open to a state that is opened to a greater extent than desired, which can easily cause accidental spillage of the contents.
[0010] Another problem with conventional dispensers is the presence of protrusions, rough edges, sharp points or the like, which can snag or tear a user's clothing or scratch a user's hand. Such hindrances tend to be present especially when the dispensers are placed in an opened state, because in this state the door, flap, closure element, or the like, which often has a surface that is rough or jagged, generally protrudes from the dispenser and hangs free.
[0011] The present invention provides a dispenser that solves the above problems, as explained below.
SUMMARY OF THE INVENTION
[0012] The present invention is directed to a dispenser for storing and dispensing small objects, comprising a housing including a bottom, a front wall, a rear wall and two opposing side walls, the housing defining an interior volume and an aperture providing access to the interior volume. A cover is movably attached to the housing and has a closed position for securing objects within the interior volume and at least one opened position for displaying and/or dispensing the objects from the interior volume. Two flanges depend from the cover. The flanges are functionally engaged respectively with the sides walls of the housing such that the cover is laterally movable with respect to the housing, selectively rotatable about an axis defined in the housing, and movable into the closed and opened positions including a stowed position in which the cover is opened and the cover is substantially flush with the housing.
[0013] Yet another embodiment of this invention is directed to a dispenser for storing and dispensing small objects, comprising a housing including a bottom, a front wall, a rear wall and two opposing side walls, the housing defining an interior volume and an aperture providing access to the interior volume. A cover is movably attached to the housing and has a closed position for securing objects within the interior volume and at least one opened position for displaying and/or dispensing the objects from the interior volume. Two flanges depend from the cover. The flanges are functionally engaged respectively with the sides walls of the housing such that the cover is laterally movable with respect to the housing, selectively rotatable about an axis defined in the housing, and movable into the closed and opened positions including a stowed position in which the cover is opened and in which the cover does not extend substantially beyond planes of the front wall and the side walls.
[0014] Yet another embodiment of this invention is directed to a dispenser as in the previous embodiment wherein, when the cover is in the stowed position, the cover also does not extend substantially beyond the plane of the rear wall.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIGS. 1 A- 1 E are top perspective views of a dispenser of the invention. In particular, FIG. 1A shows a cover of the dispenser in the fully closed position. FIG. 1B shows the cover in a first opened position. FIG. 1C shows the cover rotating. FIG. 1D shows the cover in a fully opened position. FIG. 1E shows the cover in a fully opened and stowed position.
[0016] FIGS. 2 A- 2 E are bottom perspective views of a dispenser of the invention, showing the cover of the dispenser in the same positions as shown in FIGS. 1 A- 1 E, respectively.
[0017] FIGS. 3 A- 3 E are sequential schematic illustrations of the relative movement and cooperative relationship between the components of a dispenser of the invention. In these figures, the positions of the cover correspond respectively to those of FIGS. 1 A- 1 E and 2 A- 2 E.
[0018] [0018]FIG. 4 illustrates, from the underside, a cover of a dispenser of the invention disengaged from a housing.
[0019] [0019]FIGS. 5A and 5B are schematic views showing, when viewed from the interior or underside, the upper portion of the housing and portions of the cover visible through the aperture of the housing or around the edges of the upper portion of the housing. FIG. 5A shows the cover in a fully closed position, for illustrating the operation of stops in stopping the cover from moving beyond the front wall of the housing and the operation of the catch in locking the cover in the fully closed position. FIG. 5B shows the cover in a first stable opened position, for illustrating the operation of a rib in stabilizing the cover in the first stable opened position and in facilitating the shift in movement of the cover from sliding to rotating.
[0020] [0020]FIG. 6 is a perspective view showing a housing of a dispenser of the invention in an opened or unassembled state.
[0021] [0021]FIG. 7 is a perspective view showing how the cover of FIG. 4 is engaged with the housing of FIG. 6, when the housing of FIG. 6 is in a closed or assembled state.
[0022] [0022]FIG. 8 is a schematic view for illustrating an embodiment of the invention in which the cover is fully stowed underneath the housing in an opened position, whereby the cover does not extend beyond the boundaries of the housing.
[0023] FIGS. 9 A- 9 C are schematic views for illustrating an embodiment of the invention in which the dispenser is formed more in the shape of a cube and additional grooves are provided in the side walls of the housing, whereby the cover is stowed flush against the rear wall of the housing rather than against the bottom of the housing.
[0024] [0024]FIG. 10 is a schematic view for illustrating an embodiment of the invention in which grooves are provided on extended flanges of the cover and projections engaging the grooves are provided at the rear of the side walls of the housing.
[0025] FIGS. 11 A- 11 F are perspective views for illustrating an embodiment of the invention in which flanges of the cover hang down on the inside of the side walls of the housing, and grooves are formed on the inside of the side walls.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The present invention is directed to a dispenser for small objects, such as candy, pills, tablets, and other objects having a similar size. As used herein the term “small objects” refers to pieces of candy, pills, tablets, and any other object having a similar size that may be stored in and dispensed from the dispenser of the invention.
[0027] First Embodiment
[0028] A first embodiment of the invention, with modifications, will now be described.
[0029] A dispenser in accordance with the invention is generally illustrated in FIGS. 1 A- 1 E, 2 A- 2 E and 3 A- 3 E. FIGS. 1 A- 1 E show the dispenser in a top perspective view, with the cover in different positions from fully closed to fully opened and stowed. FIGS. 2 A- 2 E show the dispenser in a bottom perspective view, with the cover in the same positions as shown in FIGS. 1 A- 1 E. FIGS. 3 A- 3 E illustrate schematic views of the relative movement and cooperative relationship between the components of the dispenser, with the cover in the same positions as shown in FIGS. 1 A- 1 E. Dispenser 10 comprises a housing 11 , a dispensing aperture 12 in housing 11 , an interior volume 13 within housing 11 , and a cover 14 removably and selectively movably attached to housing 11 . Dispenser 10 is designed to hold and dispense candy or other small objects, such objects being visible in FIGS. 1 B- 1 E. Cover 14 has a fully closed position, as illustrated in FIGS. 1A, 2A, and 3 A, and multiple dispensing and displaying positions, selectively illustrated in FIGS. 1 B- 1 E, 2 B- 2 E and 3 B- 3 E.
[0030] In this illustrated embodiment, dispenser 10 has a preferred shape of ergonomic curvature, although it will be readily appreciated that the shape may be altered. Housing 11 has a top 15 , a bottom 16 , a front wall 17 , a rear wall 18 , and parallel side walls 19 . Bottom 16 , rear wall 18 , and side walls 19 are roughly planar, although with smoothed or rounded edges. Top 15 and front 17 are gently curved, also with smoothed or rounded edges. Top 15 is partly cut-out. Each of the two side walls 19 has a groove 20 provided therein.
[0031] Cover 14 comprises a front tab portion 21 , a rear flap portion 22 , and two side flanges 23 each overlapping a side wall 19 of housing 11 . Each side flange 23 has a projection 24 provided therein facing side walls 19 . Projections 24 fit into grooves 20 in side walls 19 such that cover 14 can slide back and forth along grooves 20 . As shown, for example, in FIG. 3A, when cover 14 is slid forward, projections 24 are moved in grooves 20 in the direction of front wall 17 . As shown, for example, in FIG. 3B, when cover 14 is slid backward, projections 24 are moved in grooves 20 in the direction of rear wall 18 .
[0032] In addition to sliding, cover 14 can also be partly rotated about pivotal axis A when cover 14 is slid sufficiently rearward along grooves 20 , as illustrated in FIGS. 1C, 1D, 2 C, 2 D, 3 C and 3 D. As shown in FIGS. 3 A- 3 E and also by the dotted line in FIG. 5B, pivotal axis A is defined by the line joining the center points of projections 24 when projections 24 are at the rearmost position in grooves 20 . Thus, pivotal axis A is parallel to planes including top 15 , bottom 16 , front wall 17 , and rear wall 18 , and pivotal axis A is perpendicular to side walls 19 . As shown in FIG. 3A, if cover 14 is not slid sufficiently rearward along grooves 20 , then rear flap portion 22 of cover 14 is blocked by top 15 of housing 11 , and cover 14 will not be able to rotate about pivotal axis A. Only when cover 14 is slid sufficiently rearward, as shown in FIG. 3B, can rear flap portion 22 of cover 14 clear rear wall 18 of housing 11 , such that cover 14 may be rotated, as shown in FIGS. 3C and 3D.
[0033] Thus, cover 14 can be positioned in a closed position (e.g. FIGS. 1A, 2A and 3 A) or in any one of a plurality of opened positions (e.g. FIGS. 1 B- 1 E, 2 B- 2 E and 3 B- 3 E). The closed position and at least some of the opened positions are stable positions such that, once the cover 14 is placed in such a position by the user, cover 14 will not easily slide out of the position of its own accord without the application of intentional force from the user. A first stable opened position is shown in FIGS. 1B, 2B and 3 B. In this position, the cover is opened a small amount. This position is designed for dispensing or displaying single objects or small amounts of objects from the dispenser. A second stable opened position is shown in FIGS. 1E, 2E and 3 E. In this position, the cover is fully opened and also stowed beneath the housing. This position is designed for dispensing or displaying large amounts of the objects in the dispenser. Because the dispenser allows for a plurality of opened positions, the convenience with which the dispenser may be used and the number of ways in which the dispenser may be used is increased. In addition, accidental spillage of the contents of the dispenser is avoidable because the dispenser admits of a stable opened position designed for dispensing single objects or small amounts of objects from the dispenser.
[0034] Moreover, since, as explained, cover 14 cannot be rotated until it is slid sufficiently rearward in grooves 20 , cover 14 cannot be moved directly, that is, in a single, uninterrupted motion, from a completely closed position (e.g. FIGS. 1A, 2A and 3 A) to a completely opened position (e.g. FIGS. 1D, 1E, 2 D, 2 E, 3 D and 3 E). This too prevents accidental spillage of the contents of the dispenser, precluding the dispenser from being suddenly—and without the user's intention—opened to a wide opened position.
[0035] After rotation about pivotal axis A, cover 14 may be again slid along grooves 20 . Specifically, cover 14 may now be slid along grooves 20 so as to be stowed underneath housing 11 , while dispenser 10 remains in a fully opened position. In the stowed position (FIGS. 1E, 2E and 3 E), cover 14 is substantially flush with housing 11 and (except for the slight thickness of cover 14 itself) does not extend substantially beyond the boundaries of housing 11 , i.e., beyond top 15 , bottom 16 , front wall 17 , rear wall 18 , and side walls 19 , except for a small portion of cover 14 which extends beyond rear wall 18 . In the stowed position, cover 14 is relatively unobtrusive and removed from view, and the dispenser as a whole retains its compact size. In this position, virtually the entire contents of dispenser 10 may be displayed and objects may easily be dispensed from dispenser 10 at a high dispensing rate. In addition, in this position, the exterior surfaces of dispenser 10 become almost as smoothed all over as they are when cover 14 is in the fully closed position (FIGS. 1A, 2A and 3 A). That is, when cover 14 is in the fully opened and stowed position, as when cover 14 is in the fully closed position, the totality of exterior surfaces of dispenser 10 is relatively free of projections, rough edges, sharp corners, or the like, which could get caught in or snag a user's clothing or scratch a user's body.
[0036] As shown in FIGS. 4, 5A and 5 B, cover 14 may also have one or more stops 25 provided on the underside of cover 14 , a catch 26 on a leading edge of cover 14 (here shown on the leading edge of front tab portion 21 ), and a rib 27 on the underside of cover 14 toward the rear of cover 14 . Stops 25 serve to stop cover 14 from sliding further forward when cover 14 has reached the fully closed position. Catch 26 serves to prevent cover 14 from opening (sliding backward) accidentally from a closed position, which could cause unwanted spillage. If catch 26 is provided, then cover 14 is lifted slightly to begin rearward sliding motion of cover 14 to open dispenser 10 . Rib 27 serves to keep cover 14 from accidentally sliding backward, and hence to keep cover 14 fixed in position, when cover 14 is in the first stable opened position discussed above and illustrated in FIGS. 1B, 2B and 3 B. Rib 27 also facilitates the rotation of cover 14 , helping to stop cover 14 from continuing to slide backward and helping to translate the user's application of force to slide cover 14 rearward into a force acting to shift cover 14 upward so as to rotate cover 14 .
[0037] The formation of dispenser 10 will now be discussed with reference to FIGS. 4, 6 and 7 .
[0038] Housing 11 may be formed from a single piece of flexible material by, e.g., vacuum molding, injection molding, or blow molding. As shown in FIG. 6, housing 11 is preferably formed as a single piece comprising an upper portion 28 and a lower portion 29 joined by a living hinge 30 . However, housing 11 can be formed as multiple pieces that are molded separately, and attached one to the other by any means known in the art, such as, e.g., a hinge comprising a pin that allows two pieces to be rotatably connected.
[0039] With housing 11 formed in the preferable manner identified, dispenser 10 may be filled either by opening housing 11 into its two component portions, as shown in FIG. 6, or by opening cover 14 , as discussed above. Forming housing 11 as two connected portions also facilitates cleaning the interior of housing 11 .
[0040] [0040]FIG. 4 shows cover 14 by itself, and FIG. 7 shows how cover 14 and housing 11 may be assembled together. Front tab portion 21 , rear flap portion 22 and flanges 23 of cover 14 are preferably not separately formed elements, but formed simply as integral sections of cover 14 , whereby front tab portion 21 , rear flap portion 22 , flanges 23 and the remainder of cover 14 constitute one continuous, smooth-surfaced member. However, these elements could be formed as separate pieces attached by any means known in the art.
[0041] As seen in FIG. 7, flanges 23 may be formed of material sufficiently flexible that a user may pull them outward from side walls 19 , disengaging projections 24 from grooves 20 , so that cover 14 may be removed entirely from housing 11 , and later snapped back on. Of course, flanges 23 should be formed of a material sufficiently resilient, and/or grooves 20 should be sufficiently deep and projections 24 sufficiently long, that when cover 14 is engaged with housing 11 , there is no danger of cover 14 accidentally coming apart from housing 11 .
[0042] Housing 11 , cover 14 and all of their component parts may be formed from any appropriate material, such as, e.g., polystyrene, polyvinyl chloride, or polypropylene. To allow viewing of the contents, housing 11 and/or cover 14 may be formed from a clear plastic, such as, e.g., polystyrene or clarified polypropylene.
[0043] Other Embodiments
[0044] [0044]FIG. 8 shows another embodiment of the dispenser of the invention. In the preceding embodiment, cover 14 is only partly stowed under housing 11 , in the sense that a small portion of cover 14 including front tab 21 extends beyond the boundaries of housing 11 , specifically, beyond the plane of rear wall 18 . In the present embodiment, cover 14 may be fully stowed, in the sense that cover 14 does not extend beyond the boundaries of housing 11 . Specifically, in the present embodiment, grooves 20 are made longer. That is, grooves 20 are formed so as to extend farther toward front wall 17 . This allows cover 14 , after rotation, to be slid along grooves 20 farther in the direction of front wall 17 , so that cover 14 no longer extends beyond rear wall 18 . In addition, in this embodiment, rear flap 22 of cover 14 is made slightly shorter so that, when cover 14 is thus slid farther along grooves 20 toward front wall 17 , into the fully stowed position, rear flap 22 does not extend beyond the plane of front wall 17 . In this way, cover 14 may be stowed such that it does not extend beyond the boundaries of housing 11 . It is noted that extending grooves 20 in the direction of front wall 17 does not pose a problem of allowing cover 14 to be slid too far forward when the user is placing cover 14 in the closed position, because stops 25 prevent cover 14 from being slid too far forward, as shown in FIG. 5A.
[0045] FIGS. 9 A- 9 C illustrate another embodiment of the dispenser of the invention. In this embodiment, cover 14 is stowed flush against rear wall 18 rather than against bottom 16 , as in the previous embodiments. This is achieved by forming dispenser 10 more in the shape of a cube and extending grooves 20 in side walls 19 . Specifically, at the rearmost points of grooves 20 , grooves 20 are extended, at a 90 degree angle, in the direction of bottom 16 . In this arrangement, when cover 14 is slid back in grooves 20 , cover 14 is rotated only 90 degrees, and is then slid downward in the direction of bottom 16 along the extended portions of grooves 20 . In this way, cover 14 may be stowed flush against rear wall 18 rather than against bottom 16 .
[0046] [0046]FIG. 10 shows another embodiment of the dispenser of the invention. In this embodiment, the position of grooves 20 and projections 24 are reversed. That is, grooves 20 are formed in cover 14 , and projections 24 are formed on housing 11 . In order to achieve this, flanges 23 of cover 14 are formed in a longer, rectangular shape so as to accommodate grooves 20 . Projections 24 are provided at the rear of side walls 19 of housing 11 .
[0047] FIGS. 11 A- 11 F show another embodiment of the dispenser of the invention. In this embodiment, side flanges 23 hang down on the interior of side walls 19 of housing 11 , rather than on the exterior. In addition, grooves 20 are formed on the interior of side walls 19 rather on the exterior. Each side flange 23 has a projection 24 provided therein facing a respective side wall 19 , and projections 24 fit into grooves 20 such that cover 14 can slide back and forth along grooves 20 . Continuous slots may be formed in top 15 , rear wall 18 and bottom 16 , as necessary to allow cover 14 to rotate as in the first embodiment.
[0048] This invention is not limited by the embodiments disclosed herein and it will be appreciated that numerous modifications and embodiments may be devised by those skilled in the art. Therefore, it is intended that the appended claims cover all such modifications and embodiments that fall within the true spirit and scope of the present invention.
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A dispenser for small objects, such as candy, pills, tablets, and other objects of similar size. The dispenser includes a housing having a bottom, a front wall, a rear wall and two opposing side walls. The housing defines an interior volume and an aperture providing access to the interior volume. A cover is movably attached to the housing and has a closed position for securing objects within the interior volume and at least one opened position for displaying and/or dispensing the objects from the interior volume. Two flanges depend from the cover. The flanges are functionally engaged respectively with the sides walls of the housing such that the cover is laterally movable with respect to the housing, selectively rotatable about an axis defined in the housing, and movable into the closed and opened positions including a stowed position in which the cover is opened, the cover is substantially flush with the housing and, except for the thickness of the cover, the cover does not extend substantially beyond the planes of the front wall and the side walls.
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit under 35 U.S.C. §119(e) of Spanish Patent Application No. ES 200901039, filed Apr. 21, 2009, which application is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to fittings for attaching the vertical tail stabilizer of an aircraft and more particularly to fittings manufactured in composite.
BACKGROUND OF THE INVENTION
Despite the trend in recent years to implement the use of composites, such as the CFRP (Carbon Fiber Reinforced Plastic), in the largest possible number of components of an aircraft due to the weight savings that this material entails with respect to aluminum (the preferred metallic material used in aircraft), most aircraft manufacturers are hesitant to use carbon fiber to manufacture fittings, because their complexity makes them rather expensive to manufacture.
This is especially applicable to the fittings used for attaching vertical tail stabilizers which continue to be made with metallic materials.
The use of metal fittings as elements for attaching components made with composite materials in fuselage areas of the aircraft also made with composite materials brings forth several problems, such as their greater weight, and particularly those problems relating to the reduction of the effective skin area and to the assembly difficulties.
It is possible to manufacture fittings with composites having a shape similar to that of metallic fittings but, besides the cost resulting from the complex shape, they present, among others, the drawback that it is very difficult to achieve with this shape an optimized laminate structure able to perform the required load distribution.
The present invention aims to solve these drawbacks.
SUMMARY OF THE INVENTION
An object of the present invention is to provide fittings integrally manufactured with composite material for attaching the vertical tail stabilizer in the rear area of a structured aircraft fuselage based on a skin manufactured with composite material as a unitary piece, and on frames also manufactured with composite material.
It is another object of the present invention to provide fittings for fixing the vertical tail stabilizer in the rear area of an aircraft fuselage which can be easily assembled.
In a first step, these and other objects are achieved with a fitting comprising:
A first piece manufactured with composite material comprising lugs for fixing the vertical tail stabilizer and vertical walls for fixing the fitting to the fuselage frames. At least one pair of additional pieces manufactured with composite material comprising horizontal walls for fixing the fitting to the fuselage skin.
In a first kind of fitting, these pair of additional pieces have an angular shape and are designed so that their horizontal walls are fixed to the skin by their inner face, and so that their vertical walls are fixed to the first piece. A suitable fitting for fixing the vertical tail stabilizer with a vertical load is thus achieved.
In another kind of fitting, the fitting also comprises a second pair of additional pieces, also manufactured with a composite material, with an angular shape, designed so that their horizontal walls are fixed to the skin by their upper face, being their vertical walls fixed to the lugs of the first piece. A suitable fitting for fixing the vertical tail stabilizer with an inclined load is thus achieved.
In a second step, these and other objects are achieved by providing assembly processes for these fittings.
In a preferred embodiment, the assembly of the fitting intended for fixing the vertical tail stabilizer with a vertical load comprises the following steps:
Assembling the first piece on the inner part of the skin, having previously incorporated the bushings in the boreholes of the lugs. Assembling the pair of additional pieces fixing the horizontal walls to the skin by means of a mechanical attachment and fixing the vertical walls to the first piece by means of a mechanical attachment or a chemical attachment.
A very simple assembly process requiring no additional tasks in the final assembly line is thus achieved.
In another preferred embodiment, the assembly of the fitting intended for fixing the vertical tail stabilizer with an inclined load comprises the following steps:
Assembling the first piece on the inner part of the skin. Assembling the first pair of additional pieces fixing the horizontal walls to the skin by means of a mechanical attachment and fixing the vertical walls to the first piece by means of a mechanical attachment or a chemical attachment. Assembling the second pair of additional pieces fixing the horizontal walls to the skin by means of a mechanical attachment and fixing the vertical walls to the lugs by means of a chemical attachment or by means of installing the bushings which must be incorporated in the boreholes of both elements.
A simple assembly process for this type of fitting is thus achieved.
Other features and advantages of the present invention will become apparent from the following detailed description of illustrative embodiments of its object in relation to the attached drawings.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a fitting for fixing a vertical tail stabilizer fixed on an aircraft rear fuselage, according to the known art.
FIG. 2 is a perspective view of the fitting of FIG. 1 .
FIGS. 3 a and 3 b are, respectively, cross sections of FIG. 1 according to axes A-A and B-B.
FIGS. 4 a and 4 b are perspective views of a fitting for fixing a vertical tail stabilizer with a vertical load according to the present invention.
FIG. 5 is a cross-section view of the fitting of FIGS. 4 a and 4 b.
FIGS. 6 a and 6 b are perspective views of a fitting for fixing a vertical tail stabilizer with an inclined load according to the present invention.
FIG. 7 is a cross-section view of the fitting of FIGS. 6 a and 6 b.
DETAILED DESCRIPTION OF THE INVENTION
In order to better understand the invention, we will first describe a fitting for fixing a vertical tail stabilizer known in the art in relation to FIGS. 1-3 .
It relates to a fitting 11 of a piece comprising lugs 15 , 15 ′ to receive the load element of the vertical stabilizer, a pair of horizontal walls 21 , 21 ′ which are fixed to the skin 5 and a pair of vertical walls 27 , 27 ′ (continuous or segmented in two parts as shown in FIG. 2 , depending on the location of the fitting) which are fixed to the frames 7 of the fuselage. FIGS. 3 a and 3 b show the corresponding attachments in detail.
As a person skilled in the art will understand, the terms “horizontal” and “vertical” must not be interpreted in a strict geometric sense, but rather as terms to merely identify the mentioned components of the fitting. In addition, the shape of the central body 13 of the fitting 11 can differ from some fittings to others depending on their location.
As previously indicated, the basic problems brought forth with metallic fittings having the shape of fitting 11 , apart from their weight, are determined by their assembly conditions. Since it is a unitary machined piece, the adjustment for the assembly must be done in contact with the skin 5 and the boreholes 19 , 19 ′ of the lugs 15 , 15 ′ must be re-worked in situ in order to assure that their axis is located in the correct position, which requires an in situ installation of the bushings that must be assembled therein in order to adjust to the attachment bolt for fixing the element of the vertical tail stabilizer with the lugs 15 , 15 ′ between which it is introduced.
These same types of problems will occur in the case of a fitting of composite material having a similar shape and, in addition, the problem relating to the difficulty of optimizing its laminates, since the conditioning factors of the load distribution would require high thickness in some components, particularly in the lugs 15 , 15 ′, as suggested in the graphic depiction of FIG. 2 .
In relation to the state of the art, the basic idea of the present invention is to configure the fitting in two or more parts which facilitate both the optimization of the laminates of its different components, together with its assembly.
In a preferred embodiment of the invention for fittings for fixing vertical tail stabilizers with a vertical load, the fitting 41 , illustrated in FIGS. 4-5 , comprises three pieces, all of which are manufactured in a composite material:
A first piece 43 comprises lugs 45 , 45 ′ for fixing the vertical tail stabilizer and vertical walls 47 , 47 ′ for the fixing to the fuselage frames. The unitary-piece configuration of this piece 43 facilitates its assembly. A pair of pieces 49 , 49 ′ (colored in black in FIG. 4 a ) having an angular shape, and having horizontal walls 51 , 51 ′ for fixing the fitting 41 to the skin 5 of the fuselage, also having vertical walls 53 , 53 ′ intended to be fixed to the central body 44 of the first piece 43 .
Piece 43 is fixed on the inner part of the skin 5 of the fuselage (requiring a smaller cavity), having a configuration allowing it to be easily placed in its correct position whereby the boreholes 48 , 48 ′ of the lugs 45 , 45 ′ can incorporate the aforementioned bushings 50 , 50 ′, preventing having to assembly them in situ.
Next, the pieces 49 , 49 ′ are fixed to the central body 44 of the piece 43 in the final assembly line, whereby their correct positioning is assured, preferably by mechanical means and particularly by means of rivets, although in the case of the vertical walls 53 , 53 ′ they can also be attached by chemical means and particularly by means of adhesives. The possible gap between the horizontal walls 51 , 51 ′ and the skin 5 of the fuselage can be covered with a suitable filling layer.
This partition of the fitting 41 into pieces 43 , 49 , 49 ′ allows optimizing its corresponding laminates depending on the loads each of them has to support. Piece 43 needs a high percentage of plies in the same direction as the leading load whereas pieces 49 , 49 ′ need a stacking that is more oriented towards passing the shear loads to the skin 5 of the fuselage.
In another preferred embodiment for fittings for fixing vertical tail stabilizers with an inclined load, the fitting 71 , illustrated in FIGS. 6-7 , comprises five pieces, all of which are manufactured with composite material:
A first piece 73 comprises the lugs 75 , 75 ′ for fixing the vertical tail stabilizer and vertical walls 77 , 77 ′ for the attachment to the fuselage frames. A pair of pieces 79 , 79 ′ (colored in black in FIG. 6 a ) having an angular shape, having horizontal walls 81 , 81 ′ for fixing the fitting to the skin of the fuselage, being their vertical walls 83 , 83 ′ intended for being attached to the central body 74 of the first piece 73 . A second pair of additional pieces 90 , 90 ′ (colored in black in FIG. 6 a ) having an angular shape, designed so that in the operation for fixing the fitting, their horizontal walls 91 , 91 ′ are fixed to the skin by their upper face, being their vertical walls 93 , 93 ′ fixed to the lugs 75 , 75 ′ of the first piece 73 .
The first piece 73 of the fitting 71 is fixed on the inner part of the skin 5 of the fuselage like in the previous case and, in a similar way, can be easily placed in its correct position whereby the boreholes 78 , 78 ′ of the lugs 75 , 75 ′ are located in their final position, without the need of being reworked.
The pieces 79 , 79 ′ are fixed, like in the previous case, to the central body 74 of the piece 73 in the final assembly line, whereby their correct positioning is assured, preferably by mechanical means and particularly by means of rivets, although in the case of the vertical walls 83 , 83 ′ they can also be attached by chemical means and particularly by means of adhesives. The possible gap between the horizontal walls 81 , 81 ′ and the skin 5 of the fuselage can be covered with a suitable filling layer.
For their part, pieces 90 , 90 ′ are fixed on the outer part of the skin 5 in the final assembly line, whereby their correct positioning is assured. Their vertical walls 93 , 93 ′ are fixed to the lugs 75 , 75 ′ by means of adhesives or simply by means of the bushings 80 , 80 ′ which are introduced in the boreholes 78 , 78 ′ of both pieces, being their horizontal walls 91 , 91 ′ fixed to the skin 5 by means of rivets. The possible gap between the horizontal walls 91 , 91 ′ and the skin 5 of the fuselage can be covered with a suitable filling layer.
This partition of the fitting 71 into pieces 73 , 79 , 79 ′, 90 , 90 ′ allows optimizing its corresponding laminates depending on the loads each of them has to support.
The complementary function provided by the vertical walls 93 , 93 ′ of pieces 90 , 90 ′ for the lugs 75 , 75 for withstanding the inclined load of the stabilizer can be observed in this sense. In fact, and as it is shown in FIGS. 6 a and 6 b , the surface of these vertical walls 93 , 93 ′ is larger than that of the lugs 75 , 75 ′.
It must be taken into account to that respect that when the load acting on the fitting 71 does not vertically comes into contact with the lugs 75 , 75 ′, the direction of the load does not coincide with the direction of 0° of its laminates, which is the main one, which would force, when using the conventional configuration, to a very high thickness of the lugs 75 , 75 ′, causing the length of the bushings 80 , 80 ′ to possibly be greater than the distance between said lugs 75 , 75 ′.
The modifications comprised within the scope defined by the following claims can be introduced in the embodiments described above.
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A fitting is provided to fix a vertical tail stabilizer of an aircraft to a composite skin and a composite frame of the aircraft in an area of a rear fuselage thereof. The fitting includes a first composite piece having lugs to attach to the vertical tail stabilizer and having vertical walls to fix the fitting to the composite frame of the rear fuselage. The fitting further includes at least one pair of additional composite pieces, each having a horizontal wall to fix the fitting to the composite skin of the rear fuselage. A second pair of additional composite pieces may be provided to further secure the fitting to the skin of the aircraft.
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FIELD OF THE INVENTION
[0001] The present invention relates to methods for making and using the antimicrobial fiber for healthcare and medical use. The present invention relates to antimicrobial fiber which is made from plant fiber and contains, preferably, about 0.1% to 1.5% by weight of nanosilver particles (diameter between 1 nm and 100 nm) attached thereto. A nanosilver content outside the aforementioned range may also provide satisfactory results. The nanosilver particles are prepared without the use of additional reducing agents. The antimicrobial fiber is preferably used in making cloth particularly for treatment of patients with burns or wounds. The cloth can be used to make clothes such as underwear, socks, shoe cushions, shoe linings, bed sheets, pillow cases, towels, women hygiene products, laboratory coats, and medical robes.
DESCRIPTION OF THE RELATED ART
[0002] Metals including silver, copper, mercury, and zinc are known for anti-bacterial properties. Bacteria treated by these metals do not acquire resistance to the metals. Therefore, the bactericidal metals have advantages over the conventional antibiotics which often cause the selection of antibiotic-resistant microorganism.
[0003] Silver is generally a safe and effective antimicrobial metal. Silver ions function in adversely affecting cellular metabolism to inhibit bacterial cell growth. When silver ions are absorbed into bacterial cells, silver ions suppress respiration, basal metabolism of the electron transfer system, and transport of substrate in the microbial cell membrane. Silver has been studied for antibacterial purposes in the form of powder, metal-substituted zeolite, metal-plated non-woven fabric, and silver-containing crosslinked compound.
[0004] Nano technology is the study and treatment of substance and material in a nanometer range. Nanometer equals to 10 −9 meter. The internationally acclaimed range for research and study for the nano technology is between 0.1 nm and 100 nm. The technology has been applied in the areas of information technology, energy, environment, and biotechnology. Particularly, the technology has been used in medicine including drug carrier, cell dye, cell separation, clinical diagnosis, and disinfection.
[0005] In the late eighteenth century, western scientists confirmed that colloidal silver, which had been used in oriental medicine for centuries, was an effective antibacterial agent. Scientists also knew that the human body fluid is colloidal. Therefore, colloidal silver had been used for antibacterial purposes in the human body. By the early nineteenth century, colloidal silver was considered the best antibacterial agent. However, after the discovery of antibiotics, due to the fact that antibiotics were more potent which could in turn generate more revenue, antibiotics had substituted colloidal silver as the main choice for antibacterial agents.
[0006] Thirty years after the discovery of the antibiotics, many bacteria developed resistance to the antibiotics, which became a serious problem. Since 1930s, silver, particularly colloidal silver, has once again been recognized for antibacterial use, particularly due to its ability for not causing drug-resistance.
[0007] Antibacterial cloth containing metallic particles (particularly copper, silver, and zinc in the form of zeolite) is known in the field for a long time. Many methods for incorporating the metal ions directly into a cloth or fabric have been proposed. However, in the methods in which the metals are used directly, the incorporation of metals lead to very expensive products, with heavy weights as they are necessarily used in a large amounts.
[0008] There are also methods teaching the use of a polymeric substance to hold the metallic ions. For example, the method of binding or adding fine wires or powder of the metals themselvers to a polymer and the methods of incorporating compounds of the metals into a polymer. However, the products obtained by these methods shows poor durability of antibacterial performance and can be utilized only for restricted purposes because the metal ions are merely contained in or attached to the polymer and, accordingly, they easily fall away from the polymer whiles being used.
[0009] For example, Japanese Patent No. 3-136649 discloses an antibacterial cloth used for washing breasts of milk cow. The Ag + ions in AgNO 3 are crosslinked with polyacrylonitrile. The antibacterial cloth has demonstrated anti-bacterial activity on six (6) bacterial strains including Streptococcus and Staphylococcus.
[0010] Japanese Patent No. 54-151669 discloses a fiber treated with a solution containing a compound of copper and silver. The solution is evenly distributed on the fiber. The fiber is used as an anti-bacterial lining inside boots, shoes, and pants.
[0011] U.S. Pat. No. 4,525,410 discloses a mixed fiber assembly composed of low-melting thermoplastic synthetic fibers and ordinary fibers which are packed and retained with specific zeolite particles having a bactericidal metal ion.
[0012] U.S. Pat. No. 5,180,402 discloses a dyed synthetic fiber containing a silver-substituted zeolite and a substantially water-insoluble copper compound. The dyed synthetic fiber is prepared by incorporating a silver-substituted zeolite in a monomer or a polymerization mixture before the completion of polymerization in the step of preparing a polymer for the fiber.
[0013] U.S. Pat. Nos. 5,496,860 and 5,561,167 disclose antibacterial fiber including an ion exchange fiber and an antibacterial metal ion entrapped within the ion exchange fiber through an ion exchange reaction. The ion exchange fiber has sulfonic or carboxyl group as the ion exchange group.
[0014] U.S. Pat. No. 5,897,673 discloses fine metallic particles-containing fibers with various fine metallic particles therein, which have fiber properties to such degree that they can be processed and worked, and which can exhibit various functions of the fine metallic particles, such as antibacterial deodorizing and electron-conductive properties as provided.
[0015] U.S. Pat. No. 5,985,301 discloses a production process of cellulose fiber characterized in that tertiary amine N-oxide is used as a solvent for pulp, and a silver-based antibacterial agent and optionally magnetized mineral ore powder are added, followed by solvent-spinning.
[0016] The materials of the prior art involving the use of zeolite do not have sufficiently antibacterial activity due to lack of sufficient surface contact between the bactericidal metal and the bacteria, especially in water. The bactericidal activity of these materials rapidly diminishes as the silver ions become separated from the supports, especially in water. Most importantly, these materials do not show bactericidal activity over a prolonged period of time and the crosslinking may introduce compounds that cause allergy in patients.
[0017] There is yet another approach of making antibacterial cloth such as by inserting a layer of metallic yarn between a woven fabric. For example, Japanese laid-open patent publication (unexamined) No. Hei 6-297629 discloses an antibacterial cloth in which an inner layer member containing copper ion in a urethane foam resin is inserted in a cloth-like outer layer member. The outer layer member is composed of a cotton yarn serving as a weft formed by entangling an extra fine metallic yarn of copy or the like and a rayon yarn serving as a warp. A warp is the thread of a woven fabric which are extended lengthwise in the loom. A weft is the thread of a woven fabric that cross from side to side of the web and interlace the warp. This type of antibacterial cloth is heavy and hard. In addition, the extra fine metallic yarn is easy to cut, thus, causing problems to wash the cloth repeatedly. It may also injure a user due to the cut metallic yarn.
[0018] Recently, Chinese Patent No. 921092881 discloses a method for making antibacterial fabric with long lasting broad-spectrum antibacterial effect against more than 40 bacteria. The fabric is manufactured by dissolving silver nitrate in water, adding ammonia water into the solution to form silver-ammonia complex ion, adding glucose to form a treating agent, adding fabric into the treating agent, and ironing the fabric by electric iron or heat-rolling machine.
[0019] The present invention provides an antimicrobial fibers having nanosilver particles adhered thereto that is very effective over a broad spectrum of bacteria, fungi, and virus. The antimicrobial fiber of the present invention does not lose the antimicrobial strength over time, and the fiber is especially effective in water. The preferred fibers used in the present invention are entirely or at least partially plant fibers. Other types of fibers which are derivate of glucose may also be used to provide satisfactory results; their color can be natural or dyed. The antimicrobial fibers of the present invention is non-toxic, safe and thus suitable for use in healthcare related purposes.
[0020] The present invention also provides a method for making the antimicrobial fibers which is very simple, fast and easy to carry out. The use of reducing agents is completely eliminated in the process of the present invention, thus, the silver-containing processing solution is more stable and can be stored for much longer without precipitation of silver particle. The method of the present invention also produces reliable results and can be applied in small and industrial scale production.
SUMMARY OF THE INVENTION
[0021] The present invention provides an antimicrobial fibers which contains nanosilver particles in the diameter of about 1-100 nm. The total weight of silver in the fibers is preferably about 0.1%-1.5% by weight. The nanosilver particles are attached to the fibers. Cotton, linen, blending fabric, or any combination therewith can be used as materials for the fibers. The fibers can be in its natural color or dyed with different colors.
[0022] The silver of the nanosilver particles is made by reducing silver ion or silver-ammonia complex without using additional reducing agent.
[0023] The fibers has antimicrobial effects against bacteria, fungi, and/or chlamydia, which include, but are not limited to, Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus ( Salmonella morgani ), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, and Salmonella paratyphi C.
[0024] The antimicrobial fibers can be used to make cloth (such as bandage, gauze, and surgical cloth) with antimicrobial activity, particularly to be used for treating patient with burn and scald-related skin infection, wound-related skin infection, dermal or mucosal bacterial or fungal infection, surgery cut infection, vaginitis, and acne-related infection.
[0025] Additionally, the cloth with antimicrobial activity can be used make antibacterial clothes or clothing such as underwear, socks, shoe cushions, shoe linings, bed sheets, pillow shams, towels, women hygiene products, laboratory coat, and patient clothes.
[0026] The present invention also provides methods for manufacturing the antimicrobial fibers. The method includes the following steps: (1) preparing a silver-containing solution with silver nitrate or other suitable silver salts with appropriate solubility in water, which dissociate to silver ion (Ag + ), or with other silver salts without appropriate solubility in water and ammonia water, which form silver ammonia complex ion with improved, needed solubility in water. (2) soaking the plant fiber in the silver-containing solution or spraying the silver-containing solution to the plant fiber. (3) dehydrating or drying the plant fiber having absorbed silver-containing solution to form the antimicrobial fiber attached by silver particles with the size of 1-100 nm. Preferably, the plant fiber is predegreased before soaking in the silver-containing solution. After soaking in the silver-containing solution, the plant fiber may be treated with heat, for example, at 120° C.-200° C. for about 40-60 minutes. Other temperatures and duration may also provide satisfactory results.
[0027] For each liter of the silver containing solution, it is preferred that it contains 1 g-15 g of silver. The resulting nanosilver particles are sized between 1 nm to 100 nm in diameter and the antimicrobial fibers containing about 0.1% to 1.5% by weight of silver in a form of attached nanosilver particles.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The present invention provides methods to manufacture plant fiber which has a long-lasting effect and can be in the form of raw material, yarn, used in weaving and knitting to form cloth, or nonwoven cloth, composed of either natural or man-made fibers, or blend with synthetic fibers. The antimicrobial fibers contains nanosilver particles having diameters in the range of 1 nm to 100 nm. The nanosilver particles are attached to the fibers and contribute to the antimicrobial effects. The silver content in the antimicrobial fiber is 0.1% to 1.5% by weight of the total weight of the fibers.
[0029] The plant fibers are cotton, linen or blending fabric with synthetic fiber, or a combination therewith. The fibers can be either in its natural color or dyed with various colors, and the antimicrobial capacity of the fiber (either in natural color or dyed with various colors) is retained.
[0030] The antimicrobial fibers of the present invention is non-toxic, safe, and thus, suitable for use in medical or healthcare related purposes. The antimicrobial fibers can be used to make an antimicrobial yarn, cloth and nonwoven cloth. The cloth and nonwoven cloth are suitable for use as bandage, gauze or surgery cloth. They can also be used in making clothes or clothing such as underwear, panty, shoe cushions, shoe insole, shoe lining, bedding sheets, pillow sham, towel, feminine hygiene products, medical robes etc.
[0031] The term “antimicrobial” as used in the context of “antimicrobial fiber”, “antimicrobial yarn”, “antimicrobial cloth”, “antimicrobial nonwoven cloth”, and/or “antimicrobial clothes or clothing” in the present invention means that the fiber, yarn cloth, nonwoven cloth, or clothes (or clothing) has demonstrated antibacterial, antifingal, and anti- chlamydia effects by killing and/or suppressing growth of a broad spectrum of fungi, bacteria, and chlamydia, such as Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus ( Salmonella morgani ), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, and Salmonella paratyphi C.
[0032] The antimicrobial effect of the present invention is derived from silver ions which have advantage over the conventional antibiotics, as it does not induce resistance in the microorganisms. The antimicrobial fibers of the present invention does not lose the antimicrobial strength over time, and the antimicrobial effects are especially stronger in water.
[0033] Specially, the antimicrobial fibers of the present invention is suitable for use as cloth or clothes in disinfecting and treating patient with burn and scald-related skin infection, wound-related skin infection, skin or mucosa bacterial or fungal infection, surgery cut infection, vaginitis, and acne-related infection.
[0034] The well-known Silver-Mirror Reaction uses the reaction of silver nitrate aqueous solution with ammonia water to form silver ammonia complex ion, then the ion is reduced by glucose to form metallic silver.
[0000]
[0035] The existence of glucose reducing agent makes the mixed solution quick to react forming silver precipitate even at room temperature and the process difficult to control.
[0036] Some organic substances such as sugar and starch, can react with silver nitrate to form tiny silver particles. Sugar and starch are derivatives of glucose. The cellulose of the plant fibers is derivative of glucose too. As a particular example of the present invention, we found plant fiber can make silver nitrate solution (Ag + ) or silver-ammonia complex ion solution [Ag(NH 3 ) 2 + ] reduce to form tiny silver particles at 120° C.-200° C. The silver-containing solution without reducing agents is stable and can be stored at room temperature for much longer time without forming silver particles, so the said silver-containing solution without additional reducing agents is suitable for processing solution to manufacture antimicrobial fiber containing silver, and the process is easy to control.
[0037] The antimicrobial activity of the silver can further be explained by the following reaction:
[0000]
[0038] Silver nitrate is one of the most powerful chemical germicides and is widely used as a local astringent and germicide. However, the nitrates irritate the skin. Thus, it is preferable to reduce the silver nitrate to metallic silver. When the metallic silver is in contact with an oxygen metabolic enzyme of a microorganism, it becomes ionized. And, as shown in the above reaction, the silver ion interacts with the sulfhydryl group (—SH) of the enzyme in the microorganism and forms an —SAg linkage with the enzyme, which effectively blocks the enzyme activity.
[0039] The antimicrobial fiber of the present invention is prepared according to the following flow chart:
[0000]
[0040] First, dissolving silver nitrate in water to form an aqueous solution of silver nitrate. Then the above solution is diluted with additional water to make the volume up to the needed. The silver containing aqueous solution is used as the soaking solution for the fiber. For 200 kg of fiber, about 1 kg-10 kg of silver nitrate, and about 500 L (liters) of water are required.
[0041] The plant fiber is preferred to be de-greased prior to the soaking. The degreased process for the fiber is commonly known in the art. After soaking in the silver containing solution for an appropriate period of time, the soaked fiber is dehydrated followed by drying under heat.
[0042] The resulting antimicrobial fiber has advantages of long-lasting effect, broad spectrum antimicrobial activity, non-toxic, non-stimulating, natural, and suitable for medicinal uses. The antimicrobial activity of the fiber is stronger when in water. Because reducing agents are not used in the process for making the antimicrobial fiber, the process is more economical and easy to control. The process of the present invention is suitable for both small scale and industrial scale production.
[0043] The following examples are illustrative, and should not be viewed as limiting the scope of the present invention. Reasonable variations, such as those occur to reasonable artisan, can be made herein without departing from the scope of the present invention.
Example 1
Preparation of the Small Scale of Antimicrobial Yarn
(1) Preparation of Silver Containing Solution
[0044] (a) Silver nitrate solution:
[0000]
AgNO
3
3.9
g
Dissolved
in
150
ml
of
water
[0045] (b) Silver-containing solution:
[0046] The silver-containing solution was prepared by diluting the silver nitrate solution with additional water to make the volume up to 250 ml.
(2) Preparation of Antimicrobial Yarn
[0047] The antimicrobial yarn was prepared as follows:
[0048] (a) Naturally white, degreased yarn (10 g) was immersed in the silver containing solution of (1). The yarn was squeezed and rolled in the solution so that the yarn was fully absorbed with the processing solution.
[0049] (b) The silver containing solution was partly removed from the yarn by centrifugation (such as in a washing machine) and dried in an oven at 120-160° C.
[0050] (c) The dried yarn was washed with water, and dried again in the oven to obtain the antimicrobial yarn of the present invention which showed an orange color.
Example 2
Preparation of Industrial Scale of Antimicrobial Yarn
(1) Preparation of Silver Containing Solution
[0051] (a) Silver nitrate solution:
[0000]
AgNO
3
5.5
g
Dissolved
in
200
L
of
water
[0052] The silver nitrate aqueous solution was prepared by dissolving 5.5 kg of silver nitrate in 200 L of water at room temperature in a 500-litre container.
[0053] (b) Silver containing solution:
[0054] The silver containing solution was prepared by mixing the silver nitrate solution with the additional water. Additional water was added to the mixture to make the volume up to 500 L.
[0055] (2) Preparation of Antimicrobial Yarn
[0056] The antimicrobial yarn was prepared as follows:
[0057] (a) Naturally white, degreased yarn (200 g) was immersed in the silver containing solution of (1). The yarn was squeezed and rolled in the solution so that the yarn was fully absorbed with the silver containing solution.
[0058] The silver containing solution was partly removed from the yarn by dehydration such as using centrifugation. The yarn was further dried in an oven at 120-160° C. for about 40-60 minutes.
[0059] (b) The dried yarns were washed with water, and dried again in the oven to obtain the antimicrobial yarn of the present invention which showed a yellow-orange color.
Example 3
Electron Microscopic Studies of the Antimicrobial Yarn
(1) Purpose
[0060] The yarn produced by the method described in Example 1 was analyzed for the dimension and distribution of nanosilver particles attached.
(2) Method
[0061] Five samples of the antimicrobial yarn prepared in Example 1 (supra) was examined according to the procedure described in the JY/T011-1996 transmission electron microscope manual. JEM-100CXII transmission electron microscope was used with accelerating voltage at 80 KV and resolution at 0.34 nm.
(3) Result
[0062] Six batches of the antimicrobial yarn samples were examined and all contained nanosilver particles which were evenly distributed to the yarn. Batch No. 010110 contained about 62% of nanosilver particles that were under 10 nm in size, about 36% that were about 10 nm, in size, and about 2% that were 15 mn in size. Batch No. 001226 contained about 46% of nanosilver particles that were under 10 nm in size, about 47% that were about 10 nm in size, and about 7% that were about 15 nm in size. Batch number 001230 contained about 65% of nanosilver particles that were under 10 nm in size, about 24% that were about 10 nm in size, and about 11% that were about 15 nm in size. Batch No. 010322-1 contained about 89% of nanosilver particles that were under 10 nm in size, about 8% that were about 10 nm in size, and about 3% that were about 15 nm in size. Batch No. 011323 contained about 90% of nanosilver particles that were under 10 nm in size, about 7% that were about 10 nm in size, and about 3% that were about 15 nm in size. Batch No. 010322-2 contained 70% of nanosilver particles that were under 10 nm in size, about 12% that were about 10 nm in size, and about 13% that were about 15 nm size. Chemical testing indicated that the silver content in the yarn was about 0.4%-0.9% by weight.
[0063] (4) Conclusion
[0064] The foregoing results demonstrated that the antimicrobial yarn contained nanosilver particles with diameters below 20 nm. These nanosilverparticles were evenly distributed to the yarn.
Example 4
Broad Spectrum of Antimicrobial Activity of the Yarn
(1) Purpose
[0065] The antimicrobial yarn prepared in Example 1 was examined to determine the antimicrobial activity of the yarn.
(2) Method
[0066] Both the antimicrobial yarn of the present invention (the experimental group) and the yarn without the attachment of nanosilver particles (the control group) were tested in the test tubes.
[0067] Microbial strains tested were Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus ( Salmonella morgani ), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, and Salmonella paratyphi C. These strains were either isolated from clinical cases or purchased as standard strains from Chinese Biological Products Testing and Standardizing Institute.
[0068] Two sets of test tubes, each containing a triplicate of various microbial strains were prepared by inoculating the microbial strains into the test tubes containing a meat broth. Then, equal weights of the yarns from the present invention and from the control group were inserted into the test tubes. The test tubes were then cultured at 37° C. for 18-24 hours. At the end of the incubation, an aliquot of the broth from each of the test tube was taken out and spread onto a Trypticase soy blood agar plate. The blood agar plate was incubated at 37° C. for 18-24 hours.
(3) Results
[0069] No colony or sign of any microbial growth was observed on the blood agar plate of the experimental group, as opposed to those of the control group where signs of microbial growth were seen.
(4) Conclusion
[0070] The antimicrobial yarn of the present invention demonstrated effective antimicrobial activity against various bacteria, fungi, and chlamydia.
Example 5
Long Lasting Effect of Antimicrobial Activity of the Yarn
(1) Purpose
[0071] The antimicrobial yarn of Example 1 of the present invention was examined for the antimicrobial activity over a prolonged period of time. The antimicrobial activity of the yarn after repeated washes was also conducted.
(2) Method
[0072] The antimicrobial yarn of the present invention was washed according to the washing procedure as provided in the Function Treatment of the Fabric, Chinese Textile Publishing House (January 2001) as follows:
[0073] (a) 2 g of neutral soap solution (1:30) was dissolved in one litre of water to obtain a wash fluid;
[0074] (b) a yarn from the experimental group or the control group as described in Example 4 was washed using the wash fluid of (a) at room temperature for 2 minutes;
[0075] (c) The yarn was rinsed in water;
[0076] (d) After every five washes in the wash fluid, the yarn was dried at 60° C.
[0077] (e) After 100 times of washing procedure according to (a) to (d), nine batches of antimicrobial yarn were tested for antimicrobial activity of Staphylococcus aureus, Escherichia coli, Candida albicans, and Pseudomonas aeruginosa according to the method provided in Example 4.
(3) Result
[0078] No colony or any signs of microbial growth were observed in the yarn of the experimental group, as opposed to those in the control group where signs of microbial growth were observed.
(4) Conclusion
[0079] The above results indicate that the yarn of the present invention was very effective and long lasting as antimicrobial agent even after repeated washes.
Example 6
Antimicrobial Activity of the Yarn Made with Different Materials or Dyed with Different Colors
(1) Purpose
[0080] The antimicrobial activity of the yarn of the present invention prepared from different materials or dyed with various colors was examined.
(2) Method
[0081] (a) The yarn (from the experimental group or the control group) which was made from cotton, linen, blending fabric, or which was dyed in black, blue, red, orange, and yellow was prepared.
[0082] (b) The yarns of (i) were tested for antimicrobial activity on Staphylococcus aureus, Escherichia coli, Candida albicans, and Pseudomonas aeruginosa, according to the method provided in Example 4.
(3) Result
[0083] No colony or any signs of microbial growth were observed in the yarn of the experimental group, as opposed to those in the control group where signs of microbial growth were observed.
(4) Conclusion
[0084] The antimicrobial yarn of the present invention made from different materials, which included cotton, linen, silk, wool, leather, blending fabric, or synthetic fiber, or dyed with different colors, was very effective as antimicrobial agent, suggesting the materials or dying methods would not and did not hinder the antimicrobial activity of the nanosilver particles-containing yarn.
Example 7
Preparation of Antimicrobial Nonwoven Fabric
(1) Preparation of Silver-Containing Solution
[0085] 107 g of powdered silver oxide and 100 g of citric acid hydrate was, in sequence, added to 15 L of deionized water with stirring at room temperature, forming a suspension of salt of citric acid. Concentrated ammonia water was then added to the suspension with stirring until clear solution formed. Additional water was added to the solution to make the volume up to 20 L.
(2) Preparation of Antimicrobial Nonwoven Fabric
[0086] 1 kg of nonwoven fabric was immersed in silver-containing solution to absorb the solution. The part of the absorbed solution was removed. The dehydrated fabric was dried in an oven at 120-160° C. for 40-60 minutes. After being washed with water, the fabric was dried again. Thus, antimicrobial nonwoven fabric was obtained.
(3) Determination of Silver Content
[0087] (a) Method
[0088] USPXXII (1990)P1768
[0089] (b) Result
[0090] The content of silver of the batch 030115 is 0.59% by weight.
(4) Electronmicroscopic Examination
[0091] (a) Method
[0092] The same as in Example 3.
[0093] (b) Result
[0094] The particle size of the sample of batch 030115 is smaller than 25 nm.
(5) Antimicrobial Test
[0095] (a) Method
[0096] The Ministry of Health P. R. China.
[0097] <<Technical Standard For Evaluation Of Disinfectant>>
[0098] Ed. 3, Div. 1, Section: Shaken Flask Test Method
[0099] (b) Result
[0100] The sample 030115 fully (100%) inhibited 3 test microbes ( E. coli 8099, S. aureus ATCC6538, C. albicans ATCC10231).
Example 8
Preparation of Antimicrobial Cotton
(1) Preparation of Silver-Containing Solution
[0101] 1.6 g of powdered silver oxide and 3.3 g of citric acid hydrate were, in sequence, added to 130 ml of deionized water with stirring at room temperature, forming a suspension of salt of citric acid. Concentrated ammonia water was then added to the suspension with stirring until clear solution formed. Additional water was added to the solution to make the volume up to 150 ml.
(2) Preparation of Antimicrobial Cotton
[0102] 10 g of degreased cotton was immersed in silver-containing solution and squeezed several times to fully absorb the solution. The cotton having absorbed the solution was centrifuged to remove part of the absorbed solution. The dehydrated cotton was dried in an oven at 120-160 C for 40-60 minutes. After being washed with water, the cotton was dried again, thus, antimicrobial cotton was obtained.
(3) Determination of Silver Content
[0103] (a) Method
[0104] USPXXII(1990)P1768
[0105] (b) Result
[0106] The silver content of 4 batches (011113-1, 011113-2, 011115-1, 011115-2) is 1.32%, 1.82%, 1.24% and 1.58% by weight respectively.
(4) Electronmicroscopic Examination
[0107] (a) Method
[0108] The same as in Example 3.
[0109] (b) Result
[0110] The particle size of the sample of 2 batches (011113-1, 011115-1) is smaller than 25 nm.
(5) Antimicrobial Test
[0111] (a) Method
[0112] The Ministry of Health P.R. China.
[0113] <<Technical Standard for Evaluation of Disinfectant>>
[0114] Ed.3, Div. 1, Section 2.12.2 Inhibitory Circle Test Method.
[0115] (b) Result
[0000]
Diameter of
Test microbe
inhibitory circle
S. aureus ATCC6538
16-17
mm
E. coli 8099
15-18
mm
C. albicans ATCC10231
7.5-9
mm
[0116] The diameter of inhibitory circle of the sample against 3 test microbes was larger than 7 mm. The sample 011130-1 significantly inhibited 3 test microbes.
[0117] While the invention has been described by way of examples and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications as would be apparent to those skilled in the art. Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications.
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The present invention also provides a method for making the antimicrobial plant fibers. The characteristic of the method is no need of additional reducing agent. The present invention provides plant fibers with antimicrobial effects. The antimicrobial antifungal effect of the fibers is derived from nanosilver particles (diameter between 1 and 100 nm) which are attached to the fibers. The fibers which are made of cotton, linen, blending fibers, or any combination thereof. The fibers can be used to make yarn cloth to be used particularly for treating patients with burns or wound. The cloth made from the antimicrobial fibers can be further used to make clothes such as underwears, socks, shoe cushions, shoe linings, bed sheets, pillow cases, towels, women hygiene products, laboratory coats, and medical robes.
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BACKGROUND OF THE INVENTION
This invention concerns certain pyridazinylurea compounds and their use as plant regulators.
Plant regulators are hormone-like substances which influence growth and development of plants, as inhibitors or promoters of growth. Sometimes the same compound can both inhibit and promote growth, depending upon the rate of application. Plant regulatory activity is reflected in a variety of ways, including one or more of cell enlargement, leaf and organ abscission, retardation of senescence, release of apical dominance, fruit set and growth, leaf growth, light response, protein synthesis, and other effects. In economic crops and ornamentals, plant regulators have enormous potential as herbicides, rooting promoters, flowering stimulants, fruit developers, and as agents to control or induce seedlessness, plant shape, and the setting, thinning and dropping of fruit. The most familiar classes of plant regulators are the auxins, gibberellins, cytokinins, abscisic acid and ethylene, but the search continues for even more active plant regulating compounds, including compounds having specific forms of regulator activity.
Representative of research efforts in the field are the compounds disclosed in U.S. Pat. Nos. 4,063,928 (substituted pyridinyloxy(thio)phenyl acetamides, ureas and urea derivatives), 4,193,788 (N-(2-chloro-4-pyridyl)ureas and thioureas), 4,308,054 (other pyridyl ureas) and 4,331,807 (N-(4-pyridazinyl)-N'-phenylureas).
SUMMARY OF THE INVENTION
A new class of plant regulating compounds has now been found. The compounds are pyridazinylureas of the formula (I): ##STR2## and acid addition salts thereof; wherein R is alkyl or cycloalkyl; R 1 is hydrogen or alkyl; each X independently is halogen, alkoxy, alkylthio or alkylsulfonyl; and p is 0, 1 or 2.
The compounds exhibit plant regulatory activity in terms of one or more of stunting, dessication, axillary growth stimulation, nastic response, growth stimulation, defoliation, intumescence, negative root geotropism, darker green basal leaves, leaf alteration and retardation of senescence.
DETAILED DESCRIPTION
In formula I, R, R 1 and X may contain any number of carbon atoms and any form of branching, for example, 1 to 20 carbon atoms or more. However, 1 to 8 carbon atoms are preferred, more preferably 1 to 4 carbon atoms in the case of all groups other than cycloalkyl, from the standpoint of ease of synthesis. The cycloalkyl group preferably will contain 3 to about 10 carbon atoms, such as cyclopentyl, cyclohexyl and cycloheptyl. "Halogen" means chloro, bromo, fluoro and iodo, preferably in that order, and includes mixed halogens when p is 2.
When X in formula I is halogen, such as chloro, plant regulator activity of the compounds is greater if the halogen is in the 5- and/or 6-position on the pyridazinyl ring.
The acid addition salts of the compounds of formula I include organic and inorganic salts such as the hydrochlorides, sulfates, phosphates, citrates and tartrates.
The compounds of formula I wherein R is other than cycloalkyl are prepared in a generally known manner by nitrating pyridazine with a mixture of fuming sulfuric and nitric acids, reducing the nitro group to amino by hydrogenation over palladium on carbon, and coupling with an isocyanate (R--NCO). For preparation of compounds of formula I wherein R is alkyl or cycloalkyl and R' is alkyl, the amino intermediate is reacted with phenyl chloroformate to form a phenyl N-(pyridazinyl)carbamate intermediate which is then reacted with an alkyl amine (mono or di) or a cycloalkyl amine to form the corresponding monoalkyl, dialkyl or cycloalkyl product. Alternatively, an aminopyridazine intermediate is prepared by aminating a chloropyridazine and hydrogenating over palladium on carbon. The aminopyridazine is then reacted with an appropriate isocyanate (R--NCO) to form the pyridazinyl urea. The reactions are conducted in appropriate organic solvents with appropriate pressure and temperature controls. The work-up and isolation procedures are conventional.
Further details of synthesis are given in the representative examples below. Table I following the examples lists the compounds of the examples and other compounds of the invention. In compound 6 of Table I, p is 2. In all other compounds of Table I, p is 1 or 0 (X=hydrogen).
EXAMPLE 1
Synthesis of N-(4-pyridazinyl)-N'-(1-methylethyl) urea (Compound No. 1)
Step A: 4-Aminopyridazine
A solution of 10.1 grams (0.055 mole) of 3,4,5-trichloropyridazine in 100 ml of absolute ethanol, in a 200 ml pressure bottle, is cooled to 0° C. and saturated with ammonia gas. The bottle is sealed and the reaction mixture stirred at ambient temperature for 4 days. The reaction mixture is purged with nitrogen for 2 hours, then filtered to remove ammonium chloride. The filter cake is washed with anhydrous ethanol. The filtrate and washes are placed in a Parr hydrogenation bottle and 5.2 grams (0.13 mole) of sodium hydroxide and 0.6 gram of 10% palladium on carbon are added. The volume of the mixture is brought to 200 ml with absolute ethanol. The mixture is hydrogenated for 4 hours using a Parr hydrogenator, during which time the theoretical amount of hydrogen is taken up. The hydrogenation bottle is purged with nitrogen and the reaction mixture filtered through diatomaceous earth. The filtrate is concentrated under reduced pressure to a residue. The residue is dried under reduced pressure at ambient temperature for several hours. The residue is triturated with 250 ml of ethyl acetate, and the mixture allowed to stand for 7 days under anhydrous conditions. The mixture is filtered to collect a solid, which is dried under reduced pressure at 40° C. to yield 3.9 grams of 4-aminopyridazine. The nmr spectrum is consistent with the proposed structure.
Step B: N-(4-pyridazinyl)-N'-(1-methylethyl)urea
To a stirred solution of 2.3 grams (0.024 mole) of 4-aminopyridazine (prepared as in Example 1, Step A) and 0.5 gram (0.004 mole) of 1,4-diazabicyclo[2.2.2]octane in 20 ml of dimethylformamide is added dropwise 3.3 ml (0.033 mole) of (1-methylethyl) isocyanate. Upon completion of addition the reaction mixture is stirred at ambient temperature for two days. The reaction mixture is concentrated under reduced pressure and the solid residue dried at 60°-70° C. The solid is stirred with ethanol and collected by filtration to yield 1.9 grams of N-(4-pyridazinyl)-N'-(1-methylethyl)urea; m.p. 206°-209° C. then 266°-269° C. The nmr spectrum is cnsistent with the proposed structure.
EXAMPLE 2
Synthesis of N-(4-pyridazinyl)-N'-cyclopentylurea (Compound No. 9)
Step A: Phenyl N-(4-pyridazinyl)carbamate
A stirred suspension of 2.6 grams (0.027 mole) of 4-aminopyridazine (prepared as in Example 1, Step A) in 100 ml of tetrahydrofuran is cooled to 0° C. and 4.6 ml (0.033 mole) of triethylamine is added in one portion. A solution of 4.1 ml (0.033 mole) of phenyl chloroformate in tetrahydrofuran is added dropwise during a 30 minute period. Upon completion of addition the reaction mixture is allowed to warm to ambient temperature where it is stirred for three days. The reaction mixture is concentrated under reduced pressure to a residue. The residue is taken up in 500 ml of chloroform and filtered to collect 1.9 grams of phenyl N-(4-pyridazinyl)carbamate; m.p. 184°-185° C. The filtrate is washed with water, then dried with magnesium sulfate. The mixture is filtered and the filtrate placed on a column of silica gel. Further elution is accomplished using 10% methanol in methylene chloride. The appropriate fractions are combined and concentrated under reduced pressure to yield an additional 1.8 grams of phenyl N-(4-pyridazinyl)carbamate. The nmr spectra are consistent with the proposed structure. The reaction is repeated several times.
Step B: N-(4-pyridazinyl)-N'-cyclopentylurea
A stirred solution of 2.0 grams (0.009 mole) of phenyl N-(4-pyridazinyl)carbamate and 1.0 ml (0.010 mole) of cyclopentylamine in tetrahydrofuran is heated under reflux for 18 hours. The reaction mixture is filtered and the filtrate concentrated under reduced pressure to a residue. The residue is purified by column chromatography on silica gel. Elution is accomplished with 10% methanol in methylene chloride. The appropriate fractions are combined and concentrated under reduced pressure to yield 0.2 gram of N-(4-pyridazinyl)-N'-cyclopentylurea. This material is combined with the identical product from a previous reaction to yield 0.5 gram; m.p. 192°-195° C., dec. The nmr spectrum is consistent with the proposed structure. The reaction is repeated several times.
EXAMPLE 3
Synthesis of N-(4-pyridazinyl)-N'-cycloheptylurea (Compound No. 11)
This compound is prepared in the manner of Example 2, Step B, using 4.0 grams (0.019 mole) of phenyl N-(4-pyridazinyl)carbamate and 2.1 grams (0.019 mole) of cycloheptylamine in tetrahydrofuran. The yield of N-(4-pyridazinyl)-N'-cycloheptylurea is 2.0 grams; m.p. 226°-228° C. The nmr spectrum is consistent with the proposed structure. The reaction is repeated several times.
EXAMPLE 4
Synthesis of N-(6-chloro-4-pyridazinyl)-N'-(1-methylethyl)urea (Compound No. 2)
Step A: 3-hydrazino-4-amino-6-chloropyridazine
A stirred solution of 2.0 grams of 4-amino-3,6-dichloropyridazine and 2.5 ml of hydrazine hydrate in 20 ml of ethanol is heated under reflux for three hours. After this time water is added to the reaction mixture and the resultant precipitate collected by filtration. The filter cake is recrystallized from ethanol to yield 2.3 grams of 3-hydrazino-4-amino-6-chloropyridazine; m.p. 190° C.
Step B: 4-amino-6-chloropyridazine
A stirred solution of 1.2 grams of 3-hydrazino-4-amino-6-chloropyridazine and 15 ml of aqueous 8% sodium hydroxide solution is heated under reflux for 30 minutes. The reaction mixture is treated with decolorizing carbon and filtered. The filtrate is neutralized with aqueous 50% acetic acid and the resultant precipitate is collected by filtration. The filter cake is recrystallized from water to yield 0.8 gram of 4-amino-6-chloropyridazine, m.p. 153°-154.5° C.
Step C: N-(6-Chloro-4-pyridazinyl)-N'-(1-methylethyl)urea
To a stirred solution of 0.8 gram of 4-amino-6-chloro-pyridazine in 30 ml of dimethylformamide is added 0.2 gram of 1,4-diazabicyclo[2.2.2]octane, followed by 0.6 gram of 1-methylethyl isocyanate. The reaction mixture is stirred at ambient temperature for 18 hours, then at 60° C. for six hours. The majority of the dimethylformamide is removed under reduced pressure, and the residue is slurried in water. The resultant solid is collected by filtration and dried to yield N-(6-chloro-4-pyridazinyl)-N'-(1-methylethyl)urea.
EXAMPLE 5
Synthesis of N-(5,6-dichloro-4-pyridazinyl)-N'-(1-methylethyl)urea (Compound No. 6)
Step A: 4,5-dichloro-3-pyridazone
A stirred solution of 3.9 grams of mucochloric acid in water is warmed to 8°-100° C., and a mixture of 3.1 grams of hydrazine sulfate and 3.0 grams of sodium acetate is added. A solid is collected by filtration and recrystallized from water to yield 3.0 grams of 4,5-dichloro-3-pyridazone; m.p. 199°-200° C. The reaction is repeated several times.
Step B: 3,4,5-trichloropyridazine
A stirred solution of 20.0 grams of 4,5-dichloro-3-pyridazone in 150 ml of phosphorus oxychloride is heated under reflux for five hours. The excess phosphorus oxychloride is removed under reduced pressure, and the residue poured into ice water. The mixture is extracted with diethyl ether. The extract is dried with magnesium sulfate, filtered, and the filtrate concentrated to a residue. The residue is distilled under reduced pressure. A fraction, b.p. 117°-118° C./14-15 mm, 20 grams, solidifies on standing. The solid is recrystallized from acetone-water to yield 3,4,5-trichloropyridazine; m.p. 61° C.
Step C: Mixture of aminodichloropyridazines
Dry ethanol is saturated with ammonia gas and placed in a sealed tube with 8.0 grams of 3,4,5-trichloropyridazine. The reaction mixture is heated at 120°-130° C. for five hours. The tube is opened and the reaction mixture concentrated under reduced pressure. The residue is dissolved in 20 ml of chloroform and the solution heated under reflux for 20 minutes. The solution is allowed to cool to ambient temperature for several hours in place. A solid precipitate is collected by filtration and repeatedly recrystallized from water to yield 2.8 grams of 4-amino-3,5-dichloropyridazine; m.p. 176°-178° C. The filtrate is concentrated under reduced pressure and the residue recrystallized from water to yield 2.0 grams of 4-amino-5,6-dichloropyridazine; m.p. 150°-151° C.
Step D: Phenyl N-(5,6-dichloro-4-pyridazinyl)carbamate
A stirred suspension of 2.0 grams (0.012 mole) of 4-amino-5,6-dichloropyridazine in 75 ml of tetrahydrofuran is cooled to 0° C. and 1.5 grams (0.015 mole) of triethylamine is added in one portion. A solution of 2.3 grams (0.015 mole) of phenyl chloroformate in tetrahydrofuran is added dropwise during a 30 minute period. Upon completion of addition the reaction mixture is allowed to warm to ambient temperature where it is stirred for three days. The reaction mixture is taken up in 500 ml of chloroform and filtered to collect 0.98 gram of phenyl N-(5,6-dichloro-4-pyridazinyl)carbamate. The filtrate is concentrated under reduced pressure to a residue. The residue is subjected to column chromatography on silica gel to yield an additional 0.9 gram of phenyl N-(5,6-dichloro-4-pyridazinyl)carbamate.
Step E: N-(5,6-dichloro-4-pyridazinyl)-N'-(1-methylethyl)urea
A stirred solution of 1.0 gram (0.004 mole) of phenyl N-(5,6-dichloro-4-pyridazinyl)carbamate and 0.27 gram (0.005 mole) of 1-methylethylamine in tetrahydrofuran is heated under reflux for 18 hours. The reaction mixture is filtered and the filtrate concentrated under reduced pressure to a residue. The residue is purified by column chromatography to yield 0.1 gram of N-(5,6-dichloro-4-pyridazinyl)-N'-(1-methylethyl)urea.
EXAMPLE 6
Synthesis of N-(4-pyridazinyl)-N'-cyclopentyl-N'-methylurea (Compound No. 12)
A stirred solution of 2.0 grams of phenyl N-(4-pyridazinyl)carbamate (prepared as in Example 2, Step A) and 0.9 gram of N-cyclopentyl-N-methyl amine in tetrahydrofuran is heated under reflux for 18 hours. The reaction mixture is filtered and the filtrate concentrated under reduced pressure to a residue. The residue is purified by column chromatography on silica gel to yield N-(4-pyridazinyl)-N'-cyclopentyl-N'-methylurea.
TABLE I__________________________________________________________________________ ##STR3##Cmpd. No. R R.sup.1 X Name__________________________________________________________________________ 1 ##STR4## H -- N(4-pyradazinyl)-N'(1-methyl- ethyl)urea 2 ##STR5## H 6-chloro N(6-chloro-4-pyridazinyl)-N' (1-methylethyl)urea 3 ##STR6## H 6-OCH.sub.3 N(6-methoxy-4-pyridazinyl)-N' (1-methylethyl)urea 4 ##STR7## H 6-SCH.sub.3 N(6-methylthio-4-pyridazinyl)- N'(1-methylethyl)urea 9 5 ##STR8## H 6-SO.sub.2 CH.sub.3 N(6-methylsulfonyl-4-pyri- dazinyl)-N'(1-methylethyl )urea 6 ##STR9## H 5,6-dichloro N(5,6-dichloro-4-pyridazinyl)-N' (1-methylethyl)urea 7 C.sub.4 H.sub.9 CH.sub.3 -- N(4-pyridazinyl)-N'butyl- N'methylurea 8 C(CH.sub.3).sub.3 CH.sub.3 -- N(4-pyridazinyl)-N'(1,1-di- methylethyl)-N'methylurea 9 C.sub.5 H.sub.9 H -- N--(4-pyridazinyl)-N'cyclopentylurea10 C.sub.6 H.sub.11 H -- N(4-pyridazinyl)-N'cyclohexylurea11 C.sub.7 H.sub.13 H -- N(4-pyridazinyl)-N'cycloheptylurea12 C.sub.5 H.sub.9 CH.sub.3 -- N(4-pyridazinyl)-N'cyclopentyl- N'methylurea13 C.sub.6 H.sub.11 CH.sub.3 -- N(4-pyridazinyl)-N'cyclohexyl- N'methylurea14 C.sub.2 H.sub.5 H -- N(4-pyridazinyl)-N'ethylurea15 C.sub.4 H.sub.9 H -- N(4-pyridazinyl)-N'butylurea16 C(CH.sub.3).sub.3 H -- N(4-pyridazinyl)-N'(1,1-di- methylethyl)urea__________________________________________________________________________
PLANT REGULATOR UTILITY
The pyridazinylurea compounds of the invention exhibit various forms of plant regulator activity when tested in vitro and in whole plant assays as described more particularly hereinbelow. Briefly, such activity is apparent in preemergence and postemergence plant response screens on a variety of plants, particularly soybean and cotton, where morphological responses include stunting, axillary growth stimulation, nastic response, defoliation, darker green basal leaves, and some herbicidal activity. In antisenescence assays, compounds of the invention cause retention of chlorophyll in excised wheat leaves and in soybean leaves and pods, while reducing abscission, thus indicating ability to retard senescence.
The plant regulators of this invention are effectively employed as plant regulators in a number of broad-leafed and grain crops, for example, soybean, lima bean, wheat, rice, corn, sorghum, and cotton, and turf grasses.
The plant regulator compounds, like most agricultural chemicals, are generally not applied full strength, but are formulated with agriculturally acceptable carriers or extenders (diluents) normally employed for facilitating the dispersion of active ingredients and various additives, and optionally with other active ingredients, recognizing that the formulation and mode of application of the active component may affect the activity of the material. The present compounds may be applied, for example, as powders or liquids, the choice of application varying with the plant species and environmental factors present at the particular locus of application. Thus, the compounds may be formulated as emulsifiable concentrates, wettable powders, flowable formulations, solutions, dispersions, suspensions and the like.
A typical formulation may vary widely in concentration of the active ingredient depending on the particular agent used, the additives and carriers used, other active ingredients, and the desired mode of application. With due consideration of these factors, the active ingredient of a typical formulation may, for example, by suitably present at a concentration of from about 0.5% up to about 99.5% by weight of the formulation. Substantially inactive ingredients such as adjuvants, diluents, and carriers may comprise from about 99.5% by weight to as low as about 0.5% by weight of the formulation. Surface active agents, if employed in the formulation, may be present at various concentrations, suitably in the range of 1 to 30% by weight. Provided below is a general description of representative formulations which may be employed for dispersion of the plant regulators of the present invention.
Emulsifiable concentrates (EC's) are homogeneous liquid compositions, usually containing the active ingredient dissolved in a liquid carrier. Commonly used liquid carriers include xylene, heavy aromatic naphthas, isophorone, and other nonvolatile or slightly volatile organic solvents. For application, these concentrates are dispersed in water, or other liquid vehicle, forming an emulsion, and are normally applied as a spray to the area to be treated. The concentration of the essential active ingredient in EC's may vary according to the manner in which the composition is to be applied, but, in general, is in the range of 0.5 to 95%, frequently 10 to 80%, by weight of active ingredient, with the remaining 99.5% to 5% being surfactant and liquid carrier.
The following are specific examples of emulsifiable concentrate formulations suitable for use in the present invention:
______________________________________ % by Wt.______________________________________Formulation 1:Active ingredient 53.01Blend of alkylbenzenesulfonate salt 6.00and polyoxyethylene ethersEpoxidized soybean oil 1.00Xylene 39.99Total 100.00Formulation 2:Active ingredient 10.00Blend of alkylbenzenesulfonate salt 4.00and polyoxyethylene ethersXylene 86.00Total 100.00______________________________________
Wettable powders, also useful formulations for plant regulators, are in the form of finely divided particles which disperse readily in water or other liquid vehicles. The wettable powder is ultimately applied to the plant as a dry dust or a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas, and other highly absorbent or adsorbent inorganic diluents. The concentration of active ingredient in wettable powders is dependent upon physical properties of the active ingredient and the absorbency characteristics of the carrier. Liquids and low melting solids (m.p. 100° C.) are suitably formulated in the concentration range of 5 to 50% by weight, usually from 10 to 30%; high melting solids (mp 100° C.) being formulated in the range of 5 to 95% by weight, usually 50 to 85%. An agriculturally acceptable carrier or diluent, frequently including a small amount of a surfactant to facilitate wetting, dispersion and suspension, accounts for the balance of the formulation.
The following are specific examples for wettable powder formulations suitable for use in the present invention:
______________________________________ % by Wt.______________________________________Formulation 3:Active ingredient 40.00Sodium ligninsulfonate/sodium 4.00alkylnaphthalenesulfonateAttapulgite clay 56.00Total 100.00Formulation 4:Active ingredient 90.00Dioctyl sodium sulfosuccinate 0.10Synthetic fine silica 9.90Total 100.00Formulation 5:Active ingredient 20.00Sodium alkylnaphthalenesulfonate 1.00Sodium ligninsulfonate 4.00Attapulgite clay 75.00Total 100.00Formulation 6:Active ingredient 25.00Base:96% hydrated aluminum magnesium silicate 75.002% powdered sodium ligninsulfonate2% powdered anionic sodium alkyl-naphthalenesulfonateTotal 100.00______________________________________
Flowable formulations are similar to EC's except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like EC's, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
The following are specific examples of flowable formulations suitable for use in the present invention:
______________________________________ % by Wt.______________________________________Formulation 7:Active Ingredient 46.00Colloidal magnesium aluminum silicate 0.40Sodium alkylnaphthalenesulfonate 2.00Paraformaldehyde 0.10Water 41.42Propylene glycol 7.50Acetylinic alcohols 2.50Xanthan gum 0.08Total 100.00Formulation 8:Active ingredient 45.00Water 48.50Purified smectite clay 2.00Xanthan gum 0.50Sodium alkylnaphthalenesulfonate 1.00Acetylinic alcohols 3.00Total 100.00______________________________________
Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1 to 15% by weight of the composition.
Other useful formulations include simple solutions or suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents. This type of formulation is particularly useful for ultra low volume application.
The following illustrate specific suspensions which are suitable for use in the present invention:
______________________________________ % by Wt.______________________________________Formulation 9:Oil Suspension:Active ingredient 25.00Polyoxyethylene sorbitol hexaoleate 5.00Highly aliphatic hydrocarbon oil 70.00Total 100.00Formulation 10:Aqueous Suspension:Active ingredient 40.00Polyacrylic acid thickener 0.30Dodecylphenol polyethylene glycol ether 0.50Disodium phosphate 1.00Monosodium phosphate 0.50Polyvinyl alcohol 1.00Water 56.70Total 100.00______________________________________
The concentration of the compound in use dilution is normally in the range of about 2% to about 0.1%. Many variations of spraying and dusting compositions in the art may be used by substituting or adding a compound of this invention into compositions known or apparent to the art.
The compositions may be formulated and applied with other suitable active ingredients, including nematicides, insecticides, acaricides, fungicides, other plant regulators, herbicides, fertilizers, etc.
In applying the foregoing chemicals, an effective growth regulating amount of the active ingredient must be applied. While the application rate will vary widely depending on the choice of compound, the formulation and mode of application, the plant species being treated and the planting density, a suitable use rate may be in the range of 0.1 to 10 kg/hectare, preferably 0.05 to about 5 kg/hectare.
The compounds of the invention were tested for plant regulator activity, first in a whole plant response screen and then in excised wheat leaf and soybean whole plant antisenescence tests.
PLANT RESPONSE SCREEN
In this assay the test compounds are applied as water-acetone (1:1) solutions, containing 0.5% v/v sorbitan monolaurate solubilizer, at a rate equivalent to 8.0 kg/ha, preemergently to planted seeds of test plants and postemergently to foliage of test plants. The test plants are soybean, cotton, corn, wheat, field bindweed, morningglory, velvetleaf, barnyardgrass, green foxtail and johnsongrass.
Compound Nos. 1, 9, 10, 11, 14 and 15 when thus-tested exhibited various forms and degrees of plant regulator activity, although not against all of the plants and to the same degree in each case. Generally, the test compounds were more active when applied post-emergently. Compound Nos. 9 and 15 were the most responsive of the test compounds, exhibiting 50 to 70% growth control against the cotton and soybean post-emergence test plants and varying forms and degrees of other regulator activity against the same and other plants, including stunting, auxiliary growth stimulation, defoliation, intumescence and darker green basal leaves. Some herbicidal activity was exhibited at the exceptionally high application rate of the tests.
WHEAT LEAF ANTISENESCENCE
In this test leaves were excised from wheat seedlings (Triticum aestivum cv. Prodax), weighed and placed in vials containing solutions of test compound in water-acetone (1:1) at concentrations of 25 ppm and 2.5 ppm. Wheat leaves were similarly placed in vials containing only deionized water, as controls. After four days of incubation at 30° C. in the dark, the test vilas were examined visually and given a numeric rating of 0 (color similar to color of the leaves in the control vials) or 1 (more green than the leaves in the control vials). The control leaves had yellowed, indicating loss of chlorophyll. The test results are set forth in Table II below, from which it will be noted that treatment at 25 ppm caused chlorophyll retention, whereby retarding senescence.
TABLE II______________________________________Chlorophyll RetentionCmpd No. Concentration (ppm) Visual Rating______________________________________ 1 25 1 2.5 0 9 25 1 2.5 010 25 1 2.5 011 25 1 2.5 014 25 1 2.5 015 25 1 2.5 0______________________________________
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Pyridazinylurea plant regulators of the formula ##STR1## and acid addition salts thereof; wherein R is alkyl or cycloalkyl, R 1 is hydrogen or alkyl, each X independently is halogen, alkoxy, alkylthi or alkylsulfonyl, and p is 0, 1 or 2.
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FIELD OF THE INVENTION
The present invention relates to a cooling sorption element with a gas-impermeable sheeting, wherein cold is generated by means of evaporation of a working medium and subsequent in vacuo sorption of the working medium vapor in a sorbent material and to a method for producing and activating these cooling elements.
BACKGROUND OF THE INVENTION
Adsorption devices are apparatuses in which a solid adsorbent material sorbs a second medium which boils at a lower temperature, the so-called working medium, in the form of a vapor while releasing heat (sorption phase). In the course of this process, the working fluid evaporates in an evaporator while sorbing heat. After the sorbent material is saturated, it can be re-desorbed when heat at higher temperatures is added to it (desorption phase). At that time, the working medium evaporates from the adsorbent material. The working medium vapor can be recondensed and can subsequently be re-evaporated in the evaporator, etc.
Absorption devices are apparatuses in which a liquid absorbent material is used. The broader term “sorption devices” includes both adsorption and absorption systems.
Adsorption apparatuses for cooling with solid sorbent materials are known from EP 0 368 111 and from DE-OS 34 25 419. Sorbent containers filled with sorbent materials draw off the working fluid medium which forms in an evaporator and sorb it while releasing heat. This heat of sorption must be dissipated from the sorbent. The cooling devices can be used for cooling and heating food products in thermally insulated containers.
WO 01/10738 A1 describes a self-cooling beverage can in which an evaporator is disposed inside and a sorber outside the can. Cooling is initiated by opening a vapor passageway between the evaporator and the sorber. Via the surfaces of the evaporator, the cold generated in said evaporator is transferred to the beverage to be cooled inside the can. The heat generated in the sorbent material is stored in a heat buffer. Compared to a conventional can, this self-cooling beverage can is modified considerably and is expensive to manufacture.
Additional theoretical embodiments of self-cooling assemblies are listed in WO 99/37958 A1. None of these devices can be implemented and produced inexpensively.
U.S. Pat. No. 6,474,100 also describes a self-cooling cooling element disposed on the outer surface of a pouch for holding liquids or bulk products. The sorbent material is enclosed in a flexible, multilayered sheeting material. Contact with the hot sorber filling is reduced to a minimum by insulating and flow materials as well as by heat-storage materials interposed in between. The temperature compensation between the hot sorber filling and the cold evaporator, large surfaces of which face each other, has to be reduced by means of a complicated insulating system.
SUMMARY OF THE INVENTION
The problem to be solved by the present invention is to make available inexpensive cooling sorption elements for generating cold as well as a method for producing same.
During the sorption process, sorbent materials may reach temperatures of more than 100° C. The multilayered sheeting materials used in the packaging industry are not suitable for such high temperatures. Especially the polyethylene layers used for sealing soften at a temperature as low as 80° C. and cause the covering layer to become permeable in vacuo. A sealing layer made of polypropylene, on the other hand, is able to withstand considerably high temperatures. Its melting point is higher than 150° C.
In combination with high temperatures, sharp edges, corners and pointed tips of sorbent granules lead to inadmissible leaks. This risk is eliminated according to the present invention by using a minimum of one polyester layer within the multilayer sheeting material. Polyester sheeting materials are especially tear- and puncture-resistant. The actual gas barrier is implemented by a layer of a thin metal sheeting material or a metallized layer. For this purpose, it proved to be useful to employ thin aluminum foil layers with a layer thickness of approximately 8 μm. Metallized plastic sheeting materials are less impermeable. If the length of storage time is short, however, it is possible to use these metallized sheeting materials as well, especially since they can be produced less expensively than the metal sheeting materials.
The separate layers of a multilayer sheeting material are joined to one another by means of adhesive layers. Commercially available adhesives contain solvents which, during bonding, are not completely removed from the adhesive layer. Over relatively long periods of time, these solvents diffuse through the inner-lying layers, in particular the polyethylene layer, and have a negative effect on the vacuum inside the cooling element. The diffusion increases at higher temperatures, such as are observed during the sorption and production process of the cooling elements. The adhesives used therefore must also be designed to be able to resist high temperatures.
According to the present invention, the multilayer sheeting materials used have a polyester layer thickness of 12-50 μm, an aluminum layer thickness of 6-12 μm, and a polypropylene layer thickness of 50-100 μm. Such sheeting materials are used, e.g., for packaging food products which after packaging are sterilized at temperatures of more than 120° C. so as to preserve them.
Even more stable multilayer sheeting materials are obtained when an additional polyester layer with a thickness of approximately 15 μm is glued between the aluminum layer and the polypropylene layer. In this case, sharp-edged or sharply pointed sorbent components are unable to advance to the gas barrier, i.e., the aluminum layer.
Multilayer sheeting materials are available, e.g., from the firm of Wipf AG in Volketswil, Switzerland. The use of such sheeting materials makes it possible to ensure leakage rates of less than 1×10 −7 mbar l/sec. Thus, a storage ability over several years is ensured, without impairment to the cooling ability.
In the food industry, the steps of heat-sealing of multilayer sheeting materials to form pouches and filling bulk materials into such pouches and subsequently evacuating them are part of prior art.
In said industry, pouches in a very large number of sizes and shapes are used. Especially worth mentioning are stand-up pouches, pouches with pour openings, pouches with cardboard reinforcement, easy-tear pouches, peel pouches for easier opening, and pouches with valves. All of these pouches with their specific properties can be used to advantage for the cooling elements according to the present invention.
When filling a solid sorbent material into pouches, dust is generated, which dust is deposited on the inside surfaces of the sheeting material. Dust on the future sealing surfaces can lead to leaks if the layer of dust is excessively thick with respect to the polypropylene layer. Polypropylene layer thicknesses between 50 and 100 μm suffice to melt fine dust particles securely and hermetically into the polypropylene layer.
The use of sheeting materials according to the present invention makes it possible to directly enclose in vacuo hot, sharp-edged and dust-releasing sorbent material without additional protective intermediate layers and to store it over a period of several years, without foreign gases which interfere with or even completely prevent the sorption reaction being able to advance from the sheeting material as such or through said material into the cooling element.
The sorbent material preferably used is zeolite. In its normal crystal structure, said zeolite can reversibly sorb up to 36 wt % water. When used according to the present invention, the industrially feasible ability to absorb water is in a range from 20-25%. Zeolites continue to have a remarkable ability to sorb water vapor even at relatively high temperatures (above 100° C.) and therefore are especially suitable for the application according to the present invention.
Zeolite is a crystalline mineral which contains silicon and aluminum oxides in its skeletal structure. This highly regular skeletal structure contains cavities in which water molecules can be sorbed while releasing heat. Within the skeletal structure, the water molecules are subjected to high field forces, the strength of which depends on the quantity of water contained in the skeletal structure and on the temperature of the zeolite.
Natural types of zeolite occurring in nature take up markedly less water. Per 100 g of natural zeolite, only 7-11 g of water are sorbed. This reduced ability to sorb water is attributable to the specific crystal structures of said zeolites, on the one hand, and to the nonactive impurities of the natural product. As a result, the use of synthetic zeolites with their higher sorbability is to be preferred for cooling elements which, during a relatively long cooling period, are also able to release heat of sorption via the outer covering layer. According to the present invention, natural zeolites are used for cooling elements with a high cooling capacity and/or a short cooling time during which the sorbent material remains relatively hot. The reason is that at high temperatures of the sorbent material, synthetic zeolites no longer have an advantage over natural zeolites. Typically, in cases of a retarded release of the heat of sorption and, associated with this, high temperatures of the sorbent material of more than 100° C., both types are able to sorb only 4-5 g of water vapor per 100 g of dry sorbent material. In this specific case, the use of the natural zeolites is economically even preferable since their price is considerably lower.
Natural zeolites have yet another advantage. The nonactive admixtures are typically in a range from 10-30%. Thus, they are not actively participating in the generation of cold, but they are still heated by the neighboring zeolite crystal. As a result, they serve as an additional built-in, inexpensive heat buffer. This has the effect that the zeolite filling becomes less hot and thus is able to sorb additional water vapor at lower temperatures.
Natural zeolite granules consist of broken and crushed fragments and therefore have sharp-edged and sharply pointed geometric shapes which, in vacuo and at increased temperatures, can pierce or cut through the outer covering layer.
Another disadvantage of natural, but also of synthetically produced, zeolites is that, depending on their occurrence and the mining techniques used, they contain impurities which, in vacuo and especially at higher temperatures, release gaseous components that have a negative effect on the cooling process.
This problem of gas release is solved in that prior to producing the cooling element, natural zeolites are heated to at least the future temperature of the sorbent material and are subsequently subjected to a vacuum. According to the present invention, in the course of this procedure, zeolites are able to release the interfering impurities. This thermal treatment is especially effective if the previously sorbed water can be evaporated at the same time. To be able to carry out this treatment at increased temperatures and to withstand the sharp-edged corners and sharply pointed tips, gas-impermeable multilayer sheeting materials with an inner polypropylene layer and a minimum of one polyester layer are used according to the present invention.
Of the approximately 30 different natural zeolites, the following can be advantageously used for the cooling elements according to the present invention: clinoptilolite, chabazite, mordenite and phillipsite.
Substances occurring in nature can also be returned to nature without worry about environmental regulations. After their use in cooling elements, natural zeolites can be used, e.g., as soil conditioners, as liquid-binding agents, or to improve the quality of the water in stagnant bodies of water.
Among the synthetic types of zeolites, the use of types A, X and Y in their inexpensive Na form is recommended.
In addition to the combination of zeolite and water, other solid sorbent material combinations are also possible for use in cooling elements according to the present invention. Especially worth mentioning are bentonites and salts which, together with water as the working medium, constitute suitable combinations. Even activated charcoal in combination with alcohols can offer an advantageous solution. Since these material combinations also work at a reduced pressure, they can be sealed into the multilayer sheeting materials according to the present invention.
According to the present invention, the quantity of sorbent material used should be dimensioned and disposed in such a way that the inflowing water vapor needs to overcome only a minimum pressure drop within the sorbent material. Especially when water is used as the working medium, the pressure drop should be less than 5 mbar. Furthermore, the sorbent material should have a sufficiently large surface for the inflowing working medium vapor to accumulate on. To ensure uniform sorption within the sorbent material as well as a low pressure drop, it was found that sorbent granules are especially useful. The best results were obtained with granule diameters between 3 and 10 mm. Such granules can be readily packed in pouches made of the sheeting material. After evacuation, said pouches form a hard, pressure-resistant and dimensionally stable sorbent container which retains the shape forced on it during the evacuation. Also of advantage are, however, stable, shape-retaining zeolite blocks preshaped from zeolite powder, with flow passageways already incorporated into them and in shapes that conform to the geometry of the desired cooling elements. In the area of the future opening for vapor, the stable zeolite blocks may have hollow spaces which facilitate the cutting of the sheeting material by means of a cutting tool and which are able to retain the punched-out piece of sheeting material so as to not inhibit the flow through the vapor passageway.
During the sorption reaction, heat of sorption which heats the sorbent material is released. At higher temperatures of the sorbent material, the sorbability for water decreases markedly. To maintain a high cooling capacity over a longer period of time, it is recommended that the sorbent material be cooled.
On direct contact of the sorbent material with the multilayer sheeting material, heat of sorption that forms can be dissipated unimpeded through the sheeting material to the outside. As a rule, the heat will be dissipated to the surrounding air. Another highly effective way to cool the sorbent material container is to use fluids, in particular water.
Since the heat transfer to an air flow from the outside of the sorbent-containing pouch is within the same range as the heat transfer from sorbent material granules to the inside of the pouch, it is recommended that large sheeting material surfaces without fluting, such as cylindrical, platelike or tubular geometries, be used. Since especially zeolite granules have a low heat conductibility, the sorbent containers should be designed so that the average heat conduction path within the sorbent material does not exceed 5 cm.
The cooling elements according to the present invention can be classified according to the following fields of application: a) Rapid cooling of a liquid (e.g., cooling an 0.75 L champagne bottle from 25° C. to 8° C. within a period of 15 min); b) Long-term cooling of an air flow (e.g., cooling an air flow in a respiratory air cooler); c) Keeping beverages and food products cold and/or warm (e.g., keeping a meal warm while simultaneously keeping a previously cooled beverage cold over a relatively long transport time); and d) Delaying the thawing process of a frozen product (e.g., keeping an ice cream container cold (below −10° C.) after removal from the freezing compartment up to the subsequent consumption or during transport).
The cooling elements according to the present invention can meet the requirements demanded by practically all of these different applications. All applications are marked by the fact that a cooling element is stored at a given temperature over an indefinite period of time. To initiate the cooling effect, the shut-off means is activated at the time desired. Beginning at this point in time, working medium vapor can flow to and accumulate in the sorbent material. The sorbent material adsorbs the vapor within its crystal structure. The evaporator cools down and can be used as a refrigeration source. In applications that require rapid cooling (e.g., cooling of a liquid), the time will generally not be long enough to substantially cool the sorbent material. The ability to sorb working medium vapor will therefore be limited because of the high temperatures of the sorbent material unless admixtures serve as heat buffers.
With a cooling element having a longer cooling time, the sorbent material will be able to dissipate heat via the multilayer sheeting material and, depending on the application, transfer this heat at a higher temperature level to a product that is to be kept warm.
In applications in the freezing temperature range, sufficiently large flow passageways and possibly additives to the working fluid that lower the freezing point will have to be considered.
To minimize the heat flow from the hot sorbent material to the cold evaporator, it is necessary to either provide for insulating materials or, as proposed by the present invention, to ensure that the two components are spatially sufficiently separated.
Especially inexpensive cooling elements can be obtained if the evaporator is also sealed into a gas-impermeable sheeting material. In vacuo, the flow passageways to the sorbent material must be retained. For this purpose, the present invention provides for spacers which allow the working medium vapor to unimpededly dissipate from the working fluid and, at the same time, ensure good thermally conducting contact between the cold surfaces and the sheeting material.
For this purpose it is also of advantage to use flexible spacers made of a plastic material, which spacers are adapted to the cooling application at hand. A prerequisite, however, is that the plastic spacers do not outgas during the storage time and thus have a negative effect on the vacuum. It is recommended that the plastic used for this purpose be polycarbonate or polypropylene since these materials can be heated to high temperatures and thus be outgassed prior to or during the manufacturing process. It is of special advantage if this increase in temperature takes place at the same time that the sorbent material is heated during the manufacture of the cooling element.
Spacers made of a plastic material can be inexpensively manufactured using conventional manufacturing methods, such as thermoforming, extrusion or blow molding. It is recommended that care be taken to ensure that no materials that will outgas at a later point in time, such as softening agents, are added during the manufacturing process.
The cooling elements can also be classified according to the shut-off means used: e) The vapor passageway from the evaporator to the sorbent material is opened (e.g., by piercing a pouch which is made of the sheeting material and which encloses the sorbent material); and f) The fluid line from a storage tank to the evaporator is opened (e.g., by bursting a water-containing pouch and allowing the water to be discharged into the evaporator). From there, it evaporates and flows on to the sorbent material.
In the first example, the multilayer sheeting material enclosing the sorbent material can be pierced. For this purpose, it is suitable to use sharp-edged cutting tools which cut a sufficiently large hole into the sheeting material. The cutting tool can be activated both from the side of the sorbent material and from the side of the evaporator. Since the sheeting materials according to the present invention are flexible, the cutting tool is actuated according to the present invention by a deformation exerted on the sheeting materials from the outside. In this manner, it is possible to design the shut-off means inexpensively and actuate them gas-impermeably.
In all cases, the cutting tool must be sufficiently sharp-edged to cut the sheeting material through the cross section required. Suitable for this purpose are, for example, cylindrically shaped expanded metals or sharp-edged injection-molded components made of a plastic material which, in addition, are also able to squeeze or move the sorbent material behind the sheeting material so as to securely cut through the sheeting material.
The same principle obviously also applies to shut-off means (scenario f) that need to provide only a small opening for the pouch made of the sheeting material and containing the fluid working medium. According to the present invention, an additional pouch made of the sheeting material and containing the appropriate quantity of working medium and having a connecting passageway can be molded onto the evaporator sheeting material. According to the present invention, the passageway disposed between the sorbent material and the fluid working medium can be shut off by providing that the sheeting material has one or more kinks in this area, thereby compressing the polypropylene layers to one another. In combination with the air pressure exerted from the outside, this measure leads to a sufficient seal between the pouch containing the working medium and the evaporator. The kinked passageway thus forms a closed fluid valve. To open said passageway, the sheeting material in the area of the passageway is simply folded back into its original shape, and the working medium is optionally pressed into the evaporator by exerting pressure on the pouch containing the working medium.
Another useful embodiment is obtained by inserting a separate pouch containing fluid working medium into the evaporator. By means of external pressure on the covering material of the evaporator, the pouch containing the working medium can be made to burst, thus allowing the fluid working medium to flow, e.g., into a nonwoven evaporator. In this case, the torn-open leakage site forms the fluid valve.
According to other embodiments, the evaporator in combination with the sorbent material can be disposed inside the sorbent-containing pouch. Only when the fluid valve allows the working medium to enter the evaporator is it possible for the working medium to evaporate from said evaporator and to flow in the form of a vapor into the sorbent material. The advantage of this type of shut-off means is that only a relatively small cross section must be opened for the fluid working medium to be able to flow through. The disadvantage, on the other hand, is that the working medium must homogeneously wet the evaporator at a sufficiently rapid speed, without being entrained in liquid form into the sorber or possibly even turning into ice as it exits the opening, which would block the further inflow.
As known, it is possible to prevent the working medium, here water, from turning to ice by admixing an agent that reduces the freezing point. An addition of common salt, e.g., can lower the freezing point down to −17° C. It suffices if the freezing point-lowering agent is simply disposed around the discharge opening of the water pouch. Only when the water exits from the opening is it mixed with the highly concentrated freezing point-lowering agent. Thus, the possibility of the water solidifying is thereby avoided. Next, the subsequently exiting water dilutes the solution and transports the working medium into all areas of the evaporator.
A homogeneous distribution of the working medium can also be implemented by means of a separate, finely branched passageway structure which homogeneously distributes the working medium after said working medium has passed through the shut-off means and before it could be entrained in liquid form by the vapor flow. Such a distribution can be inexpensively implemented by means of a layer of a finely perforated sheeting material which is disposed around the discharge opening.
Only in exceptional cases will the working medium be present in the evaporator in uncombined form. In most cases, it is distributed in an absorptive nonwoven material where it is retained by means of hygroscopic forces. Particularly inexpensive materials are absorptive papers, such as are used in many different varieties in households and industry for absorbing liquids. Like the spacers made of a plastic material or natural zeolite, the water-storing nonwoven materials should not outgas in vacuo or at high temperatures. It was found that commercially available microfibers made of polypropylene were especially suitable for this purpose. The fibers are designed to absorb water and do not emit any gases that can interfere with the vacuum.
Another solution proposed is the fixation of the working fluid in organic binding agents, e.g., in water lock of Grain Processing Corp., USA. A combination of several of the measures mentioned above may also be useful.
According to the present invention, to quickly cool a fluid in a fluid container, the outer surface of the fluid container is pressed to the evaporator surface of the cooling element. This can be very effectively implemented by disposing the fluid container directly within the evaporator sheeting material. As a result of the negative pressure between the multilayer sheeting material and the fluid container, it is possible for the spacer to press the nonwoven material at a high compressive force onto the surface of the container and thus utilize a large portion of the sometimes highly structured surface of the container for the transfer of heat.
This assembly, however, is to be recommended only if the container material as such does not emit any gas and a potentially existing closure for the future discharge of the beverage is sufficiently leakproof. If this cannot be ensured or if the outer surface of the assembly has gassing labels glue to it, the fluid container as such is first heat-sealed in vacuo into a gas-impermeable outer sheeting material. This gas-impermeable packaging can subsequently be directly disposed within the evaporator outer cover sheeting. In contrast to the multilayer sheeting material which surrounds the sorbent material, the outer cover sheeting for the fluid container need not be able to withstand high temperatures. Thus, it is possible to use, e.g., thin metallized sheeting materials with a more readily processible polyethylene layer.
Yet another solution according to the present invention provides that the evaporator structure be kept flexible and that the cold surface of the outer evaporator cover sheeting be pressed by means of a separate elastic compression means over a large surface of the outer surface of the fluid container. Suitable externally disposed elastic compression means are stretch or shrink wraps or rubber bands. The advantage of this approach is that the fluid container remains partially visible and that the cooling element does not need to be opened to pour out the fluid. A disadvantage, however, is the inferior heat transfer since gaps that impede the transfer of heat can remain between the outer surface of the container and the outer evaporator covering material.
To maintain the necessary vapor passageway cross section between the evaporator and the sorbent filling in spite of the externally exerted air pressure, this invention provides that the vapor passageway be formed and stabilized by multiple layers of a plastic network. Thus, a sufficient cross section for the flow remains intact between the network structure. When polypropylene networks are used, higher temperatures are admissible without the risk of a release of gases. Furthermore, since the networks have a flexible structure, they adapt optimally to any geometry involved.
In this context, the term fluid container is meant to comprise all known and conventionally used containers, such as bottles, cans, pouches, jugs, cardboard packaging, etc., that serve to hold liquids, such as beverages, liquid drugs, and chemical products. Obviously, the fluid container may also contain solid or freely flowable products. The normal shape and structure of the fluid container does not need to be changed in any way. Thus, all manufacturing and filling devices used so far can be used without requiring any changes.
The evaporator can have any shape and can be manufactured from any materials. An industrial requirement is that a sufficiently large opening for allowing the water vapor to flow into the sorbent material forms and is maintained during the cooling process, that working fluid in a liquid state remains in the area to be cooled, that an entrainment of liquid components is prevented, and that an excellent thermal connection to the object to be cooled is maintained.
Of industrial and economic interest are, e.g., cooling elements in the shape of trays for the transport of food with adjacent hot and cold surfaces. These can preferably be designed in the form of bowls into which the food can be placed directly. Also useful are cooling elements in which the hot and cold surfaces are disposed opposite to each other. Such elements can be optimally used to separate warm and cold areas in coolers or insulating transport packagings. In these cases, an insulating spacer material can be inserted between the hot and the cold zone, which spacer material can preferably be disposed inside the multilayer sheeting material. Disposing such cooling elements in vacuo additionally reduces the heat conduction in a highly effective manner.
To produce cooling elements according to the present invention, for example, a unilaterally open sorbent-containing pouch is manufactured from a multilayer sheeting material by means of heat sealing. The sorbent-containing pouch is filled with a sorbent material which contains a low quantity of working medium and does not contain gases that will be released at a later time, it is subsequently evacuated to a pressure of less than 15 mbar, in particular to less than 5 mbar, and then heat-sealed so as to be impermeable to gas. Subsequently, the pouch containing the sorbent material and being under a vacuum, together with a shut-off means, a spacer and a nonwoven evaporator that is saturated with the working medium, is wrapped into another outer pouch made of a multilayer sheeting material. The outer pouch is subsequently evacuated in a vacuum chamber until it reaches the vapor pressure of the working medium and subsequently also sealed so as to be impermeable to gas. When incorporating the shut-off means, care must be taken to ensure that its opening mechanism is not triggered during the flooding of the vacuum chamber.
As a rule, the pouch made of the sheeting material is thermally sealed by pressing hot sealing bars onto the outer surfaces of the sheeting material until the polypropylene layers lying inside on top of one another are liquefied and are heat-sealed to one another. As a rule, sealing is carried out in vacuo inside a vacuum chamber. The pouch can, however, also be evacuated only on the inside by means of a suction device and then be sealed. In addition to the thermal contact method, it was found that sealing procedures by means of ultrasound are useful as well.
According to the present invention, it is possible to incorporate the fluid container to be cooled at a later time into a cooling element. To keep interfering gases out of the cooling element, this fluid container as such can be sealed into an evacuated pouch prior to incorporating it into the outer pouch. To ensure that no gases that interfere with the vacuum are released during the storage period as well as during the cooling time during which the temperatures are higher, all components contained in the vacuum should have been heated during the evacuation process to a temperature of at least 80° C. or should have been outgassed at even higher temperature prior to introducing them into the vacuum.
The preferred embodiments of the present invention, as well as other objects, features and advantages of this invention, will be apparent from the following detailed description, which is to be read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a perspective and cross-sectional view of the pouch containing sorbent material.
FIG. 1 a shows an enlarged partial view of the multilayer sheeting material seen in FIG. 1 .
FIG. 2 shows a perspective and cross-sectional view of an evaporator assembly.
FIG. 3 shows a design of a spacer.
FIG. 4 shows a cooling element for cooling a beverage can.
FIG. 4 a shows the cooling element seen in FIG. 4 in a longitudinal section along KK.
FIG. 4 b shows the cooling element seen in FIG. 4 in a cross section along SS.
FIG. 4 c shows the cooling element seen in FIG. 4 in another cross section along VV.
FIG. 4 d shows the cooling element seen in FIG. 4 with the vapor passageway opened.
FIG. 5 shows a cooling element that can simultaneously cool and warm.
FIG. 5 a shows the cooling element seen in FIG. 5 in a cross section along SS.
FIG. 6 shows a cooling element assembly for cooling a bottle.
FIG. 6 a is a top view of a zeolite plate seen in FIG. 6 .
FIG. 7 shows another assembly of a pouch containing the sorbent material and a bottle to be cooled.
FIG. 8 shows a sectional view of a shut-off means with a cutting die.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The sorbent-containing pouch 1 shown as a perspective and cross-sectional representation in FIG. 1 comprises a multilayer sheeting material 2 that is thermally sealed along the edges 3 of the pouch. Located in the evacuated inside of said pouch is the desorbed sorbent material 4 which contains broken natural zeolite granules.
The multilayer sheeting material 2 previously sealed to form a pouch was filled with bulk granules that had been heated to 140-200° C. in a circulating air oven and was subsequently evacuated in a vacuum chamber to a pressure of less than 5 mbar. Both gases and water vapor were drained from the zeolites crystal structure by pumping. The sorbent-containing pouch 1 was sealed by means of sealing tongs so as to be impermeable to gas and the vacuum chamber was re-aerated. The sorbent-containing pouch 1 was cooled by submerging it in a water bath. After cooling, the water vapor pressure inside the pouch is below 1 mbar absolute. Residual gases are not measurable and will not outgas later from the multilayer sheeting material since on filling the pouch with the hot granules, said sheeting material was heated to above 100° C. as well, thereby releasing potentially existing gases. When heated to a similar temperature level during the subsequent sorption process, no other interfering gases will be released.
FIG. 1 a shows an enlarged cross-sectional view of the multilayer sheeting material 2 . It comprises, from the inside out, an 80 μm thick polypropylene layer 5 on which an 8 μm thick aluminum layer 7 is glued by means of adhesive 6 . By means of a second adhesive layer 8 , a long-wearing 30 μm thick polyester layer 9 is attached. The choice of the layers and adhesives used is made on the basis of the requirements that in vacuo (i.e., in a vacuum) and at temperatures above 100° C., the layers do not release interfering gases, the sealed seams do not rupture and the sharp-edged zeolite-containing sorbent material 4 cannot puncture the sheeting material. According to the present invention, an additional polyester layer can be glued in between the polypropylene layer 5 and the aluminum layer 7 .
FIG. 2 shows a perspective and cross-sectional representation of an evaporator. Said evaporator comprises a spacer 11 which is manufactured from a flexible extrusion-molded polycarbonate part and which has a multilayer sheeting material 13 disposed on its smooth outer surface 12 and open flow passageways 15 for the working medium vapor on its structured inner surface 14 . Interspersed between a second multilayer sheeting material 16 which covers the cold surface of the evaporator and the spacer 11 is a fibrous nonwoven material 17 which is saturated with the fluid working medium. The nonwoven material 17 comprises microfibers made of polypropylene. The two multilayer sheeting materials 16 and 13 are thermally sealed to each other along seam 10 having a sealed seam width of at least 5 mm.
FIG. 3 shows a different embodiment of spacer 18 . Said spacer is manufactured from a 1 mm thick polypropylene plate 21 , into which spacer nubs 19 are thermoformed by means of a thermoforming method, which spacer nubs ensure that there is a space relative to a nonwoven material 20 , thus allowing water vapor that evaporates from the nonwoven material 20 —unimpededly flow in the passageway between the nonwoven material 20 and the polypropylene plate 21 .
FIGS. 4 and 4 a - 4 d show a cooling element which holds a beverage can 24 with a volume of 0.5 L in the upper portion and a sorbent-containing pouch 22 with 400 g of natural clinoptilolite in the lower portion. The beverage can 24 and the sorbent-containing pouch 22 have been sealed in vacuo into an outer pouch 23 . The outer pouch 23 is manufactured from a piece of a multilayer sheeting material which was folded over once and sealed along the lower cross seam 26 and along the long seam 27 . After inserting the sorbent-containing pouch 22 , a piercing tool 25 and the beverage can 24 surrounded by evaporator 29 into the outer pouch, said outer pouch 23 was subjected in a vacuum chamber to a pressure below the vapor pressure of the working medium and subsequently also sealed along the upper edge 28 . To ensure that during the flooding of the vacuum chamber, the piercing tool 25 does not penetrate the sheeting material of the sorbent-containing pouch 22 at the piercing site 30 as a result of the contraction of the outer pouch 23 , two spacers 31 made of expanded polypropylene are attached by means of adhesive tapes 32 to the outside of the outer pouch 23 . The spacers 31 ensure that, in spite of the negative pressure, the piercing tool 25 does not pierce the sorbent-containing pouch 22 . The flow passageway is opened only once the spacers 31 have been removed by tearing off the adhesive tapes 32 and once the piercing tool 25 , as shown in FIG. 4 d , has penetrated the sorbent-containing pouch 22 and has punched out the piercing site 30 . The piercing tool 25 is manufactured from a small piece of expanded metal that has been molded to form a cylinder. On its upper end, it touches the beverage can 24 ; its lateral support is ensured by a fixing plate 33 with passageways, which fixing plate at the same time keeps the vapor path from evaporator 29 through the piercing tool 25 into the sorbent material 34 open once the spacers 31 have been removed.
FIG. 4 c shows the construction of the evaporator 29 along cross section VV (seen in FIG. 4 ). Wrapped around the beverage can 24 is a paper sleeve 35 which is saturated with 30 g of water and which is pressed to the outer wall of the beverage can 24 by means of a spacer 36 , similar to spacer 11 in FIG. 3 . Spacer 36 in turn is pressed against the beverage can 24 by means of the outer pouch 23 on which the outside air pressure is exerted. This ensures an optimum thermal contact between the evaporating water and the content of the can.
FIG. 4 b shows the cross section along line SS in FIG. 4 . As explained in the description in connection with FIG. 1 , the sorbent material 34 , in this case natural zeolite, is packaged in the sorbent-containing pouch 22 . The sorbent-containing pouch 22 is surrounded by the sheeting material of the outer pouch 23 . Said sheeting material also comprises a barrier layer made of aluminum as well as a sealable layer made of polyethylene or polypropylene. As long as it is ensured that no gases exit from the surface or the cover seal of the beverage can 24 into the evaporator region, the beverage can 24 need not be surrounded by an additional gas-impermeable evacuated sheeting material.
During the manufacture of the cooling element, care should be taken to ensure that all media located within the vacuum system do not emit any gas or only harmless quantities of gas. Preferably, the sorbent-containing pouch 22 is first placed into the cover pouch 23 . Subsequently, the spacers 31 are attached to the outside by means of adhesive tapes 32 .
The paper sleeve 35 is wrapped around the lateral surface of the beverage can 24 and saturated with water as the working medium. Relative to the weight of the sorbent material, the water amounts to 7.5%. This is followed by the spacer 36 made of polypropylene and the fixing plate 33 into which the piercing tool 25 is inserted. The fixing plate 33 and the spacer 36 can be easily affixed to the beverage can 24 by means of shrink wrap (not shown in the drawing).
The thus prepared beverage can 24 is pushed into the outer pouch 23 until the two spacers 31 touch the fixing plate 33 . The outer pouch 23 together with its contents is then evacuated in a vacuum chamber until a small quantity of water vapor flows from the working medium, here water. This working medium vapor flow outgases the working medium as such and also entrains all other gases from the outer pouch 23 . After it has been ensured that all interfering gases have been evacuated by pumping, the outer pouch 23 is thermally sealed along the upper edge 28 by means of sealing bars.
After aerating the vacuum chamber, the finished cooling element can be removed. To ensure that even after a relatively long storage time, the cooling element is gas-impermeably sealed and no foreign gases were released, the element can again be placed into a vacuum chamber for evacuation. If the cooling element is properly functioning, the outer pouch 23 will bulge only once the pressure in the chamber drops below the pressure of the water vapor.
To activate the cooling element, it is necessary to remove the two spacers 31 which, because of the negative pressure, are securely clamped between the sorbent-containing pouch 22 and the fixing plate 33 . Thanks to the flexible spacer material, the sheeting material of the outer pouch 23 and of the sorbent-containing pouch 22 is not damaged in spite of the presence of sharp-edged zeolite granules. As a result of the negative inside pressure, the piercing tool 25 will immediately penetrate the piercing site 30 of the sorbent-containing pouch 22 , punch out a portion of the sheeting material and open up the vapor passageway for the waiting water vapor. Within a few minutes, the water in the paper sleeve 35 will cool to approximately 0° C., and the sorbent material 34 will be heated to more than 100° C. After approximately 10 min, the contents of the beverage can 24 will have cooled by approximately 18 K, and the sorbent material 34 will be uniformly hot. The beverage inside the can be cooled more rapidly by occasionally shaking the beverage can 24 . The outer pouch 23 can be torn open by means of a notch on the sealed seam along long seam 27 , and the cold beverage can 24 can be removed from the evaporator 29 . The sorbent granules used can be utilized to improve the quality of the soil or stagnant water or, together with the sheeting material, can be disposed of with the residual waste.
Approximately 18 g of the water saturating the paper sleeve 35 have been evaporated and sorbed by the sorbent material 34 . Given a weight of the zeolite filling of 400 g, this corresponds to a loading of only 4.5%. But since, within the short cooling time, the zeolite filling is not able to release much heat, a noticeable drop in temperature, and thus an additional water adsorption associated therewith, is not possible. For this reason, a natural zeolite is highly suitable for use in the cooling element described here.
FIGS. 5 and 5 a show a flat cooling element which, in addition to the cold from evaporator 42 , also allows heat form the sorbent material to be utilized. A flat sorbent-containing pouch 40 comprises a zeolite plate 41 made of synthetic zeolite and an evaporator 42 without a shut-off means disposed in between. The evaporator 42 comprises an anhydrous nonwoven material 43 and a spacer 44 having a construction identical to the spacer of FIG. 2 . The zeolite plate 41 has been formed from powdered Na-A zeolite with an added binding agent. Disposed in the lower part of said zeolite plate are flow passageways 45 which make it possible for the water vapor flow to move from the spacer 44 into the sorbent material. The water used as the working medium 47 is located in a water pouch 46 which is connected by way of a connecting passageway 48 with the evaporator 42 and which, at the same time, is an integral part of the sorbent-containing pouch 40 . Disposed in the area in which the connecting passageway 48 opens out into the evaporator 42 is a piece of sheeting material 50 which ensures that inflowing water is directed into the nonwoven material 43 and does not reach the flow passageways of the spacer 44 while still in a liquid state. In addition, in the area of the mouth of the connecting passageway 48 , 0.5 g of common salt has been incorporated into the nonwoven material 43 . According to the present invention, a single pouch of a multilayer sheeting material is used; this pouch encloses and forms the sorbent material, the evaporator 42 , the connecting passageway 48 , the water as the working medium, here water, 47 , and the shut-off means. The shut-off means is implemented in that the connecting passageway 48 is kinked at an angle of 180° upward from its originally plane position. Thus, during the storage time, the water pouch 46 which, during manufacturing, is in the position shown as a broken line in FIG. 5 is disposed on the evaporator 42 . As a result of the sharp fold 49 in the area of which the two superimposed polypropylene layers are tightly squeezed against each other, a very inexpensive shut-off means has been created, which shut-off means (by folding the water pouch 46 back into its original position (position shown as a broken line in FIG. 5 and position in FIG. 5 a )) can be easily opened without the need for an additional tool simply be exerting pressure on the outside of the water pouch 46 .
To manufacture the cooling element, the zeolite plate 41 is heated in a circulating air oven to temperatures between 150° C. and 200° C. The hot zeolite plate 41 , together with the evaporator components that have been heated to approximately 80° C., is subsequently introduced into the partially pre-manufactured sorbent-containing pouch 40 . The sorbent-containing pouch 40 is subsequently sealed so that only the connecting passageway to the water pouch 46 and the water pouch itself have a suction opening to a vacuum chamber. By evacuating the vacuum chamber to less than 5 mbar, the pressure within the sorbent-containing pouch 40 is reduced as well. This causes residual water to evaporate from the zeolite, the vapor flow of which residual water eliminates air and gases released from the hot components through the connecting passageway 48 . Thereupon, the passageway can be folded. The water pouch 46 can now be filled with outgassed water and can subsequently be sealed so as to be impermeable to gas.
To activate the cooling element, the water pouch 46 is simply folded back into its original position and thus the fold 49 is straightened out. Driven by the water vapor pressure in the water pouch 46 , water now flows through the connecting passageway 48 into the nonwoven material 43 . This water dissolves the salt crystals located in said material, which lowers the freezing point to nearly −17° C. The water that follows directs the salt solution into the nonwoven material, from which it can evaporate. The vapor is deflected via the passageways that are kept open by the spacers 44 and directed into the zeolite plate 41 and exothermally sorbed. The heat of sorption heats the zeolite plate 41 to more than 100° C. The nonwoven material 43 is cooled by the cold of evaporation to temperatures below the freezing point. Thus, in the area of the zeolite plate 41 , the cooling element can be used, for example, to keep food warm, and in the area of the evaporator 42 , it can be used to keep beverages cold. After use, it can be disposed of with the residual waste.
Although not shown in the drawing, it should be noted that the evaporator 42 of the cooling element seen in FIG. 5 can be shaped in the form of a cylinder which is suitable for holding a can or a bottle. To ensure good thermal contact between the outer surface of the bottle and the sorbent-containing pouch, the two can be compressed to each other by means of stretch wraps or rubber bands.
The bottle and the cooling element can also be very efficiently brought into contact with each other by placing both into an additional pouch which is subsequently evacuated. In this case, the heat transfer from the evaporator to the bottle is considerably improved as a result of the air pressure exerted on the pouch.
FIG. 6 shows additional components of a cooling element according to the present invention for rapidly cooling a bottle 53 that is filled with a beverage. The bottle 53 which is shown in cross section is again surrounded by a cylindrically moldable spacer 54 , which presses a nonwoven material 52 onto the cylindrical portion of the bottle, and by a fixing element 55 for holding a cutting tool 56 . The bottle 53 itself can first be sealed into a gas-impermeable evacuated sheeting material (not shown) to ensure that gases diffusing from the cork 61 of the bottle 53 cannot interfere with the vacuum needed for proper functioning of the cooling element. A sorbent-containing pouch 57 comprises 6 disk-shaped zeolite plates 58 , a top view of one of which plates is shown in FIG. 6 a . Disposed in the center of the plates are vapor passageway holes 59 , via which the water vapor is transported to the radial passageways 60 . From the radial passageways, the vapor can subsequently advance rapidly into all areas of the sorbent material by way of narrow gaps which inevitably remain between the plates. The uppermost plate 58 has a larger vapor passageway hole to accommodate the cutting tool 56 and the multilayer sheeting material that is punched out.
The other components necessary for the proper functioning of the cooling element according to the present invention are not shown in the drawing. These components follow from and are identical to those in the drawings and descriptions of FIGS. 4-4 d.
FIG. 7 shows another compact configuration of a cooling element for cooling a bottle 62 . Molded into the sorbent-containing pouch 63 is a depression in which the neck 64 of the bottle and the shut-off means 65 are disposed. The sorbent-containing pouch 63 preferably has the diameter of the bottle 62 , including the evaporator which is not shown in the drawing. The shut-off means is a cutting tool 65 which can perforate the multilayer sheeting material of the sorbent-containing pouch 63 only after manually increased axial pressure has been exerted. Again, for clarity's sake, the remaining components are not shown in the drawing. These components as well as the manufacturing and cooling method follow from the description in connection with FIGS. 4-4 d.
FIG. 8 shows a shut-off means with a cutting die 80 that can perforate a sorbent-containing pouch 81 . The sorbent-containing pouch 81 contains a zeolite filling 82 in the form of beads. Disposed on one end of the cylindrically shaped cutting die 80 is a knife edge 83 which is designed to pierce the sheeting material of the sorbent-containing pouch 81 . To safeguard against accidental cutting, a protective sheeting material 84 is placed between the knife edge 83 and the sorbent-containing pouch 81 , the properties of which protective sheeting material are such that they ensure that the cutting die 80 pierces the sorbent-containing pouch 81 only when additional external forces are exerted in the direction of arrow A on the other end of the cutting die 80 , thereby eliminating the possibility that the external air pressure alone activates the cutting die. Disposed on this other end is a cap 85 which projects beyond the diameter of the cutting die 80 and which supports the outer pouch 86 . The diameter of cap 85 is slightly larger than the punched-out hole 88 in a passageway for the working fluid vapor, which passageway is disposed between the sorbent-containing pouch 81 and the outer pouch 86 . To maintain the necessary vapor cross section, the passageway is constructed of a plurality of layers of a network 87 of polypropylene filaments. As a result of this multilayer construction, the flow diameter for the working fluid vapor within the network structure remains sufficiently large, although the difference between the pressure of the working fluid vapor and the external air pressure is acting on the vapor passageway. By exerting pressure on the outer pouch 86 in the direction of arrow A, the protective sheeting material 84 , together with the sorbent-containing pouch, is pierced by the knife edge 83 of the cutting die 80 . The zeolite filling 82 that follows pushes the punched-out portions into the inside of the cutting die cylinder and thus opens up the passageway for the vapor. The cutting die 80 can be pushed in until its cap 85 comes to rest on the perforated edges of the networks 87 . The flexible outer pouch 86 folds without becoming permeable.
Although the preferred embodiments of the present invention have been described with reference to the accompanying drawings, it is to be understood that the invention is not limited to those precise embodiments, and that other changes and modifications may be made by one skilled in the art without departing from the scope or spirit of the invention.
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A cooling element with a sorbent material ( 4 ) which in vacuo can sorb a vaporous working medium that evaporates from a fluid working medium in an evaporator ( 29 ) and with a shut-off means which, up to the moment at which the cooling process is initiated, prevents the working medium vapor from flowing into the sorbent material ( 4 ), with the sorbent material ( 4 ) being sealed into a sorbent-containing pouch ( 22 ) which comprises a multilayer sheeting material which in turn comprises at least one metallic layer or one metallized layer.
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BACKGROUND OF THE INVENTION
2-fluoronitrobenzene is useful as an intermediate in the preparation of certain known herbicides, such as the 2-substituted aryl-4,5,6,7-tetrahydro-2H-isoindole-1,3-diones disclosed in U.S. Pat. No. 4,001,272, granted on Jan. 4, 1977 to Steven J. Goddard.
2-FLUORONITROBENZENE HAS, HERETOFORE, BEEN PREPARED BY THREE DIFFERENT BASIC SYNTHETIC METHODS. The first method involves the nitration of fluorobenzene using a mixture of sulfuric acid and nitric acid. However, the product obtained from this method is an isomeric mixture of 4-fluoronitrobenzene and 2-fluoronitrobenzene, typically in a 9:1 ratio.
The second method involves the diazotization of 2-nitroaniline and conversion to 2-nitrodiazonium fluoroborate. The thermal decomposition of the dry diazonium fluoroborate gives 2-fluoronitrobenzene in only 10-19% yield. The thermal decomposition of diazonium fluoroborates is dangerous and proceeds in low yield when there is a nitro group in the position ortho to the diazonium group.
The third method is based on the halogen exchange of 2-chloronitrobenzene with an alkali metal fluoride. The halogen exchange reaction can be conducted both with and without solvent. Previous methods, however, require long reaction times and high temperatures, give only moderate yields of 2-fluoronitrobenzene, and/or require the use of rare alkali metal fluorides such as cesium or rubidium fluoride.
U.S. Pat. No. 3,240,824 discloses a process for preparing 2-fluoronitrobenzene in 60.6% yield (based on 50.5% conversion) by heating under pressure, equimolar amounts of 2-chloronitrobenzene and potassium fluoride without solvent at 290° C for 24 hours.
Finger and Kruse [J. Amer. Chem. Soc., 78 6034 (1956)] disclose a process for preparing 2-fluoronitrobenzene in dimethylformamide at 170° C for 163 hours in 40% yield, and in dimethylsulfoxide at 185° C for 4.5 hours in 38% yield.
Fukui et al. [Nippon Kagaku Zasski, 79, 889 (1958)];[Chemical Abstracts, 54, 4430 c (1958)] improves upon the yield reported above in a dimethylsulfoxide system. Fukui maintains the reaction temperature at 185° C for 10 hours and reports a 56% yield.
Fuller [German Offenlegungsschrift No. 2,527,944 (1975)] was the first to disclose the preparation of 2-fluoronitrobenzene by reaction of 2-chloronitrobenzene with potassium fluoride in a tetramethylene sulfone (sulfolane) solvent, although others had reported earlier the use of sulfolane as the solvent for fluorination (with potassium fluoride) of other materials. For example, Fuller [J. Chem. Soc., 6264 (1965)] discloses fluorination of hexachlorobenzene and Matsui et al. [Japanese Kokai, 74/110,637] discloses fluorination of 4-chloronitrobenzene (with a catalytic amount of cesium fluoride) in sulfolane. Fuller's preparation of 2-fluoronitrobenzene is conducted at 240° C for 22 hours and results in a 60.5% yield.
All previous methods for preparing 2-fluoronitrobenzene by halogen exchange have one or more of the disadvantages mentioned above; that is, they require long reaction times and/or high temperatures, give only moderate yields of the desired product, and/or require the use of rare alkali metal fluorides such as cesium or rubidium fluoride.
SUMMARY OF THE INVENTION
The present invention concerns an improved process for the preparation of 2-fluoronitrobenzene by heating 2-chloronitrobenzene with ultra-fine particulate potassium fluoride in sulfolane, with a catalyst selected from the group consisting of macrocyclic ethers and quaternary ammonium halides, at a temperature of 240° to 250° C. The process of the present invention results in conversion of the 2-chloronitrobenzene to 2-fluoronitrobenzene with shorter reaction time and higher yield and uses less solvent than previously known processes, such as those discussed above.
DETAILED DESCRIPTION OF THE INVENTION
Preferably, the molar ratio of 2-chloronitrobenzene to sulfolane is 1 : 1-0.3, the reaction temperature is 240° to 250° C, and the molar ratio of 2-chloronitrobenzene to potassium fluoride is 1 : 1.1-1.5. A catalyst is chosen from the group consisting of macrocyclic ethers, such as 1,4,7,10,13,16-hexaoxacyclooctadecane, and quaternary ammonium halides, such as benzyltriethylammonium chloride. The reaction time is 2-8 hours.
The molar ratio of sulfolane to 2-chloronitrobenzene is particularly important. If the molar ratio of sulfolane to 2-chloronitrobenzene is less than 0.3 : 1, the rate of the reaction is significantly decreased; while a ratio greater than 1 : 1, significantly decreases the yield of 2-fluoronitrobenzene due to the formation of by-products. The preferred molar ratio of 2-chlorobenzene to sulfolane is 1 : 0.9-1.0.
The molar ratio of 2-chloronitrobenzene to potassium fluoride is not quite so important. Nevertheless, an excess of potassium fluoride beyond that specified above, for example 1 : 2, is not necessary and will not lead to a greater conversion of 2-chloronitrobenzene to 2-fluoronitrobenzene. However, the particle size of the potassium fluoride is quite important and should be 1-20 microns. Larger particle sizes give significantly decreased yields. The potassium fluoride should not be caked together as this will lower the yield of the reaction. It is desirable that the potassium fluoride contain less than 0.1% by weight water since this will minimize caking.
The reaction temperature and reaction time are also quite important, and when the reaction temperature is less than 240° C, the reaction will not give sufficient conversion. At temperatures above 250° C, the formation of by-products becomes significant and will lower the yield of 2-fluoronitrobenzene. When the reaction time is less than 2 hours, the reaction will not give sufficient conversion. With reaction times greater than 8 hours, the formation of by-products becomes significant and will lower the yield of 2-fluoronitrobenzene.
A macrocyclic ether, such as 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6 ether), may be used as the catalyst. Preferred conditions when such a catalyst is used are 2-chloronitrobenzene, potassium fluoride, macrocyclic ether, and sulfolane in a molar ratio of 1 : 1.1-1.5 : 0.001-0.01 : 0.3-1.0, heated at 240°-250° C for 2-8 hours. Most preferred conditions are 2-chloronitrobenzene potassium fluoride, 18-crown-6 gl ether, and sulfolane in a molar ratio of 1 : 1.1-1.5 : 0.002-0.004 : 1, heated in 240°-242° C for 4-6 hours.
Alternatively, a quaternary ammonium halide, such as tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium fluoride or benzyltriethylammonium chloride, may be used as the catalyst. Preferred conditions when such a catalyst is used are 2-chloronitrobenzene, potassium fluoride, quaternary ammonium halide, halide, and sulfolane in a molar ratio of 1 : 1.1-1.5 : 0.01-0.05 : 0.3-1.0, heated at 240°-250° C for 2-8 hours. Most preferred conditions are 2-chloronitrobenzene, potassium fluoride, benzyltriethylammonium chloride, and sulfolane in a molar ratio of 1 : 1.1-1.5 : 0.02-0.03 : 1.0, heated at 240°-242° C. for 4-8 hours.
2-fluoronitrobenzene and unreacted 2-chloronitrobenzene can be separated from the reaction mixture by either of two methods. In the first of these methods the reaction mixture is steam distilled to give 2-fluoronitrobenzene and unreacted 2-chloronitrobenzene in the distillate and inorganic salts, sulfolane, and tars in the residue. The steam distillate is then separated into layers, and the organic layer is distilled through a suitable fractionating column to separate the 2-fluoronitrobenzene from the unreacted 2-chloronitrobenzene.
An alternative method for obtaining 2-fluoronitrobenzene from the reaction mixture is fractional distillation, whereby the sulfolane is recovered for reuse. The reaction mixture is filtered to separate the inorganic salts and the filter cake is washed with a suitable solvent such as sulfolane or methylene chloride, The filtrate and washings are then fractionally distilled with a suitable fractionating column to separate the 2-fluoronitrobenzene, unreacted 2-chloronitrobenzene and sulfolane.
In the following illustrative examples, all parts and percentages are by weight, unless specified otherwise.
EXAMPLES 1
A mixture of 158 parts 2-chloronitrobenzene, 90 parts potassium fluoride, 0.5 parts 18-crown-6 ether, and 120 parts sulfolane were heated together at 240° C for 4 hours. Gas chromatography of the reaction mixture showed 78.6% 2-fluoronitrobenzene annd 21.3% 2-chloronitrobenzene.
EXAMPLE 2
A mixture of 158 parts 2-chloronitrobenzene, 90 parts potassium fluoride, 1 part 18-crown-6 ether, and 120 parts sulfolane were heated together at 240° C for 4 hours. Gas chromatography of the reaction mixture showed 87.2% 2-fluoronitrobenzene and 12.8% 2-chloronitrobenzene.
EXAMPLE 3
A mixture of 158 parts 2-chloronitrobenzene, 90 parts potassium fluoride, 7 parts benzyltriethylammonium chloride and 120 parts sulfolane were heated together at 240° C for 6 hours. Gas chromatography of the reaction mixture showed 67.6% 2-fluoronitrobenzene and 32.4% 2-chloronitribenzene.
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An improved process for preparing 2-fluoronitrobenzene by reacting 2-chloronitrobenzene with ultra-fine particulate potassium fluoride in tetramethylene sulfone with a macrocyclic ether or a quaternary ammonium halide catalyst. 2-fluoronitrobenzene is an intermediate useful in the preparation of certain known herbicides.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates generally to truss systems for reinforcing appliance or cabinet doors and specifically to a door truss for use with a drying cabinet appliance and method of use.
[0002] Drying cabinets provide hot air for drying clothes hanging in the cabinet. Drying cabinets can be used for dewrinkling clothes by providing steam into the cabinet to remove wrinkles. Drying cabinets may be used in combination with a tumble dryer and when placed on top of the tumble dryer, preferably have door handles on the front bottom portion of the cabinet doors. However, the drying cabinet makes use of relatively tall and thin doors. Without adequate support, the doors will flex during opening. This flex creates a non-rigid feel to the user which may be perceived as poor quality construction.
[0003] In addition, the tall cabinet doors having a handle at the bottom have a potential problem of inadequate seal compression at the upper end of the doors. Although the lower ends of the doors may be adequately fastened or latched, the upper ends may be loose as there is no comparable latch at the upper ends.
[0004] A still further problem of drying cabinet doors is maintaining the shape of the doors. Each door normally includes a plastic inner door liner and an outer metal skin. In order to have adequate compression seal around the perimeter of the door, the shape of the inner and outer door panels must be maintained.
[0005] Accordingly, the primary objective of the present invention is the provision of an improved cabinet dryer door.
[0006] Another objective of the present invention is the provision of a cabinet dryer door truss system for reduced flexing of the door during opening and closing of the cabinet door.
[0007] Another objective of the present invention is the provision of a cabinet door that may be latched at the bottom yet still provide adequate seal compression at the top of the door.
[0008] Another objective of the present invention is the provision of a cabinet or appliance door having a sheet metal skin on an inner plastic liner which is assembed to maintain a preloaded shape for the assembled door.
[0009] A further objective of the present invention is the provision of an improved appliance door having sufficient seal compression around the perimeter of the door.
[0010] Still another object of the present invention is the provision of an improved appliance door which is economical to manufacture and durable in use.
[0011] These and other objectives will become apparent from the following description of the invention.
SUMMARY OF THE INVENTION
[0012] The foregoing objectives may be achieved with a door assembly for an appliance or cabinet having a plastic inner door panel and a metal outer door panel. Spacers molded into the inner door and a truss system attached to the inner door cooperate to establish seal compression between the closed door and the drying cabinet.
[0013] According to another aspect of the present invention, the truss may be attached to the inner door by a screw placed into a hole approximately centered in the truss.
[0014] According to another feature of the present invention, the door assembly has a block spacer between the inner door panel and the outer skin panel. The block spacer provides curvature to the outer skin similar to the curvature of the inner door.
[0015] According to yet another feature of the present invention, the truss positioned within the door assembly is a bar received into slots in the spacers so as to be supported by the spacers.
[0016] The foregoing objectives may also be achieved with a drying cabinet having a housing and a pair of center opening doors attached to the housing. The doors have a handle at the bottom of the doors and a truss within at least one door. The truss is secured to the door to preload the door and thereby establish a seal compression around the doors for adequate sealing of the doors against the housing.
[0017] The foregoing objectives may also be achieved by a method of generating a preload on a cabinet door to provide sealing compression. The method has the steps securing a truss member to the door and maintaining the truss member in a straight profile while curving the door for a biasing effect against a seal.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a perspective view of a clothes drying machine having a drying cabinet located on top of a tumble dryer and showing the doors in a closed position.
[0019] FIG. 2 is a view similar to FIG. 1 showing the doors opened.
[0020] FIG. 3 is an exploded perspective view of a door assembly of the present invention.
[0021] FIG. 4 is a view similar to FIG. 3 showing a door in the assembled state.
[0022] FIG. 5 is a sectional view taken along line 5 - 5 of FIG. 3 additionally including a sectional view of the truss member in position on the spacers.
[0023] FIG. 6 is a sectional view taken along line 6 - 6 of FIG. 4 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0024] FIGS. 1 and 2 shows a combination clothes drying machine 10 having a tumble dryer 12 and a drying cabinet 14 . The tumble dryer 12 and cabinet dryer 14 are housed within a cabinet or housing 16 so as to define a single appliance with dual functions. The drying cabinet 14 is shown to be mounted on top of the tumble dryer 12 , though it is understood that other configurations can be provided, and includes a drying compartment or chamber 18 . As seen in FIG. 2 , the drying cabinet 16 may include removable shelves 17 and a hanging bar 19 to hold clothes on hangers.
[0025] The drying cabinet 14 includes a pair of doors or door assemblies 20 which provide access to the drying compartment 18 . The right and left doors 20 are mirror images of one another. The right door has an emblem in the upper right hand corner. Each door assembly 20 has a metal outer skin or panel 22 that attaches to a plastic inner door panel 24 . The outer skin 22 is a sheet metal. A handle 26 is formed near the bottom of the inner door 24 . Each door assembly 20 is relatively tall and narrow and encounters torque when the door assembly 20 is opened using the handle 26 . A door strike 28 is provided on the inner panel 24 . The door strike 28 is received in latch 30 on the drying cabinet 14 to maintain the doors 20 in a closed position.
[0026] The location of the handle 26 and door strike 28 at the bottom of each door assembly 20 presents the problem of providing adequate seal compression at the top of the door assemblies 20 . Thus, a truss member 32 is provided to preload at least one door assembly 20 and bias the top 29 slightly against the seal 31 when the door assembly 20 is in the closed position.
[0027] As seen in FIGS. 3 and 4 , the truss member 32 is an angle iron having a first leg 36 and second leg 38 formed at an approximately 90 degree angle. The truss member 32 is made out of metal, typically commercial steel. The truss member 32 may be hot dipped galvanized steel that is 0.052 inches thick.
[0028] While the truss member 32 is illustrated as an angle iron, it may be employed in various other structural shapes to create a relatively inflexible member. These shapes include, but are not limited to, flat bar, C-channel and tubular shapes.
[0029] The truss member 32 is placed adjacent spacers 40 formed in the inner panel 24 . The truss member 32 and spacers 40 are located diagonally across the inner door panel 24 running from a bottom corner opposite the door strike 28 to a top corner. The spacers 40 have opposite walls 42 , 44 defining a slot that receives the first leg 36 of the truss member 32 .
[0030] A screw 46 is provided to attach the truss member 32 to the inner door panel 24 . The screw 46 goes through hole 47 approximately centered in the truss member 32 to attach to screw boss 48 on the inner panel 24 . As the screw 46 is tightened, the inner door panel 24 flexes to be drawn into its final position against the relatively inflexible truss member 32 .
[0031] Blocks 50 are used to space the outer skin panel 22 from the inner door panel 24 . The blocks 50 each have a slot 51 for mounting upon ribs 52 formed on the inner door panel 24 and are prevented from side movement by jaws 54 . As the screw 46 is tightened the inner door panel 24 is drawn upward to abut the truss member 32 and the blocks 50 raise with the inner door panel 24 so that the shape of the inner door panel 24 is conveyed to the outer skin panel 22 . Using blocks 50 , the same preloaded shape is maintained in both the inner door panel 24 and the outer skin panel 22 of the door assembly 20 .
[0032] FIG. 5 is a cross section of FIG. 3 but having the truss 32 adjacent the spacers 40 . The spacers 40 have varying heights. Spacers 40 A, 40 D, and 40 E are slightly taller than 40 B and 40 C. This height difference creates space 41 A between the truss 32 and the spacer 40 C and space 41 B between the truss 32 and spacer 40 B. These spaces remain as long as the inner door panel 24 does not have a load applied to the spacer 40 C by the screw being tightened into screw boss 48 . As illustrated in FIG. 5 , there is no bias outward away from the top 29 of the inner door panel 24 .
[0033] FIG. 6 is a cross section of FIG. 4 . The screw 46 has been inserted into the screw boss 48 drawing the inner door panel 24 inward by force F a . Force F a draws the inner door 24 into the truss 32 to remove gaps 41 A and 41 B and slightly bend the inner door 24 . Force F a creates an outward bias force F b at the top 29 of the door assembly 20 . These forces cooperate with the door strike 28 and latch 30 of the drying cabinet 14 to maintain the doors in the closed position.
[0034] The truss member 32 is illustrated in use on the right door assembly 20 . Alternatively, the truss member 32 may be on both the left and right door assemblies 20 . Typically, the drying cabinet 14 is designed such that one door assembly 20 closes over the other to form a seal. When only one truss member 32 is used, the truss 34 is preferably upon the side of the drying cabinet 14 that closes over the other side. As illustrated in the Figures, the right side door of the drying cabinet 14 closes over left side door and therefore the right side door would preferably have the truss member 32 . Even if the truss member 32 is not used within a door assembly 20 , the blocks 50 are still utilized to create curvature of the outer skin panel 22 .
[0035] In operation, the user will grip the handle 26 as seen in FIG. 1 and pull outward to open the door assembly 20 . The outward force by the user disengages the door strike 28 from the latch 30 permitting separation of a seal at the top of the door assembly 20 . The user rotates the door assembly 20 away from the centerline of the drying cabinet 14 and the door assembly 20 is prevented from flexing by the truss member 32 . The user then loads the drying cabinet with articles of clothing upon removable shelves 17 and the hanging bar 19 . The user rotates the door assembly 20 toward the centerline of the drying cabinet 14 and the door assembly 20 is prevented from flexing by the truss member 32 . The user then presses the door strike 28 into the latch 30 which concurrently engages a seal at the top of the door assembly 20 assisted in part by the seal compression created by the truss assembly 32 . Throughout opening and closing, the user is assured that the door assembly 20 is sealed prior to opening, rigid when being opened or closed, and secured and sealed after closing.
[0036] The invention has been shown and described above with the preferred embodiments, and it is understood that many modifications, substitutions, and additions may be made which are within the intended spirit and scope of the invention. From the foregoing, it can be seen that the present invention accomplishes at least all of its stated objectives.
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A cabinet dryer door includes a truss attached to the door to establish seal compression for adequate sealing of the door against the drying cabinet. The inner door has spacers molded into the inner door. The truss cooperates with the spacers to bias the door against the seal. The drying cabinet may utilize a pair of doors with at least one having a truss that establishes a seal compression in both of the doors. The truss is joined to the inner door by a screw located in the center of the truss. The method has the step securing a truss member to the door and curving the door to create a biasing force.
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This application claims the priority of U.S. Provisional Application Ser. No. 61/773,390 filed Mar. 6, 2013.
FIELD OF THE INVENTION
This invention relates to electrical boxes, and specifically to an electrical box with a siding block and a while-in-use cover.
BACKGROUND OF THE INVENTION
Electrical FS boxes for outdoor use are typically mounted on the exterior of buildings for providing convenient access to electrical outlets and other electrical devices such as switches and timers. Conventional FS boxes typically are a simple rectangular box configuration with a back wall and four side walls. When being mounted to a building, a rectangular hole must be cut in the substrate in order to mount the electrical box to the building. Cutting into the substrate creates a costly and time consuming repair job for the installer as he must typically caulk around the perimeter of the electrical box to seal against rain penetration between the box and the substrate. Although the caulk is meant to seal around the box, it is difficult to obtain a perfect seal making it likely that rain or water could seep behind the siding surrounding the box. Furthermore, cutting into the substrate can disrupt and damage the building's insulation layer that typically resides just under the substrate. There is also the problem of potentially damaging electrical wiring that is behind the area of the cut.
What is needed is an electrical box assembly that minimizes the need to cut a hole in the substrate and that accommodates siding in a manner that eliminates water seepage behind the siding. The electrical box assembly should be weatherproof, providing protection against rain and weather to a receptacle mounted therein while an electrical cord is plugged into the receptacle and also when the receptacle is not in use. The electrical box should furthermore include a cover member to accommodate large electrical plugs. The term “siding” as used herein includes stucco.
SUMMARY OF THE INVENTION
The invention is a weatherproof while-in-use electrical box assembly adapted for use on buildings that include a siding exterior or that will be finished with siding. The weatherproof while-in-use electrical box assembly includes an electrical box with an integral siding block and a cover assembly. The integral siding block provides a 360-degree channel around the electrical box for accommodating siding. The channel enables the electrical box assembly to channel water to the bottom of the box and exterior of the siding where it will drip harmlessly to the ground. The cover assembly is tamperproof and is adapted to receive large electrical plugs. The cover assembly includes cord openings that enable closing of the cover plate while electrical cords are connected to electrical outlets within the electrical box. The weatherproof electrical box assembly includes cord inserts for closing the cord openings when not in use to keep the assembly weatherproof when not in use. The tamperproof cover includes an arm adapted to accept a padlock for securing the cover to the electrical box thereby imparting a security function to the assembly.
OBJECTS AND ADVANTAGES
A first object is to eliminate the need for an installer to cut a large hole in the outer substrate of the house in order to install an electrical box on a building either covered with siding or under construction to be finished with siding. Cutting a large hole in the substrate can damage the insulation of a house and cause extra repair work for the contractor or homeowner. The present invention, by providing a siding block integral with the electrical box, eliminates the need for cutting a large hole in the substrate. The electrical box assembly of the present invention requires only a small hole to be made in the substrate in order to pull wiring into the box.
A second object of the invention is to provide an electrical box assembly that combines the utility of an FS box with an integral siding block for providing a 360-degree waterproof channel for accommodating siding around the periphery of the electrical box and channeling water away from the box and the surrounding siding.
A third object is to combine the functionality of a while-in-use cover with an FS style electrical box.
A further object is to provide a cover that is able to accept large electrical plugs of electrical cords while in use.
A further object of the invention is to provide tamperproof functionality to the electrical box assembly. The cover member is lockable to the electrical box portion of the assembly.
Another object is to provide smooth cord openings in the electrical box to eliminate fraying of electrical cords while the cords are plugged into the box.
Another object is to include reusable cord inserts to make the electrical box assembly weatherproof while the electrical box is not in use.
A further object is to enable installation of the electrical box assembly in either an old work situation or a new work situation. The electrical box assembly includes a removable base flange to convert the assembly so that it can be installed in an old work situation, wherein the siding is installed on the building.
These and other objects and advantages of the present invention will be better understood by reading the following description along with reference to the drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
Reference is made herein to the accompanying drawings, which are not necessarily drawn to scale, and wherein:
FIG. 1 is an isometric view of the preferred embodiment of an electrical box assembly with an integral siding block and a while-in-use cover in accordance with embodiments of the invention.
FIG. 2 is a front view of an electrical box which forms a portion of the electrical box assembly of FIG. 1 .
FIG. 3 is a side view of the electrical box of FIG. 2 .
FIG. 4 is an end view of the electrical box.
FIG. 5 is a sectional view of the electrical box taken along line 5 - 5 of FIG. 2 .
FIG. 6 is a rear view of the electrical box.
FIG. 7 is a front isometric view of the electrical box.
FIG. 8 is a front isometric view of a while-in-use cover member box which forms a portion of the electrical box assembly of FIG. 1 .
FIG. 9 is an isometric view of the electrical box assembly with the cover open.
FIG. 10 is a front elevation view of the electrical box assembly of FIG. 1 .
FIG. 11 is a sectional view of the electrical box assembly taken along line 11 - 11 of FIG. 10 .
FIG. 12 is an exploded isometric view of the electrical box assembly depicting the cover member separate from the electrical box.
FIG. 13 is an isometric view of an electrical box assembly according to the present invention with the cover member in the closed position.
FIG. 14 is a bottom view of the electrical box assembly of FIG. 13 , with the cover in the closed position.
FIG. 15 is an isometric view of a second embodiment of the electrical box assembly of the present invention.
FIG. 16 is a front elevation of the electrical box assembly of FIG. 15 .
FIG. 17 is a sectional view of the second embodiment of the electrical box assembly taken along line 17 - 17 of FIG. 16 .
FIG. 18 is an isometric view of a cord opening plug which forms a portion of the electrical box assembly of FIG. 1 .
FIG. 19 is a side view of the cord opening plug of FIG. 18 .
FIG. 20 is an isometric view of the electrical box assembly of the present invention with the while-in-use cover closed and plugs installed in the cord openings.
DETAILED DESCRIPTION
With reference to FIG. 1 , the present invention comprises an electrical box assembly 20 for mounting electrical components to the exterior of a finished building with siding installed on the exterior or to an unfinished building whose exterior that will be finished with siding. The electrical box assembly 20 includes an electrical box 22 with an integral siding block 24 and a while-in-use cover 26 .
Referring to FIGS. 2-3 , the electrical box 22 includes four inner sidewalls 32 , four outer sidewalls 34 , and a back wall 36 that define the inner enclosure or cavity 38 . Outer sidewalls 34 are of a larger dimension D1 than the inner sidewalls 32 of dimension D2. Two bosses 40 extend from the inner surface 42 of the outer sidewalls 34 . A peripheral wall 44 extends between the inner sidewalls 32 and outer sidewalls 34 . Bosses 40 include component mounting bores 46 therein and a groove 48 adjacent the mounting bores 46 and extending fully across each boss 40 .
The electrical box 22 includes a plurality of apertures 50 in the back wall 36 with each of the apertures 50 including a surrounding peripheral wall 52 extending inward of the back wall 36 . The back wall 36 further includes a plurality of knockouts 56 therein. A base flange 58 extends from the entire periphery of the inner sidewalls 32 . The base flange 58 is coplanar with the back wall 36 and includes breakaway grooves 60 therein. A second flange 62 extends from the outer periphery of the outer sidewalls 34 and includes a wide base portion 64 and a smaller outer portion 66 that includes a beveled edge 68 and four truncated corners 70 . The outer sidewalls 34 include a front edge 72 and a peripheral wall 74 extending laterally outward around the entire outer periphery of the front edge 72 .
As shown in FIG. 3 , electrical box 22 sidewalls 34 include a top end 76 and a bottom end 78 . Opposing outer sidewalls 34 of top end 76 include ears 80 , which are thick wall sections with apertures 82 therein. Bottom end 78 of the outer sidewalls 34 includes a leg 84 at one end. The leg 84 includes an aperture 86 therein. A tab 88 extends downward from the outer surface of one outer sidewall 34 .
Referring to FIGS. 4 and 5 , base flange 58 in combination with inner sidewalls 32 and second flange 62 define a channel 90 that aides removal of water from around the electrical box assembly and the siding (not shown) installed around its periphery. The breakaway grooves 60 in the back wall 36 of electrical box 22 enable an installer to modify the electrical box 22 for installation on an existing structure or old work situation. By scoring with a utility knife or similar sharp blade, an installer can remove the base flange 58 from the electrical box 22 . With the base flange 58 removed, a rectangular hole, large enough to receive the inner sidewalls 32 , may be cut in the siding (not shown) to accommodate the electrical box. For new construction, the base flange 58 is retained with the box 22 , and the electrical box is secured to the substrate by driving nails through apertures 50 in back wall 36 . Base flange 58 underlies the siding and shields the substrate from rain or water penetration. Any rain or water falling in channel 90 will fall to the bottom of the electrical box channel 90 and from thence fall away from the siding. As shown in FIG. 5 , the electrical box 22 includes an outer cavity 92 defined by peripheral wall 44 and outer sidewalls 34 . Outer cavity 92 is adapted to house an electrical component such as a duplex receptacle (not shown). The electrical component will seat flush against peripheral wall 44 and thus be recessed within the building wall that the electrical box 22 is secured to. Inner cavity 38 provides an enclosure for making wiring connections to the electrical component.
With reference to FIG. 6 , the breakaway grooves 60 are formed around the entire periphery of the inner sidewalls 32 . Thus flange 58 may be removed by scoring, with a utility knife or similar sharp blade, along grooves 60 and then breaking away flange 58 from the remainder of the electrical box 22 . Such a modification would be made in an old work situation, in order to adapt the electrical box to fit within a smaller hole in the siding. The breakaway grooves 60 extend completely from side 59 to side 59 of the electrical box.
Referring to FIGS. 8 and 9 , the cover 26 includes a front panel 94 , four sidewalls 96 , two ears 98 on opposing sidewalls, and apertures 101 in each ear 98 that are in axial alignment with one another. Sidewall panels 103 extend from three of the sidewalls 96 . The sidewall panels 103 and sidewalls 96 meet at a juncture 104 . An arm 105 extends from one end of the bottom sidewall 96 b and includes an aperture 107 therein. A brace 109 extends from the bottom sidewall 96 b to the arm 105 . The brace 109 is substantially planar and is orthogonal to the plane of the arm 105 . The cover 26 further includes a latch 111 with an opening 113 therein and two U-shaped openings 115 in the bottom sidewall 96 b . The cover 26 includes a beveled edge 117 at the juncture of the front panel 94 and each sidewall 96 . The ears 98 extend outward from the plane including the rear edge 102 of the sidewall panels 103 .
With reference to FIG. 9 , cover member 26 is secured to electrical box 22 by bolts 119 extending through the ears 98 of the cover 26 and through the outer sidewall 34 of the electrical box. Cover 26 further includes a jam 121 including a flat abutment surface 123 extending from the inner surface 125 of the cover. Flat abutment surface 123 is in alignment with the juncture 104 between the cover sidewall 96 and the sidewall panel 103 . The jam 121 cooperates with brace 109 in leveling the cover 26 with respect to the front edge 72 of the electrical box 22 . When cover 26 is closed on electrical box 22 , aperture 107 in arm 105 of cover 26 is in axial alignment with aperture 86 in leg 84 of electrical box 22 .
Referring to FIG. 11 , the cover member 26 is hinged to the electrical box 22 by bolts 119 . When the cover 26 is closed upon the electrical box 22 , brace 109 near the bottom of the box and flat abutment surface 123 of jam 121 each contact the front edge 72 of the electrical box 22 and maintain panel 94 of cover parallel with the front edge 72 of the electrical box 22 .
FIGS. 12 and 13 illustrate an alternative embodiment of the electrical box assembly 127 which includes an alternative means of connecting cover member 26 to the box. In this embodiment, electrical box 129 includes posts 131 integral with and extending from opposing sides of the outer sidewalls 34 . Ears 98 of cover member 26 are flexible and are slipped over the electrical box 129 and posts 131 wherein the cover becomes operatively hinged to the electrical box.
With reference to FIG. 14 , with the cover 26 closed on the electrical box 22 , U-shaped openings 115 abut the front edge 72 of the electrical box 22 and form two smooth-walled while-in-use cord openings 133 through which electrical cords (not shown) can be passed. Closing of cover 26 upon electrical box 22 further causes latch 111 of cover to engage tab 88 of electrical box to snap lock the cover 26 to the box 22 . The electrical cord openings 133 are formed on the bottom sidewall 96 b of the electrical box assembly at the juncture 132 of the cover 26 and the outer sidewall 34 of the electrical box 22 . As cover 26 is closed on the box 22 , tab 88 snaps through opening 113 in latch 111 .
With reference to FIG. 15 , there is shown another alternative embodiment of the electrical box assembly 135 . Electrical box assembly 135 includes a horizontal electrical box 137 versus the vertical electrical box of the first embodiment. Additionally, horizontal electrical box assembly 135 includes shrouds 139 surrounding the U-shaped openings 115 in the cover 26 . When cover 26 is closed on electrical box 137 , aperture 107 in arm 105 of cover 26 is in axial alignment with aperture 86 in leg 84 of electrical box 137 .
Referring to FIGS. 16 and 17 , the horizontal electrical box assembly 135 , similar to the first embodiment, includes an integral siding block 24 including a base flange 58 , a second flange 62 , and the inner sidewalls 32 defining a channel 90 for receiving siding (not shown) therein. After the horizontal electrical box assembly 135 is secured to a wall and siding is installed around the assembly, any rain falling within the channel 90 will fall to the bottom of the siding block 24 and fall away from the siding. As in the first embodiment, when the cover 26 is closed upon the electrical box 137 , brace 109 near the bottom of the box and flat abutment surface 123 of jam 121 each contact the front edge 72 of the electrical box 137 and align panel 94 of cover parallel with the front edge 72 of the electrical box 137 .
With reference to FIGS. 18 and 19 , the electrical box assembly of the present invention includes cord opening plugs 141 that include a plug body 143 with two sides 145 and 147 . Three legs 149 extend from the plug body 143 including one leg on a first side 145 and two legs on the opposing side 147 that are installed at the U-shaped openings 115 in the bottom sidewall 96 b of the cover 26 as shown in FIG. 20 . The plugs 141 are preferably molded in one piece of plastic. The legs 149 define a gap 151 that is slightly larger than the thickness of the sidewall 96 b surrounding the U-shaped openings 115 . The plugs 141 are supplied installed on the electrical box assembly 20 as shown in FIG. 20 , but can be removed or subsequently installed by the homeowner as needed. When electrical cords (not shown) are connected to the receptacle within the box, the plugs are removed to provide cord openings for the cords. If the electrical cords are removed, the plugs 141 can be installed on the sidewall 96 b at the U-shaped openings 115 in order to close the cord openings 133 (see FIG. 14 ) thereby further waterproofing the box and also preventing insects from entering the cord openings.
With reference to FIG. 11 , as a result of the wide sidewalls 96 of the cover 26 , the electrical box assembly 20 advantageously can accommodate large plugs (not shown) of electrical cords. The depth of the inside surface of the cover 26 from the front edge 72 of the electrical box 22 , shown as distance D3, is preferably at least 1.5 inches. Distance D4 in the figure, the distance between the mounting face of the electrical component and the inside surface of the cover 26 is preferably at least 2.75 inches. The volume within the cover member 26 is preferably at least 22 cubic inches. The inner cavity 38 preferably includes a volume of at least 17 cubic inches. Thus the depth of the outer cavity 92 of the electrical box is the difference between D3 and D4, which is at least 1.25″. This provides ample space for accommodating a f-inch long electrical plug within the outer cavity 92 . A large electrical plug as described herein is one that is over ¾-inch in length.
The electrical box 22 and cover plate 26 of the present invention may be manufactured of metal or plastic. Most preferably the electrical box 22 and cover plate 26 of the present invention are each molded of plastic in one piece. In the preferred embodiment of the electrical box, the siding block 24 , including the base flange 58 and second flange 62 , are thus an integral portion of the one-piece molded electrical box 22 .
The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
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A weatherproof while-in-use electrical box assembly adapted for use on buildings that include a siding exterior or that will be finished with siding. The weatherproof electrical box assembly includes an electrical box with an integral siding block and a cover assembly adapted to receive large electrical plugs. The integral siding block provides a channel around the electrical box for accommodating siding. The channel enables the electrical box assembly to channel water to the bottom of the box and exterior of the siding where it will drip harmlessly to the ground. The cover assembly includes cord openings that enable closing of the cover plate while electrical cords are connected to electrical outlets within the electrical box. Cord inserts are provided for closing the cord openings when they are not in use. The tamperproof cover includes an arm adapted to accept a padlock for securing the cover to the electrical box.
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BACKGROUND OF THE INVENTION
The present invention relates generally to computers, and more particularly, to an abnormal information output system for a computer system.
Concerning the cost issue, some of the conventional computer systems provides no baseboard management controller (BMC sub-system) but use a microprocessor to substitute the BMC sub-system for management, for example, recording operation status information like temperatures of hardware and chips in the computer systems.
However, the microprocessor may not be used to record the operation status information of the system in case the microprocessor fails. More particularly, if some abnormal events (for example, overheating of a CPU chip) occur, the computer system would fail. Under this circumstance, information of the above-mentioned abnormal events cannot be recorded by the microprocessor, and inspectors may thus fail to determine the causes of such abnormal events which occur in the system. For the above reasons, it is desired to cure such deficiencies in the conventional computer systems.
BRIEF SUMMARY OF THE INVENTION
Examples of the present invention may provide an abnormal information output system for a computer system, the computer system comprising at least a plurality of hardware devices and a plurality of sensors for detecting operation statuses of the hardware devices, the abnormal information output system comprising at least a latch module connected to each of the sensors and the hardware devices, being configured for latching operation status information of the hardware devices during an abnormal operation when the abnormal operation of the computer system is detected; and a basic input-output system (BIOS) module embedded in the computer system and connected to the latch module, being configured for analyzing the latched operation status information when the computer system returns to a normal operation so as to output corresponding abnormal information.
Some examples of the present invention may provide an abnormal information output system for a computer system, the computer system comprising at least a plurality of hardware devices and a plurality of sensors for detecting operation statuses of the hardware devices, the abnormal information output system comprising at least a latch module connected to each of the sensors and the hardware devices, being configured for acquiring operation status information of the hardware devices in real time; and detecting an abnormal operation of the computer system and latching the operation status information of the computer system and the hardware devices during the abnormal operation when the abnormal operation of the computer system is detected, and a basic input-output system (BIOS) module embedded in the computer system and connected to the latch module, being configured for: reading the latched operation status information after the computer system returns to a normal operation; and analyzing the latched operation status information based on pre-stored operation status information corresponding to the normal operation of the computer system so as to output corresponding abnormal information.
Still other examples of the present invention may provide an abnormal information output system for a computer system, the computer system comprising at least a plurality of hardware devices and a plurality of sensors for detecting operation statuses of the hardware devices, the abnormal information output system comprising at least: an acquiring unit connected to each of the sensors and the hardware devices, being configured for acquiring operation status information of the hardware devices in real time; a latch unit connected to the acquiring unit, being configured for detecting an abnormal operation of the computer system and latching operation status information of the hardware devices and the computer system during the abnormal operation when the abnormal operation of the computer system is detected; a reading unit connected to the latch unit, being configured for reading the latched operation status information from the latch unit after the computer system returns to a normal operation; and an analyzing unit connected to the reading unit, being configured for receiving the latched operation status information from the reading unit, and analyzing the latched operation status information based on pre-stored operation status information corresponding to the normal operation of the computer system so as to output corresponding abnormal information.
Additional features and advantages of the present invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The features and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings examples which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
In the drawings:
FIG. 1 is a schematic block diagram illustrating a structure of an abnormal information output system for a computer system in accordance with an example of the present invention; and
FIG. 2 is a schematic block diagram illustrating a structure of an abnormal information output system for a computer system in accordance with another example of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Reference will now be made in detail to the present examples of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
FIG. 1 is a schematic block diagram illustrating a structure of an abnormal information output system 1 for a computer system 2 in accordance with an example of the present invention. Referring to FIG. 1 , the abnormal information output system 1 includes a latch module 11 and a basic input-output system (BIOS) module 12 . Furthermore, the computer system 2 includes at least a plurality of hardware devices 21 and sensors 22 for detecting operation status of each of the hardware devices 21 . Preferably, the hardware devices 21 include but not limited to a display module, an input-output (IO) chip, a central processing unit (CPU) chip, a fan module, a peripheral component interconnect (PCI) module, a memory module, a hard disk and optical disk driving module, a power supply module, etc.
The latch module 11 which is connected to each of the sensors 22 and the hardware devices 21 , is configured for latching operation status information of abnormal hardware devices 21 when an abnormal operation of the computer system 2 is detected.
FIG. 2 is a schematic block diagram illustrating a structure of an abnormal information output system 1 for a computer system 2 in accordance with another example of the present invention. Referring to FIG. 2 , specifically, the latch module 11 includes an acquiring unit 111 and a latch unit 112 . The acquiring unit 111 which is connected to each of the sensors 22 and the hardware devices 21 , is configured for acquiring operation status information of the hardware devices 21 in real time. The operation status information includes any status information of the hardware devices 21 as the computer system 2 operates, for example, temperature of the CPU of the computer system 2 , output voltage level(s) of pin(s) of the CPU chip, output voltage of the power supply module, and output voltage level(s) of pin(s) of the IO chip, etc.
Methods of acquiring current operation status information of the computer system 2 include but not limited to the following:
(1) The operation status information is provided by the sensors 22 which sense the operation statuses of the hardware devices 21 of the computer system 2 . For example, the temperature information of the CPU is provided by a temperature sensor which senses the temperature of the CPU chip.
(2) The operation status information is directly provided by the hardware devices 21 of the computer system 2 . In one example, the acquiring unit 111 is directly connected to an output terminal of the power supply module of the computer system 2 , so that the output voltage of the power supply module can be acquired by the acquiring unit 111 . In another example, the acquiring unit 111 is directly connected to the pin(s) of the IO chip of the computer system 2 , so that the output voltage level(s) of the pin(s) of the IO chip can be acquired by the acquiring unit 111 .
It shall be appreciated that, the above-mentioned methods of acquiring operation status information of the computer system 2 are only illustrative but not intended to limit the present invention. Actually, any methods of acquiring operation status information of the computer system 2 are covered within the scope of the present invention.
The latch unit 112 which is connected to the acquiring unit 111 , is configured for detecting the abnormal operation of the computer system 2 and latching the operation status information of each of the hardware devices 21 during abnormal operation. The abnormal operation of the computer system 2 includes any conditions in which the computer system 2 fails to operate normally. More particularly, the above-mentioned abnormal operation preferably includes but not limited to a crash of the computer system 2 , automatically rebooting of the computer system 2 and displaying blue color on the screen, etc. Furthermore, preferably, the latch module 11 includes any modules which are capable of latching the operation status information outputted by the hardware devices 21 and the sensors 22 . More preferably, the latch module 11 includes any chips or digital circuits capable of latching a voltage level transition signal, which include but not limited to a PCA9535 chip.
Specifically, methods of detecting the abnormal operation of the computer system 2 by the latch unit 112 include but not limited to detecting whether the computer system 2 operates abnormally based on abnormal signals outputted by each of the hardware devices 21 . For example, the latch unit 112 determines the abnormal operation of the computer system 2 based on the acquired voltage level transition signal(s) outputted by the pin(s) of the CPU chip.
Methods of latching the operation status information of the computer system 2 during the abnormal operation, which are performed by the latch unit 112 , include but not limited to the following:
(1) Latching the acquired operation status information of each of the hardware devices 21 during abnormal operation of the computer system 2 . For example, based on transition signal(s) outputted by the pin(s) of the CPU chip, the latch unit 112 determines that the computer system 2 operates abnormally. Meanwhile, the latch unit 112 deems the currently acquired operation status information, such as the temperature value provided by the temperature sensor which detects the temperature of the CPU and the output voltage provided by the power supply module, as the operation status information of the abnormally operated computer system 2 . Then, the acquired operation status information is latched by the latch unit 112 .
(2) Latching the operation status information of the hardware devices 21 based on the acquired abnormal signals of the hardware devices 21 . For example, based on the acquired voltage level transition signal(s) transitioning from a low voltage level to a high voltage level that is/are outputted by the pin(s) of the IO chip, the latch unit 112 determines that the computer system 2 operates abnormally. Then, the high voltage level signal(s) currently outputted by the pin(s) of the IO chip is deemed as the operation status information of the computer system 2 during the abnormal operation, and the above-mentioned operation status information is latched by the latch unit 112 .
The BIOS module 12 which is embedded in the computer system 2 and connected to the latch module 11 , is configured for analyzing the latched operation status information when the computer system 2 returns to a normal operation, so as to output corresponding abnormal information.
Preferably, as shown in FIG. 2 , the BIOS module 12 includes a reading unit 121 and an analyzing unit 122 . The reading unit 121 which is connected to the acquiring unit 111 , is configured for reading the latched operation status information after the computer system 2 returns to the normal operation. For example, the reading unit 121 reads the latched operation status information of each of the hardware devices 21 during the normal self-checking process of the computer system 2 .
The analyzing unit 122 which is connected to the reading unit 121 , is configured for analyzing the latched operation status information based on pre-stored corresponding normal operation status information, so as to determine abnormal information. For example, by comparing the latched CPU temperature information and the pre-stored normal CPU temperature threshold, the analyzing unit 122 determines whether the abnormal information indicates overheating of the CPU. Furthermore, the analyzing unit 122 records the abnormal information in a malfunction log of the computer system 2 , so as to facilitate the BIOS module outputting the abnormal information to the display module of the computer system 2 .
From the above, by latching operation status information of each of the hardware devices 21 during the abnormal operation of the computer system 2 , the abnormal information output system 1 for a computer system 2 of the present invention can overcome an issue of the conventional computer system that, information of the cause for malfunction of the chip and system cannot be recorded due to abnormal operation of the system software or sudden crash of the system. Furthermore, the cause of the abnormal operation of the computer system 2 can be determined by analyzing the latched operation status information of the computer system 2 . Thereby, professionals can accurately and rapidly diagnose the issues of the hardware or chip in the computer system 2 . Moreover, the present invention features a low cost as compared with the conventional computer system that adopts the BMC sub-system to record the operation status information of the computer system. Therefore, the present invention significantly overcomes various shortcomings in the prior art and thus achieves a high value for the industry.
It will be appreciated by those skilled in the art that changes could be made to the examples described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular examples disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
Further, in describing representative examples of the present invention, the specification may have presented the method and/or process of the present invention as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process of the present invention should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present invention.
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Provided is an abnormal information output system for a computer system, wherein the computer system includes at least a plurality of hardware devices and a plurality of sensors for detecting operation statuses of each hardware device. The abnormal information output system includes at least a latch module connected to each of the sensors and the hardware devices, wherein the latch module is configured to latch operation status information of the hardware devices when abnormal operation of the computer system is detected; and a basic input-output system (BIOS) module embedded in the computer system and the BIOS module is connected to the latch module and configured to analyze the latched operation status information when the computer system returns to a normal operation so as to output corresponding abnormal information. Accordingly, the computer system is capable of recording a chip failure and information regarding reasons for system failure.
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BACKGROUND OF THE INVENTION
The invention relates to a novel display system, and to in particular illuminated display boards.
Originally, illuminated display boards were essentially display boards with an external light source. For example, a billboard with lights. Smaller displays were generally even less sophisticated and were not even illuminated.
As the market grew and the need for advertising increased so has the need for more sophisticated but just as simple display systems.
With the advent of translucent plastics, back-illuminated signs and displays have become very popular. This type of system essentially comprises a bank of lights, generally the fluorescent variety with a translucent sheet with the sign applied thereto; either by the way of painting or etching and the like. Large banks of lights are often required to illuminate the entire surface of the signs. A disadvantage of such back-illuminated signs is that a large number of lights are required, increasing running costs and maintenance costs since they are continually needing to be replaced. Furthermore, when one light needs to be replaced generally the entire sign needs to be dismantled, which is a great inconvenience when a large sign is involved.
Clear sheet materials with the sign directly applied to the surface have recently been used. However, the problem with these types of signs/displays, as with the back-illuminated signs, a number of lights are required to fully illuminate the sign. In this case the display requires a light source along each edge of the sheet in order for the sign to be illuminated and even then the middle portion of the display is not illuminated to the same degree as the edges.
The prior art has attempted to increase the degree of illumination of translucent and transparent mediums and generally these attempts have not been particularly successful when applied to larger areas which is often the case with signs. Illumination of a small area is generally easier and an attempt at increasing the illumination of a small area is discussed in U.S. Pat. No. 3,241,256. This patent dealt with providing uniform brightness on instrument dials, scales and indicator tapes, generally small in nature. A dot pattern was applied to the rear side of the light transmitting block only wherein the block is supported by a plate. As with previous systems, when larger areas are required to be illuminated, a number of light sources are required to fully illuminate the entire area of the sign.
SUMMARY OF THE INVENTION
The present invention provides a novel illuminated display system which reduces the number of lights required to illuminate the same size display and also alleviate some of the other problems of the prior art.
The invention provides an illuminated display system comprising a transparent medium having two opposing surfaces to be illuminated, wherein both of said surfaces to be illuminated have a matrix of dots substantially covering said surfaces to be illuminated.
The invention also provides an article for use in an illuminated display system comprising a transparent medium having two opposing surfaces to be illuminated wherein both of said surfaces to be illuminated has a matrix of dots substantially covering said surfaces to be illuminated.
The invention further provides an article for fixing on to a transparent sheet used in an illuminated display system comprising a transparent film with a matrix of dots applied thereto.
Surprisingly and advantageously, the illuminated display system of the present invention with a dot matrix applied to both sides of the transparent sheet, provides greater and more even illumination of the sign. This is also true for large signs. The prior art does not discuss this important finding and the theory does not predict that by applying a dot matrix to both sides would enhance illumination significantly. Also by using the system, maintenance is reduced as well as the power requirements.
The light source is generally fixed to only one edge of the transparent sheet. Only in very large signs may another light source be required on another edge.
Furthermore, the density of dots preferably increases along the transparent sheet in the from the edge where the light source is to be fixed.
To increase the density of dots the dots can either increase in number and the gaps between the dots decreases in size or alternatively, the gaps between the dots stay the same and the size of the dots increases.
"Dots" used in the specification and in the claims can be of any shape, for example square, round, rectangular, triangular and in fact can be of irregular shape. The dots are translucent or opaque and more preferably light-coloured for example, white. "Transparent medium" used in the specification and claims means one or more transparent sheets.
The dots can be applied to the transparent sheet by etching, painting, screen printing or any other means of applying a medium to a transparent sheet. Alternatively, the matrix of dots may be applied to a transparent film which then may be adhered to the transparent sheet.
The transparent medium may be glass or plastic but is preferably acrylic.
Generally to form the sign, in the case of a one-sided sign, a backing plate is provided which is generally opaque and light in colour, preferably white.
In the case of a two-sided sign, another sheet with a light coloured face, preferably white, facing the dot matrix of the transparent sheet, is attached. This other sheet may be plain or have the sign applied to the other side. This other sheet should be sufficiently translucent to allow some light to pass through and illuminate the sign. The other sheet may be made of any material including plastics and paper.
The light source can be retained in a carrier which can also act as a support for the transparent sheet. Preferably the light source is a fluorescent tube or depending on the size of the display, a number of tubes.
The article for use in an illuminated display system of the invention can be placed within a box structure wherein translucent panels are provided and the article in combination with the light source acts as an extended light source.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a preferred embodiment of an illuminated display system of the present invention.
FIG. 2a illustrates a preferred embodiment of a one-sided sign.
FIG. 2b illustrates a preferred embodiment of a two-sided sign.
Item 10 illustrates a transparent sheet 10 with the matrix of dots 13 applied to the surface 11. A matrix of dots 13 is also applied to the other side 12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The transparent medium 10 can be accommodated in a carrier 20 which also houses a light source 21. It should be noted that the light source can be affixed in alternate ways, providing the light source is substantially on the edge of the transparent medium 10.
FIGS. 1 and 2a illustrates an arrangement for a one-sided sign in accordance with the invention. Transparent medium 10 has dot matrix 13 applied to both surfaces 11 and 12 to be illuminated. A backing sheet 14 which is opaque and preferably white in colour is fixed to the transparent medium 10. FIG. 2a illustrates that there is a gap between each of the layers for clarity only, in practice the layers would be in substantial contact with each other. Sheet 15 has a sign 30 printed on its front side. The side of sheet 15 in substantial contact with transparent medium 10 is light in colour and generally white. Sheet 15 is sufficiently translucent to allow some light to pass through the sheet and illuminate the sign. Materials found to be sufficiently translucent include paper (for example posters) and plastic materials.
FIG. 2b illustrates an arrangement for a two-sided sign in accordance with the invention. In the case of a two-sided sign, sufficiently translucent sheets 16 are fixed to the transparent medium 10 with dot matrix thereon. These sheets 16 may be plain or have the sign applied to the outer face of the sheet. The face contacting the transparent sheet 10, at least, is light coloured and preferably white. Similarly if the sheet 16 is plain, the sheet is preferably light coloured and more preferably white. In the case where sheets 16 are plain, further sheets 17 may be incorporated into the sign system, wherein the sheets 17 have the sign applied thereto. Once again sheets 17 are sufficiently translucent to allow some of the light to pass through and illuminate the sign. Similarly for the one-sided sign sheet 15 may be plain and an additional translucent sheet (not shown) can be fixed in front of the plain sheet 15.
Framework (not shown) or the like, can be used to secure all of the layers together. Similarly the carrier and light source housing 20 can also retain the translucent sign sheet.
To more clearly illustrate the present invention tests were conducted on different sized signs wherein the dot matrix in the first instance is only applied to one side of the transparent medium. The dot matrix in this preferred embodiment is applied by screen printing white dots directly on to the transparent material, in this case perspex. The density of the dot matrix, as indicated previously, increases away from the light source.
Secondly, the dot matrix is applied to both sides of the transparent medium in the same way as for the one-sided application.
In both cases only one edge of the sign had a lighting means attached thereto and fluorescent lighting was used. Furthermore, only one-sided signs were formed, and thus an opaque white backing sheet was used in the trials.
Light meter readings were taken at two positions on each of the signs, midway from the light source and at the opposite end of the light source.
The results of the tests are shown below:
TABLE 1______________________________________ Light Meter Reading (Lux) (cm) DistanceSize Midway At Opposite from lightof Sign from light end of source light(cm × cm) source light source travelled______________________________________30 × 16 one-sided 2600 2400 16 two-sided 3400 240030 × 30 one-sided 1500 1250 30 two-sided 1950 145060 × 45 one-sided 475 435 45 two-sided 810 68560 × 60 one-sided 440 300 60 two-sided 720 440______________________________________
Further experiments were conducted by Optical and Photometric Technology Pty, a NATA registered organisation on two acrylic sheets which had the dimensions 10 mm (thick)×520 mm (long)×260 mm (wide). One of the sheets had the dot matrix applied to both sides, the other sheet had the same pattern applied but to only one side. The panels were illuminated on the edge along the 260 mm side. The illumination source was an Osram Deluxe SPL 11W/21 orientated horizontally and housed in a triangular aluminium extrusion. The results of the experiments on each sheet are shown in Table 2. Table 2 illustrates the sheets per se and the values represent the Luminance values at that particular location on the sheet. The light source is attached at the top of the page.
TABLE 2______________________________________260 mm (Light Source)202 200 121[52] [55] [37]224 221 146[74] [68] [48]218 204 158[80] [74] [59]184 177 146[87] [75] [60]520 mm143 140 119[79] [72] [57]109 107 92[67] [59] [54]76 72 63[61] [58] [52]59 57 52[60] [58] [54]______________________________________ Luminance values in lumens for the double sided application are in numbers without brackets, luminance values in lumens for the single sided application are in [Brackets]
The test results in both trials clearly indicate a marked improvement of the illumination of the sign when the dot matrix is applied to both sides of the transparent medium. This is especially true in the middle of the sign wherein most of the message to be illuminated is placed. Furthermore the effectiveness of the dot matrix is still good even for larger sizes.
The display system in accordance with the invention can be used in small and very large displays and advantageously providing good illumination without the large number of lights previously required. Manufacturing and maintenance of the signs is less time consuming and simpler.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.
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An edgelit illuminated display system has a transparent medium having first and second opposing surfaces and at least one edge operable with a light source for illuminating the first and second surfaces. A matrix of dots on each of the surfaces is arranged to allow interaction of light between the surfaces. The matrix of dots on at least one of the surfaces substantially covers the entire surface for providing an even increased illumination throughout the surface, wherein when a graphic image is supported over the surface the graphic image is evenly illuminated.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional Patent Application No. 61/128,219, filed May 20, 2008 in the names of Miles Clayton Russell, Gregory Allen Kern, Ruel Davenport Little and Zachary Adam King.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to solar electric power systems, and more particularly to an AC photovoltaic module including an inverter sized and configured so as to collect less heat, and to dissipate heat, and to operate under relatively cool conditions.
[0004] 2. Description of the Prior Art
[0005] It is known to provide an AC photovoltaic module including a DC photovoltaic module for converting solar energy to DC electrical energy, and an inverter for converting the DC electrical energy to AC electrical energy, and for feeding the AC electrical energy to an AC grid. See, for example, International Patent Application No. PCT/US2009/038547.
[0006] The inverter typically is mounted at or near the center of the DC photovoltaic module. It is known that the center of the DC module suffers the greatest elevation of heat during a sunny day, and after the sun has lowered and disappeared, the greatest change in temperature.
[0007] The extremes of temperatures of the inverter lead to a relatively short life span of the inverter. Inasmuch as each AC module is provided with an inverter, keeping all inverters active in an array of numerous modules can be problematic.
[0008] An object of the invention is therefore to provide an AC photovoltaic module having an inverter of a beneficial size and configuration, and mounted on the DC photovoltaic module at a relatively cool peripheral portion of the DC module.
[0009] A further object of the invention is to provide an arrangement of components in the inverter such as to concentrate heat in the inverter on one side thereof, and to provide heat sink means for dissipating the heat from that side to the surrounding environment.
[0010] A still further object of the invention is to provide film capacitors in the inverter circuitry, which operate more reliably and more effectively, with less internal resistance, and therefore generally less heat, than the same assembly circuitry with commonly used electrolytic capacitors.
SUMMARY OF THE INVENTION
[0011] With the above and other objects in view, a feature of the present invention is the provision of an AC photovoltaic module including a DC photovoltaic module for converting solar energy to DC electrical power, and an inverter for converting DC electrical power to AC electrical power, the inverter being adapted for connection to a peripheral frame portion of the DC photovoltaic module and being sized and configured to dispense heat therefrom, to prolong operational life and reliability of the inverter.
[0012] In accordance with a further feature of the invention, there is provided an AC photovoltaic module comprising a DC photovoltaic module for producing DC electrical power, and an inverter for converting the DC electrical power to AC electrical power, wherein the inverter is mounted on the DC photovoltaic module, and wherein the inverter comprises a narrow elongated body mounted proximate an outer edge of the DC photovoltaic module, such that an elongated side of the inverter is fixed in abutting relationship to the outer edge of the DC photovoltaic module.
[0013] In accordance with a further feature of the invention, there is provided an AC photovoltaic module comprising a DC photovoltaic module for producing DC electrical power, and an inverter for converting the DC electrical power to AC electrical power, the inverter having film capacitor means therein for storing and releasing electrical energy, and the inverter being mounted on the DC photovoltaic module proximate an edge of the DC photovoltaic module.
[0014] In accordance with a still further feature of the invention, there is provided an inverter assembly for converting a DC electric power input to an AC electrical power output, the inverter assembly comprising means for receiving the DC electrical power from a DC power source, one or more film capacitors for filtering input current switching ripple of a DC/DC converter, the DC/DC converter being adapted to convert input voltage from the DC power source to voltage suitable for a DC/AC inverter, a second set of one or more film capacitors for filtering switching ripple output of the DC/DC converter and input switching ripple of the DC/AC inverter, the DC/AC converter being adapted to convert DC power to AC current and feed the AC current into an AC power grid.
[0015] In accordance with a still further feature of the invention, there is provided an inverter assembly comprising means for receiving DC electrical power from a DC power source, a DC/AC inverter adapted to convert the DC electrical power to AC electrical power, and a set of one or more film capacitors for (a) filtering switching ripple of input current to the DC/AC inverter, and for (b) filtering energy difference between the inverter DC input power and the inverter AC output power, and the DC/AC inverter being adapted to feed AC current into an AC power grid.
[0016] The above and other features of the invention, including various novel details of construction and combinations of parts, will now be more particularly described with reference to the accompanying drawings and pointed out in the claims. It will be understood that the particular devices embodying the invention are shown by way of illustration only and not as limitations of the invention. The principles and features of the invention may be employed in various and numerous embodiments without departing from the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Reference is made to the accompanying drawings in which are shown illustrative embodiments of the invention, from which its novel features and advantages will be apparent, wherein corresponding reference characters indicate corresponding parts throughout the several views of the drawings, and wherein:
[0018] FIG. 1 is a plan view of a framed photovoltaic module, illustrating typical gradients of heat exhibited by a module subjected to sunlight;
[0019] FIG. 2 is a back dimensional view of an AC photovoltaic module, including an inverter mounted on a frame portion of the module;
[0020] FIG. 3 is a perspective view of a frame portion of a photovoltaic module with an inverter fixed thereto;
[0021] FIG. 4 is a length-wise cross-sectional view of the inverter of FIG. 3 ;
[0022] FIG. 5 is a width-wise cross-sectional view of the inverter of FIG. 4 ;
[0023] FIG. 6 is an end view of an inverter mounted on a frame member, and a heat sink in the form of a plate fixed to the inverter and extending therefrom, and in phantom shows an optional heat sink feature;
[0024] FIG. 7 is a diagrammatic view of an inverter adapted to receive DC electrical current from a DC source and to provide AC electrical current to an AC grid;
[0025] FIG. 8 is a diagrammatic view of an alternative inverter adapted to receive DC electrical current from a DC source and to provide AC electrical current to an AC grid;
[0026] FIG. 9 is a graphical illustration of DC input power, constant with time, and AC output power pulses; and
[0027] FIG. 10 is a graphical illustration showing ripple voltage that typically appears on an energy storage capacitor over time.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] Referring to FIG. 1 , it will be seen that a DC photovoltaic module 20 illuminated by sunlight, and in the absence of air flow, will exhibit gradients of heat, with a hottest area H appearing in a generally central area of the module. Extending outwardly from the central area are progressively cooler areas, H 2 , H 3 , H 4 , and a coolest area C at an outermost edge of the module which is typically bounded by a frame 22 .
[0029] At sunless times, and particularly at night time, the module 20 can cool to ambient, and below ambient, temperatures with the central area of the module experiencing the greatest temperature drop. Such change in temperature, particularly over an extended time, is conducive to condensation occurring in the module, which can lead to freeze-thaw mechanized stress in the unit, corrosion, and/or loss of insulation resistance. Accordingly, the most beneficial location for an inverter is proximate the frame 22 , that is, in an area well removed from the central area of the module 20 .
[0030] As shown in FIG. 2 , an AC photovoltaic module 24 includes a DC photovoltaic module 20 and an inverter 30 , the DC module converting solar energy to DC electrical power, and the inverter converting DC electrical power to AC electrical power.
[0031] Referring to FIGS. 2 and 3 , it will be seen that in accordance with the invention an inverter 30 is provided which is mechanically attachable to the frame member 22 .
[0032] The inverter 30 is of a narrow elongated configuration, such that throughout the length of the inverter, the inverter is disposed in the coolest area C of the DC module 20 . Further, the inverter 30 is mounted on a back portion of the frame 22 so as to be out of direct sunlight. Still further, the inverter is spaced from the back of the solar cells of the module 20 .
[0033] The frame 22 is typically of metal, usually aluminum, which provides a heat sink for the inverter 30 mounted thereon. Thus, heat from the inverter is transferred throughout the frame 22 which, in turn, is located in the coolest region of the module 20 .
[0034] The narrow, elongated configuration of the inverter 30 , typically about 12 inches in length and 2×2 inches in cross-section, permits an extended inverter-to-frame contact surface so that heat is readily transferred to the frame and much less likely to build up in the inverter.
[0035] Referring to FIG. 4 , it will be seen that the inverter 30 comprises a housing 32 in which is disposed a series of electrical components 34 known in the art. The electrical components 34 are mounted on an elongated circuit board 36 extending throughout most of the length of the housing 32 .
[0036] Within the inverter housing 32 , the electrical components 34 are disposed in a manner facilitating the removal of heat from the inverter. With that in view, the cooler and taller components 40 , such as inductors and capacitors are mounted on a first side 44 of the circuit board 36 , while heat-producing and shorter components 42 , such as diodes and transistors, are mounted on a second side 46 of the circuit board 36 .
[0037] Thus, as seen in FIGS. 4 and 5 , the heat-producing components 40 are necessarily disposed proximate a wall 48 of the housing 32 , the wall 48 thereby serving as a heat sink for dissipation of heat generated internally of the inverter 30 .
[0038] To further expedite the removal of heat from the inverter 30 , there may be provided in addition to, or instead of the housing wall 48 , an inverter heat sink 50 ( FIG. 5 ) for conveying heat from inside the inverter housing 32 to the surrounding environment. The heat sink 50 may be provided with a plate portion 52 ( FIGS. 3 and 6 ) extending outwardly from the inverter housing 32 , and/or may be provided with a portion 54 ( FIG. 6 ) extending from the heat sink 50 into the housing 32 proximate the “hot” components 42 .
[0039] The heat sink 50 preferably is of aluminum and of a thickness of about 0.125 inch.
[0040] To still further expedite the removal of heat from the inverter 30 , the wall 56 of the inverter housing 32 , which faces away from the module frame 22 , may be provided with a highly emissive coating or treatment 58 ( FIG. 6 ) to increase radiative heat transfer from the inverter.
[0041] To still further expedite the removal of heat from the inverter 30 , the cavity of the inverter may be filled with pottant, which provides heat transfer away from the hot components. In addition, the pottant provides thermal mass which limits temperature excursions of the hot components and the rate of change of the thermal components under varying generation of the DC source.
[0042] There is thus provided an inverter which, by nature of its size and configuration and location, and the arrangement of its internal components, provides a longer life cycle than was heretofore customary.
[0043] Another avenue by which to extend the life of the inverter is to avoid the use of historically troublesome electronic components. The most vulnerable component at present is the state-of-the-art electrolytic capacitor, which is inexpensive and adapted to store a relatively large amount of energy, but is known to deteriorate in a typical AC module environment of high temperature, temperature cycling, and voltage spikes.
[0044] In FIG. 7 , there is shown an inverter 60 in electrical communication with a DC source, which may be a DC photovoltaic module, wind, hydro, battery, fuel cell, or the like. Between the DC source and the DC/DC converter 62 is a capacitor 64 , used to filter the input current switching ripple of the DC/DC converter 62 . The DC/DC converter 62 converts the input voltage from the source to a voltage level suitable for a DC/AC inverter 66 . Between the DC/DC converter 62 and the DC/AC inverter 66 is a further capacitor 68 , for filtering the switching ripple output of the DC/DC converter 62 and the input switching ripple of the DC/AC inverter 66 .
[0045] The capacitor 68 may also be used as a main energy storage element to make up for any difference in input DC power and output AC power as a function of time; refer to FIGS. 9 and 10 .
[0046] The DC/AC inverter 66 converts a DC voltage to an output AC current which is injected into an AC power grid 70 . In the AC power grid 70 , voltage is typically regulated by a utility or a local generation facility.
[0047] As noted above, the DC source may be a photovoltaic module 20 . The capacitor 64 is a film capacitor for filtering the input current ripple of the DC/DC converter 62 . The DC/DC converter 62 is a full bridge converter. The capacitor 68 stores the difference in energy input from the DC input to the AC output. This difference in energy causes a ripple voltage to appear on capacitor 68 . The ripple voltage on capacitor 68 is sinusoidal under ideal operating conditions, at twice the frequency of the AC grid 70 .
[0048] The DC/AC inverter 66 is a full bridge inverter operated in discontinuous conduction mode. The DC/AC inverter 66 is operated such that the output current is a controlled low (5%) total harmonic distortion current wave-form. The AC grid 70 is a 120 volt 60 Hertz AC circuit.
[0049] It will be understood that many changes in the details, materials, steps and arrangements of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as explained in the appended claims.
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An AC photovoltaic module includes a DC photovoltaic module for converting solar energy to DC electrical power, and an inverter for converting DC electrical power to AC electrical power, the inverter being adapted for connection to a frame portion of the module and being sized and configured, and provided with arrangements of electrical components thereof, to dispense heat from the inverter, whereby to prolong operational life and reliability of the inverter.
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[0001] This application claims benefit of U.S. Provisional Patent Application No. 61/769,896 filed Feb. 27, 2013.
CROSS REFERENCE TO OTHER PATENT APPLICATIONS
[0002] None.
BACKGROUND OF THE INVENTION
[0003] (1) Field of the Invention
[0004] The present invention relates generally to scoops for measuring the density of fluid in pipelines and, more specifically, in one or more embodiments to novel scoop configurations that provide improved flow and more accurate density readings of the fluid.
[0005] (2) Background of the Invention
[0006] Scoops have been utilized for decades to monitor the density of the fluids in pipelines. The density of the fluids relates to how much product is transported. Accuracy of the density readings is important because the result can affect the prices paid for shipping product through the pipeline, which prices can be significant. Therefore both the pipeline companies and the users of the pipelines desire to obtain the most accurate readings as possible.
[0007] Despite the long felt need for accurate readings, prior art scoops have long had many problems that have not been resolved. Prior art scoops may not produce enough fluid flow to obtain a good sample. In some cases, differential pressure devices such as pumps are required when using prior art scoops. Differential pressure devices can introduce fluid contamination as well as increase the size and complexity of the density measurement systems.
[0008] Scoops used to take samples can be inaccurate because fluid beneath the valve is static. Therefore the sample taken may not be representative of fluid in the pipeline at the moment the sample is taken and/or can be contaminated with fluid that has accumulated beneath the valve.
[0009] In some cases, scoops are mounted utilizing a threaded receptacle that may be secured and sealed to the pipeline utilizing one of three sanctioned connections 1) pipe threads & sealant; 2) socket weld or 3) butt-weld. The threads in the threaded receptacle provide a seal with the threaded receptacle. However, mounting the scoop to the threaded receptacle can provide difficulties in orienting in the pipe in a manner that maximizes flow through the scoops.
[0010] Another problem is that scoops must on occasion be removed from the pipeline to allow pigs to pass through the pipeline. Removing and reintroducing the scoops can be time consuming with corresponding lost use of the pipeline.
[0011] Those of skill in the art have long sought a better scoop design and better scoop systems to provide more accurate readings. Consequently, those of skill in the art will appreciate the present invention, which addresses the above and/or other problems.
SUMMARY OF THE INVENTION
[0012] Accordingly, it is an object of the present invention to provide improved scoop designs.
[0013] Another possible object of the invention is to provide a scoop design that is compact and improves flow of product through the scoop.
[0014] Yet another object of the invention is to provide a scoop design that bends a pipe so the pipe remains straight but the face of the scoop is directed laterally into the flow.
[0015] Yet another object of the invention is to provide a scoop design utilizing a tubular to pipe connector wherein the pipe connector threads onto a mating threaded connector on the pie but provides a compressible connection that allows rotation of the scoop for orientation of the scoop prior to tightening of the connector.
[0016] Yet another object is providing a retractable pipe scoop design.
[0017] Yet another object is to provide a compact bi-directional tandem scoop design.
[0018] Yet another object is to provide an even more compact single scoop pipe bi-directional scoop design.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The drawings constitute a part of this specification and include exemplary embodiments to the invention, which may be embodied in various forms. It is to be understood that in some instances various aspects of the invention may be shown exaggerated or enlarged to facilitate an understanding of the invention.
[0020] FIG. 1A is a front elevational view, partially in hidden lines, of a scoop to obtain a product sample in accord with one possible embodiment of the present invention.
[0021] FIG. 1B is a side elevational view, in cross-section, of the scoop of FIG. 1A in accord with one possible embodiment of the present invention.
[0022] FIG. 2A is a side elevational view, partially in cross-section, showing the scoop of FIG. 1A and 1B mounted to a pipe utilizing a tubular to pipe connection in accord with one possible embodiment of the invention.
[0023] FIG. 2B is an enlarged elevational view, in cross-section, showing a tubular to pipe in accord with one possible embodiment of the invention.
[0024] FIG. 3A is a side elevational view, partially in cross-section, showing a retractable scope and yoke design that in a retracted position with respect to a pipeline in accord with one possible embodiment of the present invention.
[0025] FIG. 3B is a side elevational view, partially in cross-section, showing the retractable scope and yoke design of FIG. 3A in an extended position with respect to a pipeline in accord with one possible embodiment of the present invention.
[0026] FIG. 3C is a front elevational view, partially in hidden lines, showing the retractable scoop and yoke design of FIG. 3A and 3B prior to mounting a threaded connector to the pipe connector in accord with one possible embodiment of the invention;
[0027] FIG. 3D is a top view of a yoke component for a retractable scoop in accord with one possible embodiment of the present invention.
[0028] FIG. 4 is a side elevational view, partially in hidden lines, showing one type of compact sampling and/or densitometer loop with tandem scoops in accord with one possible embodiment of the present invention.
[0029] FIG. 5 is a front elevational view, partially in hidden lines, showing another type of compact sampling and/or densitometer loop with tandem scoops in accord with one possible embodiment of the present invention.
[0030] FIG. 6 is a perspective view showing a prover, sampling and/or densitometer loop with tandem scoops in accord with one possible embodiment of the present invention.
[0031] FIG. 7 is side view, partially in hidden lines of a first type of bidirectional flow single tubular flow scoop that provides a sampling and/or densitometer and/or prover loop in accord with one possible embodiment of the present invention.
[0032] FIG. 8 is a side view, partially in cross-section, showing a second type of bidirectional flow single tubular flow scoop with a mixing chamber in accord with one possible embodiment of the present invention.
[0033] FIG. 9A is a side elevational view of wafer mounted tandem scoops that provides a sampling and/or densitometer and/or flow meter loop in accord with one possible embodiment of the present invention.
[0034] FIG. 9B is a cross-sectional view of FIG. 9A along lines A-A in accord with one possible embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0035] Detailed descriptions of the preferred embodiment are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system, structure or manner.
[0036] FIG. 1A and FIG. 1B show a bended scoop design 10 that comprises a single seamless pipe or tubular with first tubular portion 12 adjacent scoop end 14 . Second tubular portion 28 has a larger outer diameter 30 than outer diameter 26 of first tubular portion 12 .
[0037] One possible method of the present invention involves machining the single tubular pipe to reduce the original pipe stock diameter to outer diameter 30 of second tubular portion 28 . Then further machining reduces the outer diameter of first tubular portion 12 to outer diameter 26 . Shoulder 32 is formed between first tubular portion 12 and second tubular portion 28 . The scoop end is then bent as shown to provide scope face 16 that is oriented laterally and preferably perpendicular with respect to centerline 24 as indicated by line scoop face centerline 19 .
[0038] Accordingly, the bending of first tubular portion 12 of scoop design 10 results in forming scoop face 16 . In one embodiment, scoop face 16 provides opening 22 (See FIG. 1A ) that is preferably perpendicular and at least angled with respect to tubular centerline 24 as indicated by the perpendicular scoop face centerline 20 . At least a portion and preferably the centerline of scoop face 16 is coaxial with a surface of the straight portion of first tubular portion 12 . Scoop face 16 comprises outline 36 that preferably defines a plane that is parallel to axis 24 . Outline 36 can be elliptical or substantially elliptical in shape. A smaller axis 21 of the ellipse of outline 36 is substantially equal to an internal diameter 38 of scoop design 10 . The larger axis of the ellipse varies with respect to the bend radius.
[0039] First tubular portion 12 is bent to provide bend radius 18 as shown in FIG. 1B . Bend radius 18 is between two times and four times of scoop 10 and preferably two and four times that of outer diameter 30 of second tubular portion 28 although conceivably between two and four times outer diameter 26 of first tubular portion 12 . In another embodiment, bend radius 18 may be between two and three times outer diameter 28 . In another embodiment, bend radius 18 may be between 2.3 and 2.7 times outer diameter 28 and/or may be within a smaller range or larger range or outside these ranges. The bend radius may vary depending on the outer diameter of first tubular portion 12 . The bend radius affects the fluid flow characteristics and these ranges have been found to provide the best fluid flow through bended sample scoop design 10 .
[0040] While the features of the scoop face 16 are defined herein in terms of geometrical features such as planes, ellipses, perpendicular, and so forth, it is understood that the features are not geometrically perfect and could have variations, e.g., with 2 and/or to 5 and/or to 10 and/or to 20 range degree variations and any range there between. However, the design may fall outside these ranges and may include corresponding non-linearities.
[0041] Scoop 10 provides mark 34 shown in FIG. 1A that is aligned with the center of scoop face 16 . This allows alignment of scoop face 16 with respect to the center line of the pipeline as discussed with respect to FIG. 2 . In other words, scoop 10 can be rotated to provide that mark 34 is in-line with the axis of the pipeline, whereupon the scoop is fixed in that orientation as discussed hereinbefore.
[0042] Scoop design 10 is preferably provided in three different sizes with outer diameter 30 ranging from one inch to one and one-half inches.
[0043] FIG. 2A shows the scoop design 10 mounted in an orientable or alignable sampling assembly 200 that permits alignment of scoop face 16 with respect to the pipeline axis and flow arrow 218 . In this way, flow or fluid pressure into scoop face 16 can be maximized. Orientable sampling assembly 200 is believed to be yet another significant improvement over the prior art.
[0044] Alignable or orientable sampling assembly 200 preferably utilizes tubular to pipe connector 202 , which is commercially available off the shelf, in a highly unique manner. As used herein, tubulars do not have threads. On the other hand pipe connectors require threads. Tubular to pipe connector 202 comprises a tubular pipe connection with ferrule seals 218 , 220 and threaded pipe connection with threads 208 . Accordingly a tubular to threaded connection comprises a connection from a non-threaded cylinder to a threaded connection. Tubular to pipe connector 202 comprises compression nut 204 , which is threadably securable to pipe connector 206 utilizing threads 222 . Pipe connector 206 provides pipe connection with threads 208 to receptacle 210 , which is provided on pipe 212 . Receptacle 210 utilizes seal 214 with pipe 212 , which can be one of three sanctioned connections 1) pipe threads & sealant; 2) socket weld or 3) butt-weld. Valve 216 may be secured to an upper end of scoop design 10 and may be utilized to provide samples of the pipe fluid as desired.
[0045] FIG. 2B shows an enlarged view of tubular to pipe connector 202 . It will be seen that compression nut 204 can be utilized to compress ferrules 218 and 220 for sealing around the tubular body of scoop design 10 . As compression nut 204 is tightened by rotation on threads 222 , a seal is formed, which may be referred to as a first seal in the claims, around the tubular body of scoop design 10 . Further, threads 208 , which may be referred to as a second seal in the claims, are tightened to provide a seal between receptacle 210 and pipe connector 206 . Shoulder 32 , shown in FIG. 1A and 1B , seats onto seat 232 formed within tubular to pipe connector 202 .
[0046] In operation of one embodiment of alignment or orientation, scoop 10 is placed in tubular to pipe connector 202 until shoulder 32 of scoop 10 engages seat 232 in tubular to pipe connector 202 . Scoop 10 can then be rotated to orient scoop face 216 within pipe 212 for receiving flow in pipe 212 as indicated by arrow 218 . This is accomplished utilizing mark 34 shown in FIG. 1A that is aligned with the center of scoop face 216 . Once scoop face 216 is aligned with respect to pipe 212 , then compression nut 204 can be tightened to seal around the tubular body of scoop 10 . Two scoops like that of FIG. 2A may be used to provide a measurement loop for bi-directional flow out of pipe 212 and then retum the flow to the pipe after measurements are made as discussed hereinafter.
[0047] FIG. 3A , FIG. 3B , FIG. 3C and FIG. 3D show aspects of retractable scoop and yoke design pipeline scoop 300 in accord with one embodiment of the present invention. Retractable pipeline scoop 300 preferably utilizes scoop design 10 , which allows easy movement into and out of pipeline 304 because scoop design 10 has the same OD as a single tubular. While other types of scoops could possibly be utilized, scoop design 10 is probably the best type of scoop for use in retractable pipeline scoop 300 .
[0048] As discussed herein with other embodiments of the invention, two retractable pipeline scoops could be connected together to form a flow loop for to measure pipeline fluid with a densitometer, flow meter, prover, and/or takes samples as desired.
[0049] Unlike prior art scoops which may be time consuming to remove when a pig is sent down the pipeline, retractable pipeline scoop 300 can be easily retracted from the pipeline and inserted into the pipeline without requiring loss of the seal. Pipeline downtime is therefore greatly reduced.
[0050] In this embodiment, upper yoke 305 and lower yoke 304 are mounted on yoke screws 306 and 308 . Yoke screws 306 and 308 extend through openings 310 and 312 in overall yoke design 302 shown in FIG. 3D . Scoop 10 extends through but is fixed to opening 314 in upper yoke 305 . Openings 311 and 313 in upper yoke 305 are threaded. The corresponding openings 316 , 318 are not threaded. Opening 320 in lower yoke 304 allows scoop 10 to slidably move therethrough as seen in FIG. 3A , FIG. 3B , and FIG. 3 c.
[0051] Accordingly, one main difference between upper yoke 302 and lower yoke 304 is that openings 311 and 313 are threaded whereas openings 316 and 318 are not. As well, upper yoke 305 is secured to scoop 10 whereas lower yoke 304 allows scoop 10 to move therethrough and includes an O-ring seal when the tubular to pipe connector sealing is not yet connected (See FIG. 3C ) prior to operation as shown in FIG. 3A (scoop removed from pipeline) and FIG. 3B (scoop extended into pipeline).
[0052] As yoke screws 306 and 308 are rotated, yoke 305 is urged to move. For manual operation, a few turns can be applied to one yoke screw and then applied to the other yoke screw. The operation could be automated.
[0053] The sealing of FIG. 2 is utilized during operation as shown in FIG. 3A and FIG. 3B but utilizes O-rings at 320 prior to connection of the tubular to pipe seals as indicated in FIG. 3C . O-rings may comprise suitable resilient O-ring seal material. The O-ring seal preferably utilizes a smoother finish on the scoop pipe surface.
[0054] FIG. 3D shows the general plan layout of upper yoke 305 and lower yoke 304 with the differences discussed hereinbefore for openings 310 , 312 , and 315 .
[0055] FIG. 4 , FIG. 5 , FIG. 6 , FIG. 9A , and FIG. 9B show various compact tandem scoop configurations that utilize two scoops oriented in opposite directions on a single flange in the pipeline for sampling and/or densitometer and/or flow meter fluid flow loops. The measurement flow loops discussed hereinafter provide sufficient flow of fluid from the pipeline without the need for differential pressure devices (such as pumps or the like), thereby significantly reducing the size, complexity, and fluid contamination. In a preferred embodiment, the compact sampling loops utilize scoop 10 discussed hereinbefore but the present invention is not limited to those scoop designs.
[0056] In FIG. 4 there is shown flow axis aligned tandem scoop system 400 mounted to a single flange 406 . Scoops 402 and 404 extend through top flange 406 , which may be a typical 3″-600# mounting flange. Scoops 402 and 404 are sealed by top flange 406 , which itself is sealingly mounted to the pipeline. Flow proceeds through flow loop 416 as indicated by arrows 408 , 410 , 412 , and 414 whereby flow is taken out of the pipeline and then returned to the pipeline. Well known configurations of the flow loop may comprise densitometer 418 , sampling valves 420 , 422 , and flow control valves 424 , 426 , and 428 . As per standard API requirements, scoops 402 and 404 are designed to have a length that access the middle ⅓ rd of flow.
[0057] In tandem scoop system 400 , scoops 402 and 404 are positioned upstream and downstream of each other in line with the axis of the pipe and oriented in opposite directions. Scoops 402 and 404 are mounted into a single flange 405 and secured together at a lower end by mounting member 430 . Bends 432 and 433 are provided to allow the various connections to be made to valves 426 and 424 . Accordingly, an entire sampling system can extend through a single flange mounting.
[0058] FIG. 6 shows a perspective view of flow axis aligned scoops 602 and 604 with connections to densitometer 606 and prover 608 . A half portion of pipeline 610 is provided with flange 612 secured to flange mounting 614 provided on pipeline 610 . Valves 616 , 618 , 620 , and/or other valves can be used to control fluid flow through the measurement flow loop. Fluid samples can be taken at 622 and 624 .
[0059] Referring now to FIG. 5 , perpendicular mount tandem scoop system 500 provides scoops 502 and 504 positioned side by side or perpendicular with respect to the axis of the pipeline. In this embodiment flange 506 may comprise a 2″-150# mounting flange. Bends 508 and 510 permit connection to flow loop 506 , which in this embodiment comprises densitometer 516 and valves 518 , 520 . Flow may proceed into and out of the pipeline in a direction through flow loop 509 with flow direction indicated by arrows 512 and 514 .
[0060] FIG. 9A and FIG. 9B show wafer mount tandem scoop system 900 . In two possible examples, wafer flange 902 may comprise a 12″ 150# or 10″ 900# wafer flange. The wafer flange can be mounted between flanges in the pipeline so that wafer flange 902 surrounds the flow area going through the pipeline. In this example, scoops 904 and 906 are axially aligned with respect to the pipeline axis and extend from opposite directions and from opposite sides of wafer flange 902 . Scoops 904 and 906 are sealed and mounted within wafer flange 902 as indicated at 908 and 910 and are essentially in-line with plane 912 defined by wafer flange 902 .
[0061] In wafer mount system 200 , it is not necessary to provide a bend in scoops 904 and 906 . Flow loop 914 can comprise densitometer 916 , sampling valves 918 , 920 , flow meter 926 , and control valves 922 , 936 , 928 . Fluid flows through loop 914 in the direction indicated by arrows 928 and 930 . As indicated in FIG. 9B , flow proceeds out of the pipeline in the direction shown by arrow 934 and into the pipeline in the direction indicated by arrow 932 . Scoop faces 938 and 940 are axially aligned with pipeline centerline 942 .
[0062] Accordingly, the present invention provides three compact tandem scoop system 400 , 500 , and 900 that mount two scoops to a single flange.
[0063] FIG. 7 and FIG. 8 show bi-directional flow scoops formed within a single pipe. Bi-directional flow loop scoop 700 provides a single tubular scoop that can be utilized to provide a flow loop for density, proving, sampling, and the like as discussed hereinbefore. Bi-directional mixing scoop 800 provides a single tubular scoop that can be utilized to provide a mixing chamber with continually refreshed fluid so that the sample is representative of fluid in the pipeline at the time the sample is taken avoiding the problems of trapped sample at the sampling valve as discussed hereinbefore.
[0064] Bi-directional flow loop scoop 700 utilizes single pipe 702 with two separate internal flow paths 704 and 706 . The external shape of single pipe 702 is similar or the same as described by scoop 10 discussed hereinbefore so tubular to pipe connector can be utilized for sealing and orientation. Flow proceeds from the pipeline into scoop face 708 as indicated by arrow 710 . Fluid then flows as indicated by arrow 712 . As indicated by arrow 714 , flow goes through a measuring loop, which may be similar to that discussed hereinbefore including a densitometer, prover, sample connections, valves, and the like. Flow then returns as indicated by arrow 716 through tube 718 which enters pipe 702 and is sealed at seal 720 . Flow then continues through flowline 706 as indicated by arrow 718 and exits back into the pipeline through opening 722 as indicated by arrow 720 . The sealing can be the same as discussed hereinbefore with respect to FIG. 2 utilizing a compression nut that allows orientation of scoop face 708 . Bi-directional scoop 700 could also be utilized with the retractable yoke design 300 discussed hereinbefore to provide a retractable bi-directional measurement flow loop.
[0065] FIG. 8 provides a single pipe bi-directional scoop 800 that provides a mixing chamber 802 which is continuously refreshed. Prior art sampling systems that utilize a scoop suffer from the problem that stale fluid accumulates therein. Thus, fluid taken at a particular moment may not be representative of fluid in the pipeline. Since the samples are often timed, this could be problematic in verifying that the sample is valid.
[0066] Scoop 800 is comprised of single pipe 804 . Scoop 800 may be sealed/oriented as discussed with respect to FIG. 2A and FIG. 2B as discussed with respect to FIG. 7 or using other seals as desired. Fluid enters scoop face 806 from the pipeline as indicated by arrow 812 . The fluid travels up flow path 808 and enters mixing chamber 802 as indicated by arrow 814 . The fluid in mixing chamber 802 is thereby continuously refreshed. Fluid exits mixing chamber 802 via tube 820 and flows in the direction of arrow 816 through flow path 810 . Fluid exits single pipe 804 as indicated by arrow 888 through opening 822 .
[0067] Accordingly, the present invention provides a highly desirable scoop design 10 as indicated in FIG. 1A and FIG. 1B , a seal and orientation apparatus as indicated in FIG. 2A and FIG. 2B , a retractable scoop design shown in FIG. 3A , FIG. 3B , FIG. 3C , FIG. 3D , compact single flange bi-directional tandem mounted scoops as indicated by FIG. 4 , FIG. 5 , FIG. 6 , and FIG. 9A , and single pipe bi-directional scoops as indicated by FIG. 7 and FIG. 8 .
[0068] The foregoing description of the preferred embodiments of the invention has been presented for purposes of illustration and description only. It is not intended to be exhaustive or to limit the invention to the precise form disclosed; and obviously many modifications and variations are possible in light of the above teaching. Such modifications and variations that may be apparent to a person skilled in the art are intended to be included within the scope of this invention as defined by the accompanying claims.
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A retractable sample scoop is shown that is mountable to a pipeline for taking samples from the pipeline. A retractable mounting mechanism mounts to the pipeline wall. A tubular is extendable into the opening of pipeline and retractable from the pipeline. A first seal creates sealing around the tubular portion with respect to said pipeline while permitting insertion, retraction and rotation of said first tubular portion with respect to said pipeline. A second seal comprises a tubular without threads to pipe connector with threads.
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FIELD OF THE INVENTION
The present inventions generally relate to devices for transforming sound waves into electrical signals, and in particular, microphones.
BACKGROUND OF THE INVENTION
In recent years, various types of digital microphones, characterized as such because they output audio signals in digital format, have been developed in order to overcome disadvantages inherent in analog microphones—in particular, the injection of coupling noise, and resulting decrease in signal quality, due to ambient electromagnetic energy, signal attenuations, and filtering in the signal path. Although at least some analog circuitry is eliminated by these digital microphones, thereby resulting in a less noisy output audio signal, many, if not all, of these microphones generate an intermediate analog audio signal, which must be processed by at least one analog component. Thus, such microphones are not true digital microphones in that they are incapable of transforming audible sounds directly into digital audio signals.
Almost all microphones, whether analog or digital, are mechanical in nature in that they use moving elements to create an audio signal. These elements range from long strips of aluminum hung between magnets (Ribbon Microphone), or thin film metallicized membranes suspended in a highly electrically charged cage (Condenser Microphone), to cone shaped diaphragms with wrapped wires that induce voltage when moved in a magnetic field (Dynamic Microphone). In each of these cases, the moving elements may become mechanically stressed over time, thereby reducing the working life of the microphone.
Significantly, known digital microphones, like all microphones, generate non-secure intermediate and/or output audio signals that, if accessed, can be easily transformed back into a coherent audible sound that resembles the audible sound input into the microphone. If protection of the audible sound from unauthorized third parties is desirable, a security layer can be applied to these audio signals downstream from the microphone output. For example, to secure the audio content (e.g., a song), the audio signal can be transformed into a sound file in any one of a variety of formats, such as a Windows® Audio Volume (WAV), Windows® Media Video (WMV), or Moving Picture Experts Group Layer-3 Audio (MP3) file, and protected with a digital rights management (DRM) and enforcement system, which allows only authorized persons to perform certain operations on the audio content.
There are certain situations, however, where protecting the audio content downstream from the microphone may not be sufficient. For example, in the context of a music recording studio, several audio cuts and tracks are typically generated, which are then combined or spliced into a final file version of a song or album. When the final audio version is transferred to the commercial media (e.g., compact disks), the audio content thereon can be protected with a DRM system. However, the raw content (i.e., the audio cuts and tracks) used to produce the final audio version, which may have even more commercial value than the final product, remains unprotected, and thus, can be freely distributed.
In the case where a microphone is being used as a listening device (e.g., for transmitting audio from one location to a remote location), an unauthorized third party could potentially tap into a wire downstream from the microphone, or even within the microphone itself, to access the non-secured audio signal. Also, typical microphones, whether analog or digital, have passive elements that cannot be turned off unless the microphone has a mechanical switch that can be operated (with the exception of the condenser microphone, which requires an external power supply). Thus, with few exceptions, microphones cannot be turned off remotely, and as such, will continuously be on even though their outputs may not be in use. As such, these microphones will indiscriminately generate and transmit audio signals that can potentially be accessed by an unauthorized third party.
There thus remains a need to provide a microphone that does not generate an intermediate or output audio signal that can be easily used by unauthorized persons, that can be remotely deactivated, and that comprises non-moving mechanical elements.
SUMMARY OF THE INVENTION
In accordance with a first aspect of the present inventions, a method of processing ambient sound waves (e.g., audible sound waves) is provided. The method comprises emitting ultrasound waves (e.g., within a range of 100 KHz to 3 MHz), and combining the ambient sound waves and ultrasound waves into heterodyned sound waves. The method further comprises detecting the heterodyned sound waves and generating a sound detection signal containing information relating to the heterodyned sound waves. The heterodyned sound waves can optionally be collimated, so that they can be more easily detected. Notably, the injection of ultrasound waves into the ambient sound waves renders a resulting signal incoherent.
The method further comprises generating an ambient audio signal representing the ambient sound waves at least partially based on the sound detection signal. In some methods, a heterodyned audio signal representing the heterodyned sound waves, is generated. The heterodyned audio signal may be the same sound detection signal generated in response to the detection of the heterodyned audio signal or an intermediate signal derived from the sound detection signal. In either case, the ambient audio signal may be derived from the heterodyned audio signal, e.g., by computing the difference between the heterodyned audio signal and a reference signal used to drive the emission of the ultrasound waves. The ambient audio signal can conveniently be a digital audio signal, or even a streaming audio file, but can be an analog signal as well.
Thus, it can be appreciated that the sound path from the point at which the ambient sound waves are combined with the ultrasound waves to the point at which the ambient audio signal is generated is secured. The method may further comprise applying a security layer to the ambient audio signal, so that only authorized entities may access the ambient audio signal. In this case, a secure ambient audio signal can be transmitted downstream.
In accordance with a second aspect of the present inventions, the previously described method can be incorporated into a microphone. In this case, an ultrasound emitter is used to emit the ultrasound waves, a mixing chamber, such as a hollow cylinder, is used to combine, and optionally collimate, the ambient sound waves with the ultrasound waves in the heterodyned sound waves, and an acoustic detector is used to detect the heterodyned sound waves and generate the sound detection signal. The acoustic detector can be any detector suitable for detecting ultrasound waves, but in some embodiments, the acoustic detector is a solid state device, so that no moving parts are needed. At least one processor, e.g., a digital signal processor (DSP), is used to generate, and optionally apply a security layer, to the ambient audio signal. The processor(s) may optionally be configured for selectively activating and deactivating the microphone in response to remote signals. In this manner, the microphone, if it is used as a listening device, can be turned off when not in use in order to decrease the chances that an unauthorized third party could listen in on any happenings at the microphone location. The transducer, mixing chamber, acoustic detector, and processor(s) can conveniently be contained within a microphone housing.
In accordance with a third aspect of the present inventions, a sound processor, which can be used in a microphone or any other suitable device, is provided. The sound processor may have the same functionality as the processor(s) described above.
In accordance with a fourth aspect of the present inventions, a method of processing sound waves (e.g., audible sound waves) is provided. The method comprises detecting the sound waves with a portable device (such as a microphone) and generating an audio signal representing the sound waves. In some methods, the sound detection signal is generated in response to the detection of the sound waves, in which case, the audio signal can be generated based at least in part on the sound detection signal. The audio signal can conveniently be a digital audio signal, or even a streaming audio file, but can be an analog signal as well. The method further comprises applying a security layer to the audio signal within the portable device (e.g., by encrypting the audio signal), so that only authorized entities may access the audio signal, and then outputting the secure audio signal from the portable device. Thus, it can be appreciated that the audio signal output from the portable device is immediately protected, and can therefore be transmitted downstream from the portable device without a significant concern that an unauthorized entity could access the audio content contained within the audio signal.
If it is desired to secure the sound path within the portable device, the method may further comprise heterodyning the sound waves with ultrasound waves, generating a heterodyned audio signal representing the heterodyned sound waves, and then deriving the audio signal from the heterodyned audio signal. Notably, the injection of ultrasound waves into the ambient sound waves renders a resulting signal incoherent. Thus, it can be appreciated that, in this case, the sound path from the point at which the sound waves are combined with the ultrasound waves to the point at which the ambient audio signal is generated is additionally secured.
In some methods, the portable device is selectively activated and deactivated in response to remote signals. In this manner, the portable device, if it is used as a listening device, can be turned off when not in use in order to decrease the chances that an unauthorized third party could listen in on any happenings at the location of the portable device.
In accordance with a fifth aspect of the present inventions, the previously described method can be incorporated into a microphone. In this case, an acoustic detector is used to detect the sound waves. The acoustic detector can be any detector suitable for detecting ultrasound waves, but in some embodiments, the acoustic detector is a solid state device, so that no moving parts are needed. At least one processor, e.g., a digital signal processor (DSP), is used to generate and apply a security layer to the audio signal, and optionally selectively activate and deactivate the microphone.
In accordance with a sixth aspect of the present inventions, a secured audio system for processing sound waves (e.g., audible sound waves) is provided. The audio system comprises the previously described microphone and an external computer configured for receiving the audio signal from the microphone, removing the security layer from the audio signal, and reading audio content within the audio signal. If the audio signal is encrypted, the external computer can be configured for removing the security layer by decrypting the audio signal with a secret encryption key. The external computer may optionally send signals to the microphone to selectively activate and deactivate it.
In accordance with a seventh aspect of the present inventions, a secured audio system for processing sound waves (e.g., audible sound waves) is provided. The audio system comprises a microphone that is similar to the previously described microphone, with the exception that it configured for sending the encrypted audio signal over an Internet Protocol (IP) network, so that a client computer can receive the encrypted audio signal from the IP network. The audio system further comprises one or more servers configured for authenticating a client computer, and transmitting one or more encryption keys to the client computer if authenticated. The client computer can then use the encryption key(s) to decrypt the encrypted audio signal. In some embodiments, the server(s) are configured for receiving the encrypted audio signal from the IP network, and sending the encrypted digital audio signal to the client computer over the IP network. The server(s) may optionally send signals to the microphone to selectively activate and deactivate it.
In accordance with an eighth aspect of the present inventions, a method of processing sound waves (e.g., audible sound waves) is provided. The method comprises emitting an optical pulse train through the sound waves, so that the optical pulse train is modulated by the sound waves. In some methods, the optical pulse train is emitted along an optical path that is substantially perpendicular to the sound path along which the sound waves travel. The method further comprising sensing the modulated optical pulse train, generating a modulated electrical pulse train in response to the detected modulated optical pulse train, and generating an audio signal representing the sound waves based at least in part on the modulated electrical pulse train. The audio signal can conveniently be a digital audio signal, or even a streaming audio file, but can be an analog signal as well. Preferably, the pulse repetition rate of the optical pulse train is higher than the frequency of the sound waves, so that the sound waves can be accurately sensed. Thus, it can be appreciated that sound waves can be detected with a high resolution and without using moving parts.
In some methods, the sound waves modulate the optical pulse train by increasing time intervals between pulses in the optical pulse train in accordance with the pressure of the sound waves. In this case, the audio signal may be generated based on the time intervals between pulses in the modulated electrical pulse train. In other methods, the optical pulse train is emitted in response to a reference electrical pulse train, in which case, the method further comprises comparing the reference and modulated electrical pulse trains, e.g., by computing the difference between the reference and modulated pulse trains to obtain time interval differences between corresponding pulses in the respective pulse trains The audio signal is then generated based on this comparison.
The method may optionally comprise encrypting the audio signal, so that only authorized entities may access the audio signal. Thus, it can be appreciated that the audio signal is protected, and can therefore be transmitted downstream without a significant concern that an unauthorized entity could access the audio content contained within the audio signal.
If it is desired to secure the sound path before encrypting the audio signal, the method may further comprise heterodyning the sound waves with ultrasound waves, so that the optical pulse train, and thus, the electrical pulse train, is modulated by the heterodyned sound waves. A heterodyned audio signal can then be generated at least partially based on the electrical pulse train, and then the audio signal can be derived from the heterodyned audio signal. Thus, it can be appreciated that, in this case, the sound path from the point at which the sound waves are combined with the ultrasound waves to the point at which the audio signal is generated is additionally secured.
In some methods, the portable device is selectively activated and deactivated in response to remote signals. In this manner, the portable device, if it is used as a listening device, can be turned off when not in use in order to decrease the chances that an unauthorized third party could listen in on any happenings at the location of the portable device.
In accordance with a ninth aspect of the present inventions, the previously described method can be incorporated into a microphone. In this case, an optical source, such as a laser, emits the optical pulse train through the sound waves, and an optical sensor, such as a photo diode (PD), senses the modulated optical pulse train and generates the modulated electrical pulse train. At least one processor, e.g., a digital signal processor (DSP), is used to generate and optionally encrypt the audio signal. The processor(s) may optionally be configured for selectively activating and deactivating the microphone in response to remote signals. In this manner, the microphone, if it is used as a listening device, can be turned off when not in use in order to decrease the chances that an unauthorized third party could listen in on any happenings at the microphone location. The optical emitter, optical sensor, and processor(s) can conveniently be contained within a microphone housing.
In accordance with a tenth aspect of the present inventions, a sound processor, which can be used in a microphone or any other suitable device, is provided. The sound processor may have the same functionality as the processor(s) described above.
In accordance with an eleventh aspect of the present inventions, a method of processing sound waves (e.g., audible sound waves) is provided. The method comprises detecting the sound waves with a portable device (such as a microphone) and generating an audio signal representing the sound waves. The audio signal can conveniently be a digital audio signal, or even a streaming audio file, but can be an analog signal as well. The method further comprises selectively activating and deactivating the portable device in response to remote signals. In this manner, the portable device, if it is used as a listening device, can be turned off when not in use in order to decrease the chances that an unauthorized third party could listen in on any happenings at the location of the portable device.
The method may further comprise encrypting the audio signal, so that only authorized entities may access the ambient audio signal. In this case, a secure audio signal can be transmitted downstream from the portable device. If it is desired to secure the sound path within the portable device, the method may further comprise heterodyning the sound waves with ultrasound waves, generating a heterodyned audio signal representing the heterodyned sound waves, and then deriving the audio signal from the heterodyned audio signal. Notably, the injection of ultrasound waves into the ambient sound waves renders a resulting signal incoherent. Thus, it can be appreciated that, in this case, the sound path from the point at which the sound waves are combined with the ultrasound waves to the point at which the ambient audio signal is generated is additionally secured.
In accordance with a twelfth aspect of the present inventions, the previously described method can be incorporated into a microphone. In this case, an acoustic detector is used to detect the sound waves. The acoustic detector can be any detector suitable for detecting ultrasound waves, but in one embodiment, the acoustic detector is an device, so that it can be electronically turned off. At least one processor, e.g., a digital signal processor (DSP), is used to generate the audio signal, selectively activate and deactivate the microphone, and optionally encrypt the audio signal.
Other features of the present invention will become apparent from consideration of the following description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings illustrate the design and utility of preferred embodiments of the present invention, in which similar elements are referred to by common reference numerals. In order to better appreciate how the above-recited and other advantages and objects of the present inventions are obtained, a more particular description of the present inventions briefly described above will be rendered by reference to specific embodiments thereof, which are illustrated in the accompanying drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
FIG. 1 is an plan view of a microphone constructed in accordance with a preferred embodiment of the present invention;
FIG. 2 is a cross-sectional view of the microphone of FIG. 1 ;
FIG. 3 are timing diagrams showing the correlation between sound waves and the modulation of an optical pulse train traveling through the sound waves; and
FIG. 4 is a functional block diagram of a server system used to provide Digital Rights Management (DRM) control to the transmission of an audio signal from the microphone of FIG. 1 to a client computer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , an exemplary microphone 100 constructed in accordance with the present inventions is shown. The microphone 100 is configured for detecting ambient acoustic energy in the form of acoustic waves 200 and outputting a digital steam representing the acoustic waves 200 . In the illustrated embodiment, the acoustic waves 200 are audible and may have any dynamic frequency, but are typically in the audible range of 20-20,000 Hz. The ambient waves 200 can come from any source, e.g., vocal sounds from a person. It should be noted, however, that the microphone 100 is not limited to the audible range, but can detect acoustic energy below or above the audible range, depending on the nature of the electronic circuitry therein.
From the outside, the microphone 100 resembles a standard microphone, and includes a tubular housing 102 , which in the illustrated embodiment, is configured to be either hand held or mounted to a microphone support. The shape of the housing 102 will ultimately depend on the application of the microphone 100 . For example, if used as a listening device, the housing 102 may have a relatively small profile, so that it can be inconspicuously installed at a location to be monitored. The microphone 100 further comprises a screened head 103 suitably mounted to the housing 102 and through which the acoustic waves 200 travel into the interior of the housing 102 .
Unlike a typical microphone, the internal components contained within the housing 102 of the microphone 100 operate, such that the entire sound/audio path through the microphone, including the outputted digital stream, is secure. To this end, and with reference to FIG. 2 , the microphone 100 generally comprises an ultrasound emitter 104 configured for emitting ultrasound waves 202 , a mixing chamber 106 configured for mixing the ambient waves 200 and ultrasound waves 202 to generate heterodyned acoustic waves 204 , an acoustic detector 108 configured for detecting the heterodyned acoustic waves 200 , a sound processor 110 configured for generating a digital audio signal based on the detected heterodyned waves 200 , and applying a security layer to the audio signal, and an optional communications device 112 configured for transforming the digital audio signal into a streaming audio file, communicating with remote devices, and selectively deactivating/activating the microphone 100 in response to remote signals.
In the illustrated embodiment, the ultrasound emitter 104 comprises an ultrasound transducer 114 composed of any suitable piezoelectric material, such as Lead Zirconate Titanate (PZT), and an electrical oscillator 116 , e.g., a voltage controlled oscillator, that drives the ultrasound transducer 114 with electrical signals (e.g., pulse sequences), such that the transducer 114 emits the ultrasound waves 202 at the same frequency as the electrical signals. Preferably, the frequency of the ultrasound waves 202 is well above the audible frequency range, e.g., within the 100 KHz to 3 MHz range, but preferably around 1 MHz. In any event, the frequency at which the ultrasound transducer 114 emits the ultrasound waves 202 is fixed and predictable for reasons that will be described in further detail below. Preferably, the magnitude of the ultrasound waves 202 are of the same order as the magnitude of the ambient waves 200 received by the microphone 100 , e.g., within the 80-120 dB range.
The mixing chamber 106 comprises a hollow cylinder 118 that internally extends along a portion of the microphone housing 102 . The hollow cylinder 118 forms a cavity 120 therein that includes an input 122 at the front end of the cylinder 118 into which the ultrasound waves 202 emitted by the ultrasound transducer 114 and the ambient waves 200 entering through the screened head 103 may enter. The mixing chamber cylinder 118 is composed of a rigid acoustically conducting material, such as metal or plastic, so that the ambient waves 200 and ultrasound waves 202 mix as they travel through the cavity 120 . The cavity 120 has an output 124 at the back end of the cylinder 118 out from which the mixed ambient waves 200 and ultrasound waves 202 exit as heterodyned acoustic waves 204 along a sound path 126 towards the acoustic detector 108 .
Advantageously, the heterodyned waves 204 will be incoherent due to the interference or noise injected therein by the ultrasound waves 202 , so that even if a third party were to tap into the microphone 100 at the output 124 of the mixing chamber 106 , the ambient waves 200 contained within the heterodyned acoustic waves 200 could not be easily detected. In addition to mixing the ambient waves 200 and ultrasound waves 202 to generate the heterodyned waves 204 , the mixing chamber 106 also serves to collimate the heterodyned waves 204 towards the acoustic detector 108 , thereby maximizing the sensitivity of the microphone 100 .
The acoustic detector 108 is a high resolution detector that is capable of detecting sound waves at ultrasonic frequencies. In the illustrated embodiment, the acoustic detector 108 is a solid-state device (i.e., it comprises no moving parts) and is laser-based. In particular, the acoustic detector 108 comprises an optical pulse source 128 and a optical pulse sensor 130 . In the illustrated embodiment, the optical pulse source 128 comprises a laser device 132 , such as a light emitting diode (LED), and an electrical oscillator 134 , e.g., a voltage controlled oscillator, that drives the laser device 132 with an electrical pulse train, such that the laser device 132 emits a corresponding optical pulse train. In the illustrated embodiment, each pulse is transmitted at a wavelength of approximately 1.5 micrometers, and has a suitable pulse width, e.g., 10 psec. The repetition rate of the optical pulse train is preferably much higher than the frequency of the emitted ultrasound waves 202 , e.g., 1 GHz. The optical pulse sensor 130 may comprises any suitable device capable of receiving the optical pulse train from the pulse source 128 and, in response thereto, generating an electrical pulse train that accurately represents the received optical pulse train. In the illustrated embodiment, the pulse sensor 130 takes the form of a photodiode (PD).
The optical pulse source 128 and optical pulse sensor 130 are affixed relative to each, e.g., by mounting them to the inside surface of the microphone housing 102 , and are arranged on opposite sides of the sound path 126 , such that the optical pulse train emitted by the pulse source 128 travels along a light path 136 though the heterodyned acoustic waves 200 at a perpendicular angle to the sound path 126 . As a result, the optical pulse train is modulated by the acoustic waves 200 , in which case, the electrical pulse train generated by the pulse sensor 130 will be a modulated electrical pulse train that represents the modulated optical pulse train received by the pulse sensor 130 .
With reference to FIG. 3 , the correlation between sound waves and the modulation of an optical pulse train traveling through the sound waves will be described. Because sound waves are pressure waves, a series of sound waves will oscillate in pressure from a high pressure (where the sound waves are more compressed) to a low pressure (wherein the sound waves are more rarefied). Notably, the amplitude of sound is characterized by the amplitude of the maximum compression along the sound waves, while the pitch of the sound is characterized by the frequency of the pressure oscillations. Because the speed of light decreases with the density of the medium through which it passes, the time intervals between the optical pulses passing through the sound waves will also decrease as the sound waves become more compressed (or will increase as the sound waves become more rarefied).
Thus, as shown in FIG. 3 (which, for purposes of illustration, exaggerates the variation between time intervals), the lengths of the time intervals between the optical pulses oscillate in accordance with the pressure oscillations within the sound waves. That is, the greatest time intervals between pulses corresponds to the points along the sound waves where the greatest rarefaction occurs, whereas the smallest time intervals between pulses corresponds to the points along the sound waves where the greatest compression occurs. Therefore, the modulated optical pulse train, and thus, the modulated electrical pulse train generated by the pulse sensor 130 , will contain information relating to the amplitude and frequency of the heterodyned acoustic waves 200 output by the mixing chamber 106 . In order to expand the time interval scale, thereby increasing the sensitivity of the acoustic detector 108 , the optical pulse train can be passed through the acoustic waves 200 several times (e.g., using mirrors (not shown)) to laterally reflect the optical pulse train between opposite sides of the sound path 126 , each time being further modulated by the acoustic waves 200 .
Referring back to FIG. 2 , the sound processor 110 preferably takes the form of a digital signal processor (DSP) that is programmed to perform various functions. In particular, the sound processor 110 is configured to receive the modulated electrical pulse train from the optical pulse sensor 130 and internally derive a digital audio signal that represents the heterodyned acoustic waves 200 output from the mixing chamber 106 at least partially based on the modulated electrical pulse train received from the optical pulse sensor 130 . In the illustrated embodiment, the sound processor 110 receives the electrical pulse train used to drive the optical pulse source 128 and compares this reference signal with the modulated electrical pulse train obtained from the pulse sensor 130 .
In particular, the sound processor 110 calculates the time difference between each pulse within the modulated electrical pulse train and the corresponding pulse within the reference electrical pulse train. These time differences will track the alternating pressure compression and rarefaction of the heterodyned acoustic waves 200 , with the greater time differences corresponding to the more compressed regions within the heterodyned acoustic waves 200 and the lesser time differences corresponding to the more rarefied regions within the heterodyned acoustic waves 200 . Based on this principle, the sound processor 110 reconstructs a digital heterodyned audio signal representing the heterodyned acoustic waves 200 .
Notably, because the optical pulses travel through the air at a speed that is on the same order as the speed at which electrical pulses travel through wire, the signal paths between the respective optical pulse emitter and sensor 128 / 130 and the sound processor 110 must be taken into account when determining the differences between the pulses in the modulated electrical pulse train and the corresponding pulses in the reference electrical pulse train. Any difference between the respective signal paths must be accounted to obtain the actual time difference between corresponding pulses. Any difference between the signal paths can be determined by calibrating the microphone 100 , e.g., by operating the acoustic detector 108 in the absence of any sound (ambient or ultrasound) traveling through the mixing chamber 106 , and measuring the time difference between a pair of corresponding pulses in the electrical signal trains received from the optical source/sensor 128 / 130 pair.
Next, the sound processor 110 internally generates an digital ambient audio signal representing the acoustic waves 200 input into the mixing chamber 106 at least partially based on the digital heterodyned audio signal. In the illustrated embodiment, the sound processor 110 receives the electrical signal used to drive the ultrasound transducer 114 , digitizes this reference signal, and then subtracts the digitized reference signal from the digitized heterodyned audio signal to obtain the digital ambient audio signal.
Next, the sound processor 110 applies a security layer to the ambient audio signal, so that only authorized persons have access to the audio content contained within the audio signal, as will be described in further detail below. In the illustrated embodiment, the security layer is applied by encrypting the digital audio signal, so that only devices that possess a correct encryption key can access the audio content within the audio signal. The encryption can either be symmetrical or asymmetrical. Depending on the means for delivering the audio content, the encryption key can be carefully provided to an authorized entity in the context of a DRM system.
As previously mentioned, the communication processor 112 is optional, and lends itself well to applications where communication over an Internet Protocol (IP)-network (such as the Internet) is desired. The communications processor 112 , which, in the illustrated embodiment, takes the form of a Windows® CE embedded chip, transforms the encrypted audio signal output from the sound processor 110 into a streaming audio file (e.g., a WAV, WMV, or MP3 file), which is then packetized for delivery over the IP network to a remote site. To this end, the microphone 110 may have a 10-Base T connection (not shown) for connection to the IP network. The communications processor 112 provides communications between the microphone 110 and another IP devices, such as a server or client computer, so that the streaming audio file can be transmitted when requested, as will be described in further detail below. As will also be described in further detail below, the communication processor 112 , in response to a remote request, may also selectively activate and deactivate the microphone 100 by turning the sound processor 110 and/or acoustic detector 128 on and off, e.g., using a relay switch (not shown). It should be noted that although the sound processor 110 and communications processor 112 are shown as to distinct elements, their functionality can be combined into a single device without straying from the principles taught herein.
The microphone 100 can be used in any one of a variety of scenarios where secured audio signals are desired. For example, the microphone 100 can be used in a recording studio where it is desired to protect raw audio content from unauthorized use. In this scenario, the communication processor 112 may not be needed, since the microphone 100 will typically be connected directly to a storage device, and any transformation of the digital audio signal into a streaming audio file would presumably be accomplished by an external computer. Of course, in a virtual recording studio where it is possible to download the audio signal to a storage device over an IP network, it may be desirable to include the communications processor 112 within the microphone 100 , as will be described in further detail below.
In an actual recording studio, a DRM system can be implemented, whereby only a specific computer with a secret encryption key can be used to access the audio content within the encrypted audio signal. In this case, the encrypted digital audio signal is output from the microphone 100 into a computer, where it may be transformed into a streaming audio signal and stored on a suitable medium. The computer that generates the final version of the audio content, which may be the same computer that generates the raw audio files, can then decrypt the raw audio files using the secret encryption key, so that the final version of the audio content can be created. The final version of the audio content can then be applied to the media, such as CDs, in its unencrypted form, and commercially distributed to the public. Significantly, any non-finalized version of the content (i.e., the raw audio files) cannot be decrypted without the secret encryption key, and thus, would be protected from unauthorized commercialization.
As briefly mentioned above, the microphone 100 may be used to download audio content over an IP network, e.g., in the context of a virtual recording studio or when the microphone 100 is simply used as a listening device. In this case, a remote device, e.g., a network server, may prompt the communications device 112 of the microphone 100 to transmit the packetized audio file over the IP network to the remote device. The same remote device can be used to apply DRM control to the audio content of the audio file and to selectively activate/deactivate the microphone 100 .
For example, FIG. 4 illustrates a DRM controlled server system 300 comprising a DRM/content server 302 and a client computer 304 having a speaker 306 . The DRM/content server 302 is configured for authenticating the client computer 304 , receiving the encrypted audio file from the microphone 100 , and providing it, along with encryption key(s), to the client computer 304 . The DRM/content server 302 is also configured for activating/deactivating the microphone 100 . In certain circumstances, it may be desirable to have two servers, e.g., a DRM server that authenticates and provides encryption key(s) to the client computer, as well as activating/deactivating the microphone 100 , and an audio content server for obtaining the audio file from the microphone 100 and providing it to the authenticated client computer 304 . For purposes of brevity, however, only a single server will be described as performing these function.
When an authorized user desires to listen in on the sounds at the location where the microphone 100 is installed, he or she can log into the DRM/content server 302 . Upon proper user authentication, the user may request the microphone 100 to be turned on or activated, e.g., by clicking an icon on the client computer 304 . In response, the DRM/content server 302 will send the appropriate encryption key(s) to the client computer 304 and will send a request to the communications processor 112 to turn on the active components of the microphone 100 ; namely, the acoustic detector 108 and/or the sound processor 110 . Upon receipt of this request, the microphone 100 will be turned on, in which case, the communications processor 112 will output and send the encrypted streaming audio file to the DRM/content server 302 . The DRM/content server 302 will then send the streaming audio file to the client computer 304 , which will then, using the encryption key(s), decrypt the file as it is received, transform it into an analog audio signal, and send it to the speaker 306 , where it is transformed into audible acoustic waves for the user.
When the user is finished listening, he or she may request the remote microphone 100 to be turned off, e.g., by clicking an icon on the client computer 304 . In response, the DRM/content server 302 will send a request to the communications processor 112 to turn off the active components of the microphone 100 . Upon receipt of this request, the microphone 100 will be turned off, in which case, the communications processor 112 will cease sending the encrypted streaming audio file to the DRM/content server 302 .
In certain situations, it may be desirable to remotely activate/deactivate the microphone 100 outside of an IP network environment. In this case, the communications processor 112 may not be needed, and the microphone 100 may send the encrypted digitized audio signal directly from the sound processor 110 to the remote site over a passive line. The remote site can activate/deactivate the microphone 100 by sending signals, e.g., in the form of metadata, to the sound processor 110 , which may then turn the microphone 100 on or off.
Although particular embodiments of the present invention have been shown and described, it will be understood that it is not intended to limit the present invention to the preferred embodiments, and it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present invention. Thus, the present inventions are intended to cover alternatives, modifications, and equivalents, which may be included within the spirit and scope of the present invention as defined by the claims.
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Methods, microphones, and processors are provided for processing ambient sound waves. Ultrasound waves are combined with the sound waves to create heterodyned sound waves. The heterodyned sound waves are detected and, in response, a sound detection signal containing information relating to the heterodyned sound waves is generated. A heterodyned audio signal representing the heterodyned sound waves is generated at least partially based on the sound detection signal, and then an ambient sound signal representing the ambient sounds is derived from the heterodyned audio signal.
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This application is a divisional of application Ser. No. 08/150,948, filed Nov. 09, 1993, which is a continuation-in-part application of Ser. No. 07/600,546, filed Oct. 18, 1990 now abandoned, which in turn is a divisional application of Ser. No. 07/382,603, filed Jul. 19, 1989, now U.S. Pat. No. 4,986,271.
FIELD OF INVENTION
This invention, for example a glucose sensor, relates to a reusable miniature implantable sensor employing an enzyme such as glucose oxidase Immobilized on a bulk powder such as very fine graphite or carbon particles. The sensor is small enough to be inserted into human or animal tissues or blood streams either directly or via a catheter, and has a lifetime of stable and reliable operation long enough for up to several weeks. The enzyme immobilized on fine particles can be removed from the sensor after its use or when exhausted and replaced by fresh enzyme-loaded particles, thereby prolonging the useful life of the sensor.
This invention also relates to a refillable implantable glucose sensor employing an enzyme such as glucose oxidase immobilized on a bulk powder such as very fine graphite particles which can be exhausted from the implanted sensor when spent and replaced by fresh enzyme-loaded particles, thereby prolonging the useful life of the implanted sensor without the need for surgery.
BACKGROUND OF THE INVENTION
Glucose sensors of the type employing enzymes are well known. Many of these feature an "enzyme electrode" which consists of an immobilized enzyme such as glucose oxidase that catalyzes a chemical reaction involving glucose and oxygen--a reaction that involves the catalytic conversion of glucose to gluconic acid and hydrogen peroxide with simultaneous consumption of oxygen. The resulting decrease in consumption of oxygen may be measured by a current sensitive oxygen electrode. The production of hydrogen peroxide can also produce a current to be measured by a hydrogen peroxide electrode. Various arrangements for glucose sensors are described in the following U.S. Patents: U.S. Pat. No. 4,703,756 which utilizes first and second tandem sensor elements mounted in a catheter, one of which sensors acts as a reference and the other of which contacts glucose oxidase, whereby an electrical signal is produced indicative of the oxygen content differential between the two sensors; U. S. Pat. No. 4,240,438 which uses a hydrophobic membrane on which the glucose oxidase is immobilized and which senses the rate of oxygen consumption by the glucose contained in the blood; U.S. Pat. No. 4,655,880 which provides a multiple electrode sensor for measurement of glucose concentration by comparing electron current flow in working and counter electrodes in relation to current flow in a reference electrode; U.S. Pat. No. 3,979,274 which utilizes e laminated enzyme electrode with special filtering properties thereby eliminating the need for e compensating or reference electrode; U.S. Pat. No. 4,224,125 which has an enzyme electrode using an oxidoreductase end a redox copolymer acting as an electron mediator in an enzymatic reaction maintained in an immobilized state on an electron collector or semipermeable membrane; U.S. Pat. No. 4,376,689 wherein the coenzyme is immobilized directly on an electron collector (eliminating the need for a membrane) whereby the activity of the enzyme on a substrate can be directly measured; U.S. Pat. No. 4,418,148 employing a contiguous multilayer membrane structure enabling a more homogeneous distribution of enzyme.
At present there does not exist an enzyme type glucose sensor of small enough size to allow insertion directly into blood streams or tissue either directly or via a catheter, which contains a reservoir filled with enzyme immobilized on a powder so as to provide an extended operational lifetime and providing for reuse by refilling.
The inventive miniature glucose sensor can be used to provide continuous monitoring of blood glucose levels in trauma patients suffering from hemorrhagic shock. This will enhance the medical management of such patients in the field, while being transported, and in the hospital, thus increasing survival rates.
SUMMARY OF THE INVENTION
The present invention provides an improved arrangement for an implantable electrochemical sensor such as a glucose sensor of the type in which the enzyme material degrades due to reaction with components of bodily fluids, the improvements being that degraded enzyme material can be replaced with fresh enzyme material, and that it is of small enough size to be inserted directly or via a catheter into tissues or blood streams, or is of small enough size to allow for incorporation into a catheter assembly, thus prolonging the useful implanted life of the sensor.
According to one embodiment of the present invention there is provided a bulk powder of fine particles carrying immobilized enzyme material. The bulk powder is carried as a suspension in a gel cross-linked matrix. The sensor is constructed so as to allow the sensor to be removed, disassembled, cleaned, and recharged. The sensor has been miniaturized to fit into a 6 or smaller (down to 32) gauge tube or needle.
The sensor has a housing or body defining an outer chamber bounded at its working end, or on the side, by an outer, hydrophilic or hydrophobic membrane which enables bodily fluids to interact with a cathode. The outer membrane is adjacent to the platinum anode. The membrane passes molecules such as glucose but not large molecules of bodily fluids. The reservoir contains powder which comprises enzyme material such as glucose oxidase material immobilized on particles of the bulk powder, which is in a gel led matrix. The glucose oxidase reacts with the incoming glucose to deplete oxygen, and produce hydrogen peroxide; this is sensed by the anode to detect the amount of glucose.
Also, in accordance with another embodiment of the invention, the stability of the enzyme material may be further improved by providing in the sensor an additional replenishable enzyme such as catalase also immobilized on particles of bulk powder carried in a gel. The catalase material removes and neutralizes the hydrogen peroxide produced by the reaction of glucose with glucose oxidase, and in this embodiment the sensor will operate as an oxygen sensor measuring oxygen, instead of hydrogen peroxide. The anode and cathode are each electrically coupled to signal processing and monitoring circuitry positioned outside the body.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference is now made to the accompanying drawings in which like numerals represent like parts and in which:
FIG. 1 is a cutaway view in longitudinal cross section of a glucose sensor in accordance with an embodiment of the invention;
FIG. 2 is a schematic circuit diagram of an arrangement for indicating readouts of glucose concentrations in accordance with an embodiment of the invention;
FIG. 3 is a schematic diagram of a recharging end discharging arrangement for replenishing spent enzyme material in accordance with an embodiment of the present invention; and
FIG. 4 is a cutaway view in longitudinal cross section of a further glucose sensor in accordance with an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
According to the embodiment of the invention shown in FIG. 1 , a glucose sensor 10 in accordance with the principles of the invention has a generally cylindrical housing 11 of any suitable inert material which does not deleteriously react with bodily fluids or tissue. Located within the housing 11 is a generally cylindrical inner housing of like inert material supported in spaced apart relation from the housing 11 by an annular member 15, also of inert material. An outer membrane 17 made of any suitable well-known hydrophilic material spans the extent of one end of the housing 11, hereinafter referred to as the working end 19 of sensor 10.
An inner membrane 21 made of any suitable well-known hydrophobic material covers the working end of the inner housing 13. The inner membrane 21 underlies the outer membrane 17. Consequently, the spaced apart housings 11 and 13 together with their respective membranes 17 and 21 define an outer annular reaction chamber 23 and an inner reaction chamber 25 concentric therewith. The inner chamber 25 is effectively enclosed or bounded at its working end by both the membrane 17 and 21 and at its other end by a fluidtight transverse wall 26.
Also, according to an embodiment of the invention there may be provided a central housing 27 located within the inner housing 13 and held in spaced apart relation therefrom by annular spacers 29. The spacers 29 may be in the form of spoked rings of inert material so that enzyme material may easily pass longitudinally back and forth therethrough in the chamber 25. The central housing 27 has a hydropbobic membrane 31 a t the sensor's working end 19 spaced apart from the membrane 21 and at its other end a transverse wall 32. The housing 27, wall 32, and membrane 31 define a central chamber 33.
The other end of the sensor 10, referred to hereinafter as the feed end 35 for purposes of convenience, has a fluid tight seal 37 made of any suitable well-known material non-reactive with bodily fluids. The seal 37 defines the closed other end of the outer annular reaction chamber 23 and can, if desired, be used in place of transverse walls 26 and 32 to define the closed end of the inner chamber 25 and the central chamber 33.
An insulated, electrically conducting lead 39 passes fluid tightly through the seal 37 and extends longitudinally through the spacer member 15 into chamber 23. A reference electrode 41 composed of both silver and silver chloride is electrically connected to the lead 39 in the chamber 23. The reference electrode 41 may be immediately adjacent to or in intimate physical contact with the outer membrane 17.
Another insulated electrically conducting lead 43 passes fluidtightly through the seal 37 and longitudinally through the spacer member 15 and terminates in the outer annular chamber 23 at cathode or counter electrode 45 made of any suitable noble metal in the form of a helix or mesh or other suitable configuration to provide a large area of reaction located adjacent to or in intimate physical contact with the outer membrane 17. A third insulated electrical lead 47 passes through the seal 37 and terminates in the inner chamber 25 at a helical platinum anode or working electrode 49 immediately adjacent to or in intimate physical contact with the inner membrane
The outer membrane 17 is of any suitable wellknown material to permit the passage of bodily fluids therethrough into the chamber 23. Membrane 17 prevents the entry of large proteins or other large molecules or particulate matter into the chamber 23. The hydrophobic inner membrane 21 operates through molecular diffusion and is of any suitable well known material to enable the passage therethrough into the chamber 25 of only small molecules including limited amounts of glucose which may be present in bodily fluids. Water, large molecules, and large amounts of glucose are excluded by the membrane 21.
The inner chamber 25 is filled with the enzyme material such as glucose oxidase immobilized on and bonded to, i.e., fixed to, bulk powder material which is preferably electrically conductive and may comprise very fine particles of graphite, indicated by the numeral 51. Alternatively, the material 51 may be constituted of very fine particles of carbon, silicon oxide, aluminum oxide, silicon carbide, and such polymers as nylon, polyethylene, polystyrene, or electrically conducting polymers. The response or reaction time of the enzymes is advantageously somewhat shorter where the enzymes are carried on particles, especially electrically conductive particles, such as graphite. This reaction time is longer where the enzymes are fixed as in the prior art, on probes, rods, or membranes. This is due to the movement of the particles and the better contact because of time small size and the electrical conductivity of the particles. The central chamber is filled with a catalase enzyme material generally indicated by the numeral 53. The catalase enzyme material is also immobilized and bonded, i.e., fixed, to very fine particles of graphite in the same manner as the glucose oxidase.
The glucose oxidase enzyme material 51 for chamber 25 may be prepared as set forth in the following Example 1:
EXAMPLE 1
(a) Add 10 mg of glucose oxidase to 42.5 mg Bovine Serum Albumin in a buffer and 0.19 ml of 2.5% Gluteraldehyde to provide a cross-linked enzyme;
(b) To provide covalent linking of the glucose oxidase on modified graphite (i.e., glucose oxidase immobilized on the particles), (1) add 2 g of fine graphite powder about 44 microns in diameter or less particle size to 0.15M 1-cyclohexl-3-(2)morpholinoethyl, carbodiimide, metho-p-toluene sulfonate in 5 ml of 0.1M acetate buffer pH 4.5 at 20 degrees centigrade for 2 hours, (2) wash thoroughly with distilled water, then add 2 ml of 10 mg/ml glucose oxidase in 0.1M acetate buffer pH 4.5 at 4 degrees C for 3 hours, and (3) wash with distilled water and dry in room temperature air; store the dry powder in refrigerator;
(c) Add 120 mg of the immobilized glucose oxidase produced as in (b) above to the cross linked enzyme produced in (a) above.
The catalase 53 for chamber 33 is produced as follows:
(d) Add 1.8 mg catalase to 42.5 mg Bovine Serum Albumin and 0.19 ml of 2.5% Gluteraldehyde;
(e) Add 120 mg of fine graphite powder with catalase immobilized thereon in the same manner as described in (b) above for glucose oxidase. (End of Example.)
Also extending fluidtightly through the seal 37 is an injection or charge tube 55 for introducing fresh enzyme material such as glucose oxidase into the inner chamber 25. The tube 55 terminates in an opening 57 located in the inner chamber 25 near the inner membrane 21. A discharge or exhaust tube 59 for expelling spent enzyme material from the chamber 25 has its opening 61 located near the feed end 35 of the sensor.
A catalase enzyme charge tube 63 passes fluidtightly through the seal 37 into the central chamber 33 and has its open end 65 near the membrane 31. A catalase discharge or exhaust tube 67 also passes fluidtightly through the seal 37 into the central chamber 33 and has its open end 69 near the feed end 35 of the sensor and thus, its open end is relatively remote from the membrane 31. As is well known in the art, the catalase enzyme serves to decompose hydrogen peroxide generated by the oxidation of the glucose occurring in the inner chamber 25. This prolongs the useful life of the glucose oxidase.
Referring to FIG. 2, the leads 39, 43, and 47 for the respective electrodes--reference electrode 41, tile counter electrode or cathode 45, and the working electrode or anode 49--are connected as inputs to a potentiostat amplifier 70. Such an amplifier and the connections thereto for an enzyme glucose sensor are well known in the art such as in aforementioned U.S. Pat. No. 4,703,756 and will not be described in detail. The working electrode or anode 49 puts out an electrical current having an amplitude proportional to the chemical process catalyzed by the sensor attached to it. In particular, the chemical process involved here is very well known in the art and is characterized by the decrease in oxygen and production of hydrogen peroxide resulting from the oxidation of glucose caused by reaction of the glucose with the enzyme material in inner chamber 25.
In a manner that is well known in the art, the working electrode or anode 49 provides a current having an amplitude proportional to the abovementioned oxidation of glucose. The reference electrode 41 provides a calibrated reference voltage for the operation of the potentiostat amplifier 70. The cathode or counter electrode 45 provides a return path corresponding to the ground connection of amplifier 70. The current appearing on lead 47 is converted to a voltage proportional to such current by the amplifier 70, as is indicated by a voltage dropping resistance 70a across which may be connected a suitable monitoring or readout device such as a voltmeter 71. Of course, in a manner well known in the art, device 71 may be a voltage-controlled telemetering unit for transmitting a signal to a remote location such as a central monitoring station or may be any other suitable utilization device, such as a monitoring device attached to a patient.
Referring to FIG. 3, a charge tube or line 55 and discharge or exhaust tube or line 59 for respectively replenishing and exhausting the enzyme material 51 in chamber 25 are shown in a replenishment system according to an embodiment of the invention. This system may also be used for handling recharging and expelling of the catalase enzyme material 53 located in chamber 33 via tubes 63 and 69. Upstream from the feed end of the charge tube 55 is a reservoir 75 which may comprise a bellows and a one-way valve 77 of any suitable well known construction. A first valve 78 in the discharge line 59 and a reservoir 79 which also may be of the bellows type located downstream of the feed end of the discharge tube 59 for handling the spent enzyme material. A second one-way discharge valve 81 is located downstream of the reservoir 79. All of these elements may be implanted preferably near the sensor.
As further shown in FIG. 3, the charge and discharge tubes 55 and 59 converge at a Junction 83 immediately adjacent valves 77 and 81 for transcutaneous reception of a needle or plurality of needles 84 via needle guide 85 of any suitable well known construction.
The procedure for charging and discharging the enzyme material will now be explained. It should be understood that the same procedure applies to handling of both the glucose oxidase in chamber 25 and the catalase in chamber 33. When the enzyme material such as the glucose oxidase is spent or degraded after use, a needle is inserted in the guide 85 to deliver fresh enzyme material to the reservoir 75. The reservoirs 75 and 79 as well as the rest of the fluid handling system including the tubes 55 and 59 are at essentially atmospheric pressure. The enzyme material, for example, glucose oxidase immobilized on fine particles of graphite suspended in the fluid described above, enters the charge reservoir 75 thereby forcing the material therein to flow through tube 55 and from opening 57 into the inner chamber 25 of sensor 10. The slight differential in pressure caused by the injection of the fresh material causes the spent material to exit chamber 25 at the feed end 35 via opening 61 of the discharge tube 59 and flow via one-way valve 78 into the discharge reservoir 79. The one-way valve 78 prevents the spent material from backing into the chamber
Because the opening of tube 55 is proximate the region of the working end of the sensor near the membrane 21 and the electrode 49 in chamber during replenishment the fresh enzyme material tends to be concentrated in that region where can interact with the incoming glucose while the spent enzyme material tends to move away from that region through the opening 61 of discharge tube 59 at the feed end 35 of the sensor. When the discharge reservoir 79 becomes full, an additional needle is employed via the needle guide 85 to exhaust the spent material from the reservoir 79 at substantially the same rate the fresh material is injected into the charge reservoir 75. If desired, two needles may be used simultaneously, one for injecting fresh material and one for exhaust the spent material.
As stated previously, the recharging of the catalase material works in exactly the same way as described above for the glucose oxidase, the replenishment arrangement of FIG. 2 providing recharging of catalase via tube 63 and exhaust via tube 67 in the same manner as for respective tubes 55 and 59.
In accordance with another embodiment of the invention, the catalase enzyme material need not be employed, and thus, referring again to FIG. 1, the central housing 27 and its associated elements, the membrane 31 and the tubes 63 and 67 may be eliminated. Consequently, in accordance with this embodiment, there is provided only an outer chamber 23 and an inner chamber 25 defined by respective housings 11 and 13 and the membranes 17 and 21. Advantageously, in this embodiment the glucose oxidase enzyme material is preferably prepared as set forth in the following Example 2:
EXAMPLE 2
(1) Add 10 mg of glucose oxidase activity (50,000 units/0/29 g) to 42.5 mg of Bovine Serum Albumin (Sigma), and dissolve in 0.24 ml distilled water, then 0.55 ml phosphate buffer pH 7.4.;
(2) add 0.18 ml (2.5%) Glutaraldehyde, the solution being kept in a high moisture content atmosphere for 60 minutes, and then left overnight for cross linking to take place:
(3) Provide covalent linking of the glucose oxidase on modified graphite powder in accordance with the procedure set forth in (b) above; and
(4) Add 120 mg of the immobilized glucose oxidase produced in (3) above to the cross linked enzyme produced from steps (1) and (2) above. (End of Example.)
Indications from tests employing apparatus constructed substantially in accordance with an embodiment of the invention show sustained responsiveness of the tensor to variations glucose over a continuous four-months period. This indicates that the use of bulk amounts of immobilized and/or cross linked enzyme greatly extends the life of the sensor and thus extends the period before refill is needed.
Further, the rechargeable glucose sensor of the present invention provides these important advantages:
(i) continuous monitoring of glucose concentration;
(ii) long life time of several years afforded through recharging:
(iii) small applied voltage:
(iv) immobilization of enzymes on bulk particulate matter enabling efficient reaction with glucose and accurate measurement on a linear basis of glucose levels.
A preferred embodiment of the miniaturized version of the inventive sensor is shown in FIG. 4. Such a sensor can be of the size of a tube or needle of 6 gauge or smaller, for example down to 32 gauge. In the two electrode prototypical system illustrated in FIG. 4, a platinum wire, which in this embodiment has a diameter of about 0.25 mm, but can be larger or smaller, forms the anode 1. The stainless steel body of the needle serves as the cathode 2. It should be noted that as an alternative the cathode body 2 can be of some other metal, either by itself or plated with Ag/AgCl. The annular cavity that is provided between the two electrodes 1, 2 constitutes a reservoir that is filled at least partially, although preferably entirely, with the gelled immobilized glucose oxidase enzyme or some other enzyme immobilized on fine carbon or graphite powder; this immobilized enzyme gel is indicated by the reference numeral 3. A glucose diffusion membrane 4, which is hydrophilic or hydrophobic, is attached to the needle either on the open end as shown in FIG. 4 or over a hole in the side of the needle. The sensor electrodes 1, 2 are electrically insulated from one another by an insulating material 5, such as a polymer, glass, plastic, etc. The overall diameter of the biosensor can range from 5.2 mm to 0.10 mm, and the length thereof can range from 40 mm down to about 10 mm.
The anode and cathode leads or wires 6 and 7 are led by suitable wiring to electronic circuitry that provides an appropriate bias, and scales and converts the current flow into suitable units, using techniques that are well known in the art. For example, a measuring device such as a potentiostat can be used from which the measurement results can be read directly. In this respect, the embodiment of FIG. 4 operates in a manner similar to that described in conjunction with the embodiment of FIG. 2.
It should be noted that the embodiment of FIG. 4 is distinguished from the previously described embodiments not only by the fact that it extremely miniaturized, but also by the fact that it must be removed in order to be refilled. Thus, in order to take advantage of the reusable aspect of this sensor, the same is removed, is disassembled and cleaned, and is then partially reassembled and refilled, all outside of the body or other tissue in which it is to be implanted.
Indications from tests employing apparatus constructed substantially in accordance with a FIG. 4 type embodiment of the present invention shows sustained responsiveness of the sensor to variations in glucose over a continuous period of at least 30 days. This indicates that the use of bulk amounts of immobilized and/or cross linked enzyme greatly extends the life of the sensor and thus extends the period of use before it is necessary to remove the sensor, disassemble clean it, partially reassemble it and refill After the sensor is partially reassembled and refilled, assembly is completed by attaching the membrane 4, for example by gluing it to the cathode or body 2 of the needle, or by placing an 0-ring around the membrane, especially in the embodiment illustrated in FIG. 4. It is also possible to dip the needle into membrane material, such as polyurethane, cellulose acetate, or other polymers.
The reusable glucose sensor of the present invention provides several important advantages; long operational life because large quantities of active enzyme are immobilized on the very large surface area of fine particles; the fine particles carrying the enzyme ere a three-dimensional system; the glucose can diffuse through in a fluid state to reach active enzyme: the total available three-dimensional volume of active enzyme is far greater than that which can be obtained with any known two-dimensional technique, such as enzymes immobilized on planar surface such as membranes, rods, etc. Further advantages include continuous monitoring of glucose concentration, a long lifetime provided by the ability to remove, disassemble, clean, reassemble and refill the sensor, small applied bias voltage and immobilization of enzymes on bulk particulate matter enabling efficient reaction with glucose and accurate measurement of glucose levels.
The reusable, miniature, implantable electrochemical sensor of the present invention constructed in conformity with the embodiment shown in FIG. 4 provides a construction whereby the useful life of the sensor is prolonged, and the performance thereof is stabilized. Such a sensor can, for example, be utilized to measure a specific chemical component in an industrial process, including but not limited to the food processing industry, the pharmaceutical industry, etc., with the specific chemical component being a component of the process which it is desired to monitor or measure. The inventive sensor can also be utilized to measure a specific chemical component in fluids used in clinical laboratories, medical offices and facilities, and research laboratories, with the specific chemical component being a component of the fluid which i t is desired to monitor or measure.
While the invention has been described with respect to detection and measurement of glucose levels in bodily fluids, it should be understood that the invention applies also to other compounds or molecules including, but not limited to, amino acids, lactates, pyruvate, cholesterol, urea or the like which exist: in bodily fluids which are substrates for different enzymes to undergo enzymatic conversion. Thus the enzyme material to be immobilized on particles would be at least one of the group consisting of glucose oxidase, catalase, lactate enzymes, pyruvate enzymes, urease, and cholesterol enzymes. Further, it should be understood that the invention applies also to any to other chemical reaction which may be arranged to occur on a solid substrate (time fine particles), and produces a flow of electrons to produce a current, including but by no means limited to, for example, monoclonal antibodies. Also, the invention may be applied in a research laboratory, a clinical or hospital laboratory or industrial environment in connection with reactor vessels or other in vitro settings. Further, the invention may be applied to emergency medical treatment of trauma patients in the field.
Therefore, the present invention is, of course, in no way restricted to the specific disclosure of the specification and drawings, but also encompasses any modifications within the scope of the appended claims.
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A reusable, miniature, implantable electrochemical sensor, a method of making the same, and a powder therefor are provided. Enzyme material is immobilized on bulk particulate matter, and a reaction chamber of the sensor is then filled therewith. The sensor is implanted in an environment where it comes into contact with a specific component of a fluid with which the enzyme material chemically reacts to produce electrical signals for measuring the reaction. The method preferred for preparing the powder which is used in the electrochemical sensor involves first covalently bonding a quantity of an enzyme to fine particles in powder form to immobilize the enzyme is cross-linked to a non-enzyme protein with a cross-linking agent. Finally, the particles are added containing the immobilized enzyme cross-linked to a protein from the first step to the enzyme cross-linked to a protein from the second step to obtain the powder.
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BACKGROUND OF THE INVENTION
This invention relates to an apparatus for removing nitrogen oxides (NO x ) from a combustion flue gas, and particularly to an apparatus for removing NO x by adding a reducing agent to the combustion flue gas, thereby decomposing NO x by gas phase reduction in the absence of a catalyst, and by providing a temperature-controllable bed of catalyst downstream of the stage in said apparatus where reducing agent is added to obtain a high percent NO x removal.
Combustion flue gas from various industrial combustion equipments using a fossil fuel, such as boilers and gas turbines, contains nitrogen oxides formed in the combustion process. Nitrogen oxides themselves are toxic, and are materials causing photo-chemical smogs. Accordingly a prompt development of techniques for abating NO x in the combustion flue gas has been keenly desired.
NO x is formed in a high temperature zone of a flame in the combustion equipment, and the amount of NO x formed is increased at a higher temperature and by combustion in richer oxygen.
Nowadays, the techniques of abating NO x in boilers and gas turbines are classified into two main groups, that is, the group of techniques of combustion with low NO x content and the group of techniques of removal of NO x from flue gas. The former group is based on a combustion at a low temperature in a low oxygen content, and typical processes of this type are a two-stage combustion process, a flue gas recycle process and a diluted combustion process. The latter group of techniques for removing NO x from flue gas includes a gaseous phase reduction process comprising adding hydrocarbons, hydrogen, carbon monoxide and ammonia to a combustion flue gas at a relatively high temperature to decompose NO x in a gas phase reduction, and a catalytic reduction process comprising adding ammonia, etc. to a combustion flue gas at a relatively low temperature, for example, 250° to 450° C. and decomposing NO x in the presence of a catalyst by gas phase reduction, as disclosed, for example, in U.S. Pat. No. 3,900,554.
The gas phase reduction process is new, as compared with the catalytic reduction process, and belongs to a new technical field involving various problems, but seems to be capable of being greatly advanced by the future technical development. When hydrocarbons, hydrogen and carbon monoxide or the like are used as the reducing agents in the gas phase reduction process, these reducing agents react not only with NO x , but also residual oxygen in the combustion flue gas, and thus the consumption of the reducing agents is increased, rendering the process uneconomical. If ammonia is used as a reducing agent on the other hand, ammonia selectively reacts with NO x and thus the consumption of the reducing agent is small, and also the percent NO x removal is higher than that of the former process. Thus, the selective reduction process using ammonia is especially remarkable in the gas phase reduction processes.
However, according to the conventional gas phase reduction process using ammonia, the reacting temperature necessary for the NO x reduction is high, for example, at least 800° C., and when an application thereof to an existing combustion apparatus such as a boiler or gas turbine is taken into account, there are various problems due to such high temperature conditions e.g. a residence time of a high temperature gas is short, a uniform satisfactory diffusion of ammonia into the combustion flue gas is hardly attainable, etc. Especially in the case of a gas turbine, the temperature zone for removing NO x is within the turbine stage, and thus the application of such process is actually impossible. To solve these problems, a gas phase reduction process applicable to a low temperature range is now in development. As one of such processes, a gas phase reduction process comprising adding ammonia and hydrogen peroxide to a flue gas is available, and its principle of removing NO x is to decompose ammonia to active chemical species, for example, amino radical, imino radical, etc. in advance by reaction between ammonia and hydrogen peroxide and then to decompose NO x by reaction of these active chemical species by reduction. The effective temperature for NO x removal reaction can be lowered to such a low temperature range as about 400° C. in said process. In this process the necessary amount of ammonia for effectively decomposing NO x in the flue gas by reduction is in about 0.3-about 10 in terms of a molar ratio of ammonia to NO x (NH 3 /NO x ), and preferably about 0.5-about 3 in view of the economy and prevention of unreacted ammonia discharge. The amount of hydrogen peroxide to be added thereto is that necessary for decomposing ammonia, and is about 0.3-about 1 in terms of molar ratio of hydrogen peroxide to NO x (H 2 O 2 /NO x ).
However, in this gas phase reduction process using ammonia and hydrogen peroxide, there are such disadvantages that, since oxidation of NO by hydrogen peroxide takes place, the percent NO x removal is somewhat lower than the ammonia reduction process, and when ammonia is added in excess to increase the percent NO x removal, unreacted ammonia is discharged. That is, it is difficult to obtain a satisfactory percent of NO x removal in any of the processes for removing NO x from the flue gas.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an apparatus for removing NO x from a flue gas highly efficiently and economically at a flue gas temperature of 400° to 800° C., while overcoming the disadvantages of the gas phase reduction process using ammonia and hydrogen peroxide.
According to the present invention, a bed of catalyst having a cooling mechanism is provided in a combustion flue gas line at the downstream side of a gas phase reduction process stage using ammonia and hydrogen peroxide to decompose NO x by effluent unreacted ammonia leaving the preceding stage on the surface of catalyst through catalytic reduction, thereby improving the percent NO x removal and the decomposition of unreacted ammonia. That is, in a catalytic reduction reaction, reaction proceeds in a bed of catalyst and a boundary layer zone of temperature very near to that of the bed of catalyst, and thus the reaction of removing NO x can proceed by controlling the temperature of the bed of catalyst to an optimum temperature for removing NO x , almost independently from the gas temperature.
The present invention is based on this principle. A satisfactory catalyst in a plate form can be prepared according to the conventional technique of shaping catalysts, and it is relatively easy to cool the catalyst in such plate form by the use of water, air, or other cooling means, thereby controlling the catalyst temperature appropriately. That is, the present invention provides an apparatus for removing NO x with a high efficiency and in a very econimical manner by applying to a flue gas having a wide temperature range of 400° to 800° C. a gas phase reduction process using ammonia and hydrogen peroxide as a first stage of removing NO x , and a catalytic reduction process using the unreacted ammonia leaving the first stage and a cooled catalyst as a second stage of removing NO x , and particularly provides an apparatus applicable to removal of NO x from a flue gas from a gas turbine or a combined cycle gas turbine, whose flue gas temperature is in a range of 400° to 600° C.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the NO x removal characteristics of currently available typical techniques for removing NO x from flue gas.
FIG. 2 is a diagram showing the NO x removal characteristics according to one embodiment of the present invention.
FIG. 3 is a diagram showing the unreacted effluent ammonia concentration change under the same conditions as shown in FIG. 2.
FIG. 4 is a schematic view of one embodiment of applying the present apparatus to a gas turbine to remove NO x from a flue gas.
FIG. 5 is a partial structural view of FIG. 4, showing a catalyst temperature control by water cooling.
FIGS. 6 and 7 are partial structural views of FIG. 4, showing a catalyst temperature control by air cooling.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, the NO x removal characteristics of currently available typical techniques for removing NO x from a flue gas are shown, where curve A shows the NO x removal characteristics of an ammonia gas phase reduction process for removal from a high temperature gas at least at 800° C., curve B those of an ammonia-hydrogen peroxide gas phase reduction process applied to 400°-800° C., and curve C those of an ammonia catalytic reduction process with a high percent NO x removal at 200° to 450° C. As already described in the Background of the Invention, the ammonia-hydrogen peroxide gas phase reduction process has the most practical possibility among these processes, but has not shown a satisfactory performance yet. Thus, the disadvantage of the ammonia-hydrogen peroxide gas phase reduction process can be overcome in the present invention by combining it with the ammonia catalytic reduction process.
In FIG. 2, test results of the NO x removal by the combination of the gas phase NO x reduction with the catalytic NO x reduction aimed at in the present invention are shown. The test conditions are such that a combustion gas having a NO x concentration of 40 ppm and a gas temperature of 600° C. is passed at a flow rate of 100 Nm 3 /hr through a test duct filled with a bed of plate-shaped catalysts of metal oxide whose temperature can be controlled by water cooling, and NO x removal by NO x gas phase reduction is carried out at the upstream side of the catalyst bed by simultaneous injection of ammonia and hydrogen peroxide thereto as a first stage, whereas NO x removal by catalytic reduction of NO x with residual ammonia from the first stage NO x removal is carried out downstream of the first NO x removal stage in the bed of the catalyst kept to about 400° C. by water cooling as a second stage, where the amount of hydrogen peroxide injected is 0.75 times the moles of NO x , and the space velocity through the bed of the catalyst (gas volumetric flow rate/catalyst bed volume) is 26,000 hr -1 .
In FIG. 3, results of measuring concentrations of unreacted effluent ammonia under the same test conditions as in FIG. 2 are shown.
From the test results of FIGS. 2 and 3, it is evident that the necessary amount of catalyst can be reduced to about one-half of the amount required in the conventional NO x removal by catalytic reduction and at the same time the amount of effluent ammonia can be controlled to a low concentration as the effects of the combination of the NO x removal processes and also of the first stage NO x removal by gas phase reduction.
In FIG. 4, an embodiment of applying the present invention to a gas turbine for power generation is shown. The ordinary gas turbine comprises an air compressor 4, a combustor 5, a turbine 6, a generator 7, a flue gas duct 8, and a stack 9. Air 16 is taken into the air compressor 4, compressed, mixed with a fuel gas 17 at the combustor 5, combusted, and expanded in the turbine to drive the generator 7 and the compressor 4, and combustion flue gas is discharged into the duct 8. Temperature of combustion flue gas after having worked in the turbine is about 450° to about 600° C., and an oxygen partial pressure is 14-16% with a NO x concentration being 100-200 ppm. The flue gas leaving the turbine is discharged as a combustion flue gas 18 to the atmosphere from the stack 9 through the duct 8, but the gas temperature is hardly lowered in the duct due to a large volume of gas. By adding ammonia 19 and hydrogen peroxide 20 to the flue gas from an ammonia nozzle 10 and a hydrogen peroxide nozzle 11, respectively, NO x is decomposed by gas phase reduction. A bed of catalyst 12 provided with a cooling mechanism according to the present invention is installed at the downstream side in the duct to conduct NO x removal by catalytic reduction of NO x with unreacted ammonia. In the present embodiment, a temperature control by water cooling is shown, where a cooling water system is a closed circuit provided with a cooler 14. Cooling water is pumped through the bed 12 of the catalyst by a pump 13 to cool the catalyst, and the resulting hot water is again cooled in the cooler 14. In such an apparatus for removing NO x , ammonia is added thereto a little in excess, for example, at a molar ratio of NH 3 to NO x of 1-3 moles, and hydrogen peroxide is added thereto at a molar ratio of H 2 O 2 to NO x of about 0.3-about 1, which gives a good NO x removal performance.
The catalytic reduction reaction satisfactorily proceeds with unreacted effluent ammonia from the preceding stage of gas phase reduction process by controlling the temperature of the catalyst of metal oxide system to about 300°-about 450° C., while the flue gas temperature is kept unchanged at about 450°-about 600° C. Furthermore, the decomposition reaction of unreacted ammonia also proceeds together with the NO x removal reaction.
Furthermore, since the decrease in the gas temperature is not so large through the bed of catalyst according to the present invention, the flue gas duct 8 of the gas turbine can be applied preferably as an apparatus for NO x removal of flue gas from a combined cycle gas turbine by providing a waste heat boiler in the flue gas duct 8.
FIG. 5 relates to the embodiment shown in FIG. 4, and more specifically shows the water cooling device for the catalysts. The catalysts in the bed 12 is formed in plates, the plates are arranged in parallel to one another through a plurality of cooling water pipes 23 to provide a catalyst bed structure of the so called parallel flow type. Such structure can reduce a pressure drop through the catalyst bed and thus is suitable for gas turbines with a high flue gas velocity.
In FIG. 6, catalyst plates in the bed 12 are closely fixed to an air pipe 25 passing through the flue gas duct 8, and cooling air is supplied to the air pipe 25 by a blower 24 to control the catalyst temperature. Such catalyst bed structure can control the catalyst temperature by adjusting a cooling air rate through the air pipe. In FIG. 7, the catalyst temperature is controlled by air cooling in the similar manner to that shown in FIG. 6. An air pipe 25 is passed through a flue gas duct 8, and one end of the air pipe 25 is open to the atmosphere, and the other end thereof is open to the inside of stack 9. Catalyst plates of the bed 12 are closely fixed to the air pipe 25 within the flue gas duct 8. In such a structure, an air flow 26 is induced through the air pipe 25 by natural ventilation and suction, made by the stack, and the plates are cooled by the air flow. In the present embodiment, power is not required for air cooling, rendering the operation economical.
The present invention is applicable not only to NO x removal from flue gas from a gas turbine, but also to boilers, a heating furnace, etc. so long as the flue gas temperature is about 400°-about 850° C.
Effects of the present apparatus for NO x removal from a flue gas as described above will be summarized below:
By providing a bed of a catalyst of a metallic oxide system, provided with a temperature cooling mechanism downstream of an ammonia-hydrogen peroxide gas phase reduction process, (1) decomposition of effluent excess ammonia from the ammonia-hydrogen peroxide gas phase reduction process is promoted. (2) Since the gas phase reduction and the catalytic reduction proceed at the same time, the NO x removal process with a high efficiency (high percent NO x removal and low pressure drop) can be obtained. (3) Since the NO x removal by catalytic reduction proceeds almost independently from the flue gas temperature, it is possible to effectively conduct the NO x removal reaction for a flue gas at a relatively high temperature such as a flue gas temperature of 400°-850° C. Particularly, the present invention can be preferably applied to a gas turbine whose flue gas temperature is about 450°-about 600° C., and can provide a compact and highly efficient plant for NO x removal.
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An apparatus for removing nitrogen oxides from a flue gas comprises a first stage of injecting ammonia in a combustion flue gas and then hydrogen peroxide thereto, thereby decomposing nitrogen oxides in the combustion flue gas to nitrogen and water by gas phase reduction, and a second stage of passing the combustion flue gas leaving the first stage through a bed of catalyst whose temperature is controlled by cooling water passing through a cooling pipe provided through the bed of catalyst, thereby conducting decomposition of excess ammonia exiting from the first stage and further reaction of nitrogen oxides at the same time.
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BACKGROUND OF THE INVENTION
The subject of this patent of invention is an INTEGRATED, MULTIPHASE, ENERGY-DISSIPATING ENVIRONMENTAL SYSTEM for the protection of ports, harbours and coastal complexes. The structural elements which conform the SYSTEM are sequential, in series, and work together to prevent the wave energy from invading the protected waterspace. The combination of overflowable breakwaters, permeable quays and nonreflecting structures separated by channels or basins behaves as an integrated, hydrodynamic, energy-dissipating unit. The system works as follows: first, as the waves (wind waves) pass over the overflowable structure the watermass is broken and dispersed loosing its dynamic energy through the energy-dissipating devices placed on it's crown. As the water emultion hits the channel the choppiness created is mitigated by the channel (hydraulic dissipator) and finally annuled by the permeable quay as the water flows through. Any other residual agitation that might be created inside the port or harbour is significantly reduced by the nonreflecting perimetral structure. The SYSTEM dissipates the energy of the short-period gravity waves (wind waves, wake waves, percution waves) and prevents resonances and wave reflection inside the harbour, while enabeling:
the sea horizon to be observed
the stagnated and polluted waters inside the harbour to be renewd
and the surface air and sea breezes to circulate freely in the sheltered area
as well as allowing for the structural elements and channel areas to be occupied and enjoyed, during the benevolent weather seasons, by the users who can fullfil such activities as fishing, swimming or boating.
For at least three thousand years, man has been creating artifical, sheltered areas on coasts, mainly for the purpose of building ports, using mainly shelter breakwaters and mooring quays as structures with both frequently combined into breakwater-quays.
Surprisingly, unlike what has happened in other tecniques, the type of these maritime structures, conventional breakwaters and quays, has not substantially evolved over time and, in general, at least when wave energy is very high, have kept to the types consolidated already in times prior to the Roman Empire.
Up to the present time, while maintaining this very old tradition, these marine structures have been designed to strictly fulfill the main function for which they were intended--vessel berthing and mooring--. Over the last few decades, these structures have been designed with sophisticated studies and structural tests to determine the dynamic action of gravity waves, berthing and/or mooring stresses, seismic effects, etc., but hardly stopping to observe and much less endeavour to solve the serious functional, environmental and panoramic problems caused by these structures. Such problems are particularly marked on coasts with a short tidal range.
Conventional types of shelter structure have been classed into two large groups:
vertical or quasi vertical face breakwaters forming monolithic structures called vertical or reflecting breakwaters, and
sloping breakwaters generally built with natural or artificial blocks, regularly or irregularly arranged, forming a more or less flat slope, called rubblemound breakwaters or simply breakwaters.
Functionally speaking, both types of conventional reflecting and rubblemound breakwaters, may be classed, in turn, into nonoverflowable and overflowable.
The basic disadvantage of conventional nonoverflowable breakwaters, whether reflecting or rubblemound, has always been their huge height, since their crown level in both cases has to exceed a height such that it prevents the highest waves in maximum storms occurring during the foreseeable life of the structure to overflow, which has led to colossal constructions, with truly impressive crown levels: San Ciprian (Lugo, Spain), 22 metres, Bilbao, 21.5 metres, Gijon, 18 metres.
To rectify the many disadvantages of such exaggeratedly high structures as far as possible, the crown level in what are called conventional, partially overflowable breakwaters has been brought down to a height almost half that of conventional nonoverflowable breakwaters. Nevertheless, this reduction, which has not sufficed to prevent the serious environmental and panoramic disadvantages of nonoverflowable breakwaters, allows overflow water and spindrift to pass which, even with small volumes of water, and consequently, unable to renew the water in sheltered areas, are capable of causing heavy damage in quays, in small boats (like sport and fishing vessels) and in port facilities in the vicinity of breakwaters.
The modest protection afforded by coverings such as slabs and pavings does not suffice to guarantee the protection of conventional overflowable breakwater crowns which causes quay walls attached to them to overturn. Examples of stability failure for this reason are very numerous and, on occasions, dramatic.
Moreover, in partially overflowable, rubblemound breakwaters without crown protection (groynes), the blocks of the main protective layer, subjected to a descending flow of water, are under highly precarious stability conditions, unless the crown width is dimensioned overlong, which means serious disadvantages as regards occupation, aesthetics, economics, etc.
Berthing quays have been traditionally built with walls, sheet-piling, etc. with vertical or quasi vertical, highly reflecting face walls for short period gravity waves.
More recently, following the traditions of southeast Asia, berthing structures have been designed with permanent piers forming open structures supported by piers and/or piles, and by floating piers, moored and/or anchored which, in both cases, do not form any appreciable hydrodynamic barrier to the propagation of currents and/or gravity waves in the sheltered areas.
Thus, with the exception of piers and the actual berthed and/or anchored boats themselves, whose presence does not substantially affect the hydrodynamics of the areas sheltered, as we have said, all these conventional marine structures, breakwaters and quays, are in fact: continuous, reflecting, impermeable and nonoverflowable, since the volume of liquid entering into the sheltered areas is practically negligible, even with conventional, partially overflowable breakwaters and despite the damage it causes.
To the environmental and panoramic problems caused by the formation of climatic and visual barriers, caused by the huge height of breakwater crowns, is added the choppiness caused by the reflection of gravity waves which enter through the harbour mouth and/or are generated by boats travelling in the sheltered areas and producing multiple interferences and possible resonances.
All these problems, together with the stagnation of water in dock basins due to the difficulty in renewing such water, with an accumulation of waste, creation of anearobic conditions, etc. are the cause of the vile environmental, health and even aesthetic quality of conventional harbours.
Applying the applicant's Spanish patents: "Energy-dissipating overflow-type protecting system on dykes and/or jetties", no. 543,747 and "Stepped mosaic breakwaters" no. 537,141 and the related Spanish Utility Models nos. 289,904; 291,366; 295,249 and 295,248 (applicant's U.S. Pat. Nos. 4,834,578; 4,801,220; 4,875,804) enables the functional, environmental and panoramic disadvantages of conventional breakwaters to be eliminated, but only with significant design wave heights less than about four metres. When the significant design wave height is higher than that figure, the choppiness in the sheltered area becomes unacceptable for berthing small boats which are those generally frequenting marinas and fishing ports.
SUMMARY OF THE INVENTION
In contrast to the concept of the maritime shelter structure prevalent up to now, which consists of a single breakwater,--whether conventional (with huge size and crown height) or energy-dissipating overflowable (with low crown height but with a limited field of application)--the INTEGRATED, MULTIPHASE, ENERGY-DISSIPATING ENVIRONMENTAL SYSTEM introduces the concept of "shelter system" in Maritime Construction Technology, which means an authentic revolution in the manner of approaching this problem.
With the sequential, INTEGRATED, MULTIPHASE, ENERGY-DISSIPATING ENVIRONMENTAL SYSTEM, which is the subject of this Patent of Invention, the sheltered areas of water (channels and basins) form an integrated, hydrodynamic unit dissipating the energy of short period gravity waves (wind waves, wake waves, percussion waves, etc.), since this unit is limited, shaped, by a "shelter system" made up of an aggregate of structures formed by the combination, if necessary with repetition, of linear structuring elements (structures) of the following three types:
Overflowable, of very low crown height, preferably formed by overflowable shelter breakwaters, preferably rubblemound breakwaters.
Permeable, of low crown height, preferably made up of permeable quays.
Actually nonreflecting with a crown height preferably no higher than that of the land forming the shore, preferably made up of shoreline constructions forming the land/sea boundary.
Under normal conditions, overflowable structuring elements are preferably located on the sea side to break and/or reflect the waves and are preferably formed with shelter breakwaters with a low crown height, preferably breakwaters of either natural and/or artificial rubblemound in general, with the crown even totally or partially submerged and thus being overflowable by waves as required.
This low crown level of the overflowable structuring elements facilitates the entry of water flows caused by breaking waves into the sheltered area, improving the renewal of water in these areas and allowing these flows, if such be the case, to return at least partially to the sea, but to do so, the crown of these overflowable elements must be suitably shaped, dimensioned and protected in order to guarantee stability.
Applying the applicant's Spanish patents: "Energy-dissipating overflow-type protection system on dykes and/or jetties", no. 543,747 and "Stepped mosaic break-waters", no. 537,141 and the related Spanish Utility Models nos. 289,904; 291,366; 295,249 and 295,248 (applicant's U.S. Pat. Nos. 4,834,578; 4,801,220; 4,875,804) enables the crown of these overflowable structuring elements to be provided with suitable flat tops, preferably fitted with devices and/or shapes in high and/or bass relief, which facilitates the aeration of the liquid flux and the dispersion of the overflow waters into the air, extending the impact period and area with which the effectiveness of these overflowable elements as energy dissipators is increased.
In addition, the possible solutions afforded by applying these patents and utility models improve the features of the System's overflowable structuring element occupation, enable the size and cost of the construction work to be reduced and make it possible to simulate natural geological outcrops: basaltic, granitic, etc., with the consequent functional, environmental, panoramic, scenic and economic advantages.
In general, the permeable structuring elements are positioned as berthing quays on the shelter side of the energy-dissipating channels and in certain locations in the port basins, forming selective hydrodynamic barriers allowing currents and long period gravity waves, tides, etc. to pass through them and filtering short period gravity waves (wind waves, wake waves, percussion waves).
Applying the applicant's patent entitled "Energy-dissipating Permeable System, with laminar perforated elements", Spanish application no. P.9102080, enables these permeable structuring elements to be functionally optimized by using perforated plates with holes and/or grooves attached to the open pre-existent structures and, should such be the case, forming the permeable elements themselves with cellular caisson structures, ballasted, if necessary, with rubblemound, tubular pieces, etc. which enable maximum effectiveness of this structuring element as a selective hydrodynamic barrier to be achieved in each case. In certain cases, if convenient, thanks to this same "Energy-dissipating Permeable System, with laminar perforated elements" patent, the permeable structuring elements can be shaped as permeable-overflowable structures.
Preferably, all overflowable and/or permeable structuring elements in Integrated Environmental Systems are arranged and behave like nonreflecting elements, at least partially, but the actual nonreflecting structuring elements themselves are neither overflowable or permeable but simply nonreflecting.
These nonreflecting structuring elements have their basic application in forming the land/sea interface (dock basins, etc.), making up the boundaries of interior, nonoverflowable, impermeable structures such as shore quays, dockyards (separate or joined to land), etc.
Applying the applicant's aforementioned "Energy-dissipating Permeable System, with laminar perforated elements" patent enables the morphology and functionality of these nonreflecting structuring elements to be optimized, by preferably using cellular caisson structures with one of their panels blank, unperforated, which provides these nonreflecting elements with the necessary leak-tightness.
All the structuring elements mentioned, preferably the overflowable and permeable ones, may be discontinuous and divided into three separate stretches, with openings which, in accordance with maritime terminology we shall call mouths.
If necessary, these stretches overlap to prevent short period gravity waves being transmitted by the mouths, with overlaps preferably in continuous monotonous series, alternating series (staggered) and/or randomly.
The distances separating the adjacent stretches and the overlapping lengths between them, as well as the orientation of the mouths, have to be suitable for preventing, at least partially, any choppiness being transmitted to more sheltered areas. If necessary, these mouths may be fitted with suitable, perforated plates or other permeable devices which will filter short period gravity waves.
With the INTEGRATED ENVIRONMENTAL SYSTEM, the channel and basin unit then becomes an integrated, energy-dissipating hydrodynamic one in which overflows and, should such be the case, coastal currents enter under control, thus facilitating renewal of the water in sheltered areas. Short period gravity waves (wind waves, percussion waves, wake waves) are filtered and their reflections, interferences and possible resonances are dissipated.
Because of their particular location, there is a specific separation of the different choppiness areas: channels and basins. Choppiness in exterior channels may be relatively heavy, at least occasionally, so these channels, if necessary, may only be occupied for harbour and/or recreational purposes during times of good weather which, in our latitudes, fortunately coincide with the tourist season.
In forming sheltered areas for recreational and/or harbour uses, located on coasts with moderate energy waves, we can consider the following closed sequence as standard.
______________________________________(sea / overflowable element / hydraulic dissipator / / permeable element / hydraulic dissipator / / nonreflecting element / land).______________________________________
limited by land and sea, formed by the combination in series of a structuring element from each of the three types, but when waves are high energy or when other conditions so require, there are further sequences, if necessary, with repetition of some of the structuring elements, as in the following examples:
______________________________________(sea / overflowable element / hydraulic dissipator / / overflowable element / hydraulic dissipator / / permeable element / hydraulic dissipator -(sea / overflowable element / hydraulic dissipator / / permeable element / hydraulic dissipator / / permeable element / hydraulic dissipator -______________________________________
and/or the multiplication of the number of structuring elements, forming integrated environmental Systems with a higher degree of sequences.
In certain cases, preferably when carrying out extensions, remodelling and/or improving already existing ports and/or basins, part of the pre-existing conventional marine structures can be used and the INTEGRATED ENVIRONMENTAL SYSTEM will be simplified, reduced, for example, to the open sequence,
______________________________________(sea / overflowable element / hydraulic dissipator / / overflowable element / hydraulic dissipator -______________________________________
and the open INTEGRATED ENVIRONMENTAL SYSTEM is supplemented with other pre-existing conventional port systems.
In such cases, it is worth remodelling the conventional port elements by reducing their crown levels to levels compatible with those of the INTEGRATED ENVIRONMENTAL SYSTEM'S structuring elements.
As we pointed out earlier, when wave features are small, with a significant design wave height of less than four metres, choppiness in the body of water (channel, basin, etc.) leeward of the external structuring element is in some cases very little, practically negligible, and the INTEGRATED ENVIRONMENTAL SYSTEM can be simplified even further, by reducing, degenerating it (in the mathematical sense) to a single structuring element. In such a case, the solution may be to directly apply one of the applicant's patents: "Energy-dissipating overflow-type protection system on dykes and/or jetties", "Stepped mosaic breakwater" and, even, when fitting, the ", Energy-dissipating Permeable System, with laminar perforated elements".
As we already indicated, with the INTEGRATED, MULTIPHASE, ENERGY-DISSIPATING ENVIRONMENTAL SYSTEM, the concept of a shelter system is introduced in contrast to the concept of the simple, single, shelter structure, prevalent up to now, which means a new way of approaching the shelter problem, both for new designs and for the extension, remodelling and restoring of pre-existing structures.
Among the numerous advantages of the INTEGRATED ENVIRONMENTAL SYSTEM, we shall only point out those enabling us to evaluate the great technical attraction and novelty of this invention as indicated:
However high the design wave height is, it is possible to obtain a multiphase, short period gravity wave energy-dissipating INTEGRATED ENVIRONMENTAL SYSTEM, whose crown height can be low as required and in no case exceeds much more than one meter above sea level, which allows for the free circulation of surface air and preservation of sea views, with no other barriers than those created by nature herself.
These climatic and panoramic advantages are particularly appreciated at the present time both by coast dwellers and visitors since both the sea views and presence of breezes characterize the highly appreciated excellencies of the coastline and are essential reasons for its charm. These advantages are particularly appreciable in urban areas where the use of conventional breakwaters with crown heights generally above eight metres, and which can occasionally exceed twenty, can affect shoreline residents and users.
A very important additional advantage of the INTEGRATED ENVIRONMENTAL SYSTEM which is the subject of this invention, is its ease as regards user occupation, both the structuring elements themselves (by strollers, bathers, anglers) and the energy-dissipating channel or channels (for the occasional berthing of boats). This possibility for occupying the channel or channels in the INTEGRATED ENVIRONMENTAL SYSTEM has significant functional and economic importance, since it enables occasional mooring to be provided for small craft which do not avail of a permanent berth, cruise boats, etc.
However small the tidal range, even if nil, as in the Mediterranean, with the INTEGRATED ENVIRONMENTAL SYSTEM, it is possible to renew the dock basin water, due to the combined effect of overflow and permeability characterizing the INTEGRATED ENVIRONMENTAL SYSTEM, which prevents mud sedimentation problems, floating item accumulation and the establishment of anaerobic conditions, so frequent and undesirable both from the health and aesthetic point of view in conventional systems.
When geographical and cultural environments are suitable, the use of discontinuous structuring elements with stretches separated by mouths enables coastal areas to be sheltered with a group of structures (stretches) which simulate, if necessary, geographical compositions such as chains of islands, archipelagos, atolls, etc. which is a most outstanding advantage from the environmental and landscape point of view.
By applying the applicant's aforementioned patents "Energy-dissipating overflow-type protection system on dykes and/or jetties", "Stepped mosaic breakwaters" and "Energy-dissipating Permeable System, with laminar perforated elements" and their related Utility Models, the INTEGRATED ENVIRONMENTAL SYSTEM, built as per this invention, can adopt layouts and morphologies enabling its effectiveness as an energy dissipator to be optimized and geomorphological (dunes, cliffs) and/or geological reliefs (column basalts, granites) to be simulated, which means a great advantage and important supplement for the aforementioned geographical simulation.
The field of application for structures built with the INTEGRATED ENVIRONMENTAL SYSTEM is very broad and varied, with new, diverse functions and layouts not only in newly designed structures but also in the extension, remodelling and restoration of already existing marine structures.
In short, it is necessary to underline that shelter effects, shoreline defence, etc., equivalent to those achieved with conventional, nonoverflowable breakwaters, whether rubblemound or vertical, with huge crown heights and sizes, can be obtained with structures which hardly emerge and are even partially submerged, overflowable and/or permeable, nonreflecting and, should such be the case, discontinuous, like those specific to this INTEGRATED ENVIRONMENTAL SYSTEM, while at the same time improving functional, occupational, health, panoramic, landscape, aesthetic and financial conditions.
The definition of the INTEGRATED ENVIRONMENTAL SYSTEM can also be deduced from analysing the accompanying clarifying figures, with a nonlimiting definition of the subject of this invention.
BRIEF DESCRIPTION OF THE DRAWING
FIGS. 1-3 are each a fragmentary isometric schematic of a respective preferred embodiment of the present invention;
FIGS. 4-5 are each a fragmentary isometric schematic of a respective closed variation;
FIGS. 6-9 are each a fragmentary isometric schematic of a respective open variation;
FIG. 10 is a fragmentary side elevational schematic of an embodiment without a permeable structuring element;
FIG. 11 is a fragmentary side elevational schematic of an embodiment without a non-reflecting structuring element;
FIGS. 12-15 are each a fragmentary side elevational schematic of an embodiment eliminating one of the structuring elements; and
FIGS. 16-19 are each a plan view schematic layout of a respective embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1, 2 and 3 show three applications of the INTEGRATED ENVIRONMENTAL SYSTEM in perspective, configured as a standard shelter system with the combination in order, without repetition, of the structuring elements from the three types and the following closed sequence,
______________________________________(sea / overflowable element/ hydraulic dissipator / / permeable element / hydraulic dissipator / / nonreflecting element / land).______________________________________
bound by land and sea, where the first hydraulic dissipator acts as a channel with occasional berths useable in season and the second as a dock basin with permanent berths. All the structuring elements in FIGS. 1, 2 and 3 are linear and continuous, except the permeable structuring element in FIG. 1 which is discontinuous.
In the three FIGS. 1 to 3, and the following ones, when pertinent, the body of water is indicated with a 1 (sea, lake, reservoir, etc.); an overflowable structuring element with a 2 (in this application, formed with the applicant's "Energy-dissipating overflow-type protection system on dykes and/or jetties" patent, with the layout of an overflowable, energy-dissipating rubblemound breakwater, 10); a first hydraulic energy dissipator, acting as a energy-dissipating channel, with 3; a permeable structuring element, with 4 (in this application, formed with the applicant's "Energy-dissipating Permeable System, with perforated laminar elements" patent, with application number P.9102080, with the layout of a caisson filter quay, 11); a second hydraulic dissipator (acting as a port, recreational basin, etc.) with 5; a nonreflecting element (in this application, schematized with a caisson filter dock, 14, with the blank land side plate, 27) with 6 and terra firma, the shore, (in this application with a function as a possible service area) with 7.
In the application of FIG. 1, the permeable structuring element, 4, is discontinuous, with its stretches indicated by 12 and the discontinuities, i.e., the spaces between adjacent stretches, which using maritime terminology, we here call mouths, with a 13.
In these FIGS. 1, 2 and 3 and in the following ones, when fitting, the main protection layer of the overflowable, rubblemound, energy-dissipating breakwater, 10 is shown by 20; the secondary layer and core of this breakwater by 21; the flat crown top with 22 and the high relief, energy-dissipating elements with 23. The foundation berm of the caisson filter quay, 11, with 24 and the perforations in the lateral plates and caisson stabilizing boulders with 25 and 26 respectively.
The same 24, 25 and 26 respectively identify the foundation berm, perforation of lateral division walls and stabilizing boulders of the blank caisson filter dock, 14, which, in this application, becomes an actual nonreflecting structuring element itself, neither overflowable nor permeable, which we have already shown with a 6. The blank plate of the caisson filter dock, 14, which acts as a shore quay and is located or sited at the land limit, 7, is shown with a 27. The landward side of this nonreflecting element is occupied by a gravel fill, shown by 28.
The arrows which schematize the most frequent direction of the hydrodynamic circulation, over the overflowable sea wall, via percolation through the permeable elements and via the mouths, 13, allowing the water in sheltered areas, channels and dock basins, to be renewed, are indicated by 40.
FIG. 3 shows the application of the layouts of the two open, nonstructuring elements most common in coastal and harbour complexes: A pier, 15, supported on piers, 29, and a platform, 16, supported on piles, 30, whose presence does not substantially affect either the hydrodynamic integrity or hydrodynamic configuration of the System, but which facilitate better recreational operation and use of the INTEGRATED ENVIRONMENTAL SYSTEM.
As a nonexhaustive indication, in FIGS. 4 to 9, the layouts of the cross sections of some applications for the INTEGRATED ENVIRONMENTAL SYSTEM are shown, forming a short synoptic summary of some possible structuring sequences:
______________________________________figure 4(sea / overflowable element / hydraulic dissipator / / permeable element / hydraulic dissipator / / nonreflecting element / land)figure 5(sea / overflowable element / hydraulic dissipator / / overflowable element / hydraulic dissipator / / nonreflecting element / land)figure 6 hydraulic dissipator / / permeable element / hydraulic dissipator / / permeable element / hydraulic dissipator / / nonreflecting element / land)figure 7(sea / overflowable element / hydraulic dissipator / / overflowable element / hydraulic dissipator / / permeable element -figure 8(sea / overflowable element /hydraulic dissipator / / permeable element / hydraulic dissipator / / permeable element -figure 9 hydraulic dissipator / / permeable element / hydraulic dissipator / / permeable element / hydraulic dissipator / / permeable element -______________________________________
In the case of FIG. 4, an application is shown with only one structuring element from each of the three types in the INTEGRATED ENVIRONMENTAL SYSTEM, without repetition, forming a closed sequence, bounded by land and sea. This sequence may be considered as standard as it contains the three types of structuring elements without repetition and in the most frequent order in practical applications. This standard sequence is identical to those represented in FIGS. 1, 2 and 3 and is included in this summary only for synoptical reasons.
Two applications are shown in FIGS. 5 and 6, with repetition of the overflowable structuring elements, 2, in FIG. 5 and permeable, 4, in FIG. 6, with closed sequences.
Four applications are shown in FIGS. 6 to 9, with repetition of one of the structuring elements, with open, unlimited sequences, at one of their ends: In the system shown in FIG. 6, on its sea side; in the systems shown in FIGS. 7 and 8, on their land side. In the application shown in FIG. 9, the sequence is unlimited at both ends, land and sea.
In these figures, 8 indicates the limit of the representation of the INTEGRATED ENVIRONMENTAL SYSTEM and 9, the possible extra elements, alien to the INTEGRATED ENVIRONMENTAL SYSTEM. These extra elements, 9, may be additional structuring elements from any of the three types considered, with the whole then making up an INTEGRATED ENVIRONMENTAL SYSTEM, with a sequence of a higher degree than those sequences already considered, or may be nonoverflowable, impermeable and/or reflecting elements of a conventional system to which are added an open sequence INTEGRATED ENVIRONMENTAL SYSTEM by an extension, remodelling, etc.
In the same way as there is a possibility of sequences with a degree of complexity higher than the third, it is also possible, of course, to simplify the INTEGRATED ENVIRONMENTAL SYSTEM by eliminating one or some of the structuring elements.
In this context, FIGS. 10 and 11 show two applications with elimination of the permeable structuring element in the first, FIG. 10, and of the nonreflecting structuring element, FIG. 11.
The application in FIG. 10 is especially suited to shoreline protection while that in FIG. 11 constitutes the standard, reduced form of the INTEGRATED ENVIRONMENTAL SYSTEM, with an open sequence, applicable in the extension, remodelling and/or improvement of already existing harbour and/or costal complexes and to the protection and/or sheltering of new conventional projects with elements, should such be the case, either impermeable and/or reflecting in nature in which the condition of low crown height is imposed.
Obviously, the structuring elements of the INTEGRATED ENVIRONMENTAL SYSTEM may be shaped with any type of construction, provided they comply with specifications, low crown level, etc., characterizing this System.
In order not to overwhelm with a number of examples with possible types other than those represented in the applications shown in FIGS. 1 to 11, only some applications will be shown hereafter with reduced sequences, with only two structuring elements, and only some of the most usual conventional types are used.
An application of the INTEGRATED ENVIRONMENTAL SYSTEM with an open sequence is shown in FIG. 12
______________________________________(sea / overflowable element / hydraulic dissipator / /permeable element -______________________________________
identical to that shown in the application in FIG. 11, but with its overflowable structuring element, 2, formed here with breakwaters (groynes) without a flat crown top. The main protection layer in this application covers the breakwater crown, 31, in its entirety, which, if the crown height is low, compels a very wide width for this crown. In this case, it is not recommended to use the outside shore, on the sea side, for recreational purposes.
FIG. 13 shows an application for the INTEGRATED ENVIRONMENTAL SYSTEM with an open sequence
______________________________________(sea / overflowable element / hydraulic dissipator / / overflowable element -______________________________________
whose second overflowable structuring element is formed with a vertical, low crown height breakwater, 18, whose body, 32, rests on a berm, 24, and is protected with the pertinent guard blocks, 33. With this arrangement, the vertical breakwater, 18, may be used, at least seasonally, as a breakwater-quay.
In order to remove the water flowing over the first overflowable element, 2, the vertical breakwater, 18, must preferably be discontinuous, with its pertinent mouths.
FIG. 14 shows an application with the same sequence as the foregoing application,
______________________________________(sea / overflowable element / hydraulic dissipator / / overflowable element -______________________________________
but with its two overflowable structuring elements, 2, formed with the applicant's "Stepped mosaic system", Spanish patent no. 537,141 and Spanish utility models nos. 289,904; 291,366 and 259,249 (applicant's U.S. Pat. Nos. 4,801,220; 4,875,804) which enable the crown of both overflowable structuring elements, 19, to be configured as energy dissipators, while simulating basaltic, granitic and terrace type landscapes, which improves their functional, occupational, environmental, aesthetic and landscape quality.
FIG. 15 shows an application of the INTEGRATED ENVIRONMENTAL SYSTEM with a closed sequence
______________________________________(sea / overflowable element / hydraulic dissipator / / nonreflecting element / land)______________________________________
identical to that of the application in FIG. 10 but with its nonreflecting structuring element, 6, formed by an unobstructed quay, 34, on piles, 35, with a rockfill ramp, 36, to prevent short period gravity wave reflection (wind waves, wake waves, percussion waves).
It is thus possible to configure the INTEGRATED ENVIRONMENTAL SYSTEM with numerous sequences and varying types of structuring element arrangements, achieving applications suited to the different functions, uses and configurations of coastal complexes. To this effect, it would seem advisable to graphically illustrate the use of discontinuous elements with overlapping, nondiffracting stretches, helping in the rapid removal of overflow water and facilitating the renewal of water in sheltered areas, with some examples.
FIGS. 16 and 17 show layouts in ground plan of two applications of the INTEGRATED ENVIRONMENTAL SYSTEM, the first, FIG. 16, with its permeable structuring elements, 4, discontinuous, in alternating series, staggered, and the second in a continuous monotonous series, FIG. 17. The overflowable structuring element in FIG. 18 is discontinuous and in FIG. 19 both structuring elements are discontinuous.
In any event, the direction of the stretches, 12, of the different structuring elements must be orientated with respect to the direction of wave propagation, shown with the arrow, 37. The layout of diffraction in the mouths, 13, is shown schematically with a wave crest, 38.
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This patent consists of an INTEGRATED, MULTIPHASE, ENERGY-DISSIPATING ENVIRONMENTAL SYSTEM, applicable in forming sheltered port and coastal areas. Its channels and basins act as an integrated, hydrodynamic, energy-dissipating unit as their boundaries are formed by linear, low crown level structuring elements, preferably nonreflecting, overflowable, preferably formed by overflowable rubblemound breakwaters and/or permeable quays, if necessary with these elements discontinuous, dissipating short period gravity waves, their reflection and possible resonances and allowing overflow waters and coastal currents to circulate.
Because of its low crown level and the specificities characterizing its structuring elements, this System preserves sea views and allows surface air to freely circulate and basin water to be renewed., with consequent functional, environmental and scenic advantages. (FIG. 3).
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BACKGROUND OF THE INVENTION
This application is related to my earlier application Ser. No. 712,353, filed Aug. 6, 1976.
The present invention generally pertains to the storage of energy and the retrieval thereof as heat, and is specifically directed to physical-chemical methods and systems for storing and retrieving heat.
There is a need for an improvement in storing energy. Most forms of energy are readily converted to heat and may be stored by heating a storage medium. The storage medium may be an inert substance, such as water or rocks, wherein the heat is stored by raising the temperature of the substance and retrieved by moving a relatively cooler heat transfer fluid over the surface of the storage medium. Heat storage by raising the temperature of chemically inert material has the disadvantage of requiring thermal insulation to prevent heat loss and requiring a large volume of substance to store useful quantities of heat.
Heat also may be stored by reversible physiochemical reactions. In one such system, a salt hydrate is heated in a container to above its latent heat of fusion on its liquid state to store the heat. The heat is retrieved by passing a relatively cooler heat transfer fluid such as air or water around the salt hydrate container, thereby producing an exothermic crystallization process, whereby heat is surrendered to the heat transfer fluid. One difficulty with this system is that a stratification layer of the crystalized salt tends to form at the heat transfer surface thereby creating a barrier which reduces the rate of heat transfer.
SUMMARY OF THE INVENTION
According to the present invention, energy is stored by heating a salt to a temperature above its latent heat of fusion to convert the salt to a liquid state; and heat is retrieved by moving a heat transfer fluid consisting essentially of liquid metal or metals immiscible with (and non-chemically reactive with) the salt, and having density less than that of the salt, over the top surface of the liquid salt at such a velocity that the upper layer of the salt is emulsified with the heat transfer fluid to crystalize the salt in the upper layer to thereby exothermally surrender heat from the salt to the heat transfer fluid. The crystalized salt gravitates from the top surface thereby maintaining the top surface in a liquid state.
The present invention is fully operative with both normal salts and those having a supercooled liquid phase. Use of supercooled liquid phase salts allows heat to be stored at ambient or room temperature that are lower than the latent heat of fusion of the salt.
By using a heat transfer fluid in the form of liquid metal or metals immiscible with the salt and of a lower density than the salt, an emulsion between the two can be formed to thereby increase the heat transfer area; while at the same time a sufficient demarcation between the heat transfer fluid and the salt is defined to prevent significant entrainment of salt crystals in the heat transfer fluid outside of the emulsion layer. A higher heat transfer rate is obtained because of the larger heat transfer area between the salt and the heat transfer fluid incident to their direct contact with one another in the emulsion.
The heat transfer fluid is moved across the salt in such a pattern as to create a large shear rate between them. Two preferred patterns are a vortex pattern and an outward radial pattern. Although the heat transfer fluid is moved across the top surface of the salt at such a velocity that the upper layer of the liquid salt is emulsified with the heat transfer fluid to increase the heat transfer area, this velocity must not be so high that crystallized salt is entrained in the heat transfer fluid out side of the emulsion layer. If the salt crystals become so entrained they may coat and clog whatever means, if any, are used to move the heat transfer fluid out of the container containing the salt to a heat exchanger.
In one embodiment both the heat transfer fluid and the salt are enclosed in the same container and a coolant is moved through tubing that makes contact with the heat transfer fluid to remove heat from the heat transfer fluid through the tubing to the coolant. Because the heat transfer fluid is enclosed in the container, a larger emulsion layer can be tolerated since there is no danger of salt crystals being circulated outside of the container; and as a result a greater heat transfer area and crystalization rate can be achieved.
Preferred salts include such halide salts as lithium fluoride and sodium fluoride. Preferred heat transfer liquid include lithium and sodium, or other alkali metals of density less than that of the salt.
DRAWING DESCRIPTION
FIG. 1 is a schematic drawing of one preferred embodiment of an energy storage and heat retrieval system in accordance with the present invention;
FIG. 2 is a schematic drawing of a second preferred embodiment of the system of the present invention;
FIG. 3 is a schematic drawing showing a portion of another preferred embodiment of the system of the present invention;
FIG. 4 is a schematic drawing of a portion of still another preferred embodiment of the system of the present invention;
FIG. 5 is an elevational view of a modified system; and
FIG. 6 is a phase diagram.
DETAILED DESCRIPTION
Referring to FIG. 1, the salt 10 is stored in a cylindrical container 12. The salt is heated by energy transferred through a heating coil 14 inside the container 12 and/or by energy transferred through the container wall 16 from hot water tubes 18 mounted on the outside wall 16 of the container 12. Accordingly, the salt 10 is heated to above its latent heat of fusion to its liquid state (phase). Conductive heating strips can be substituted for the hot water tubes in a system wherein all of the energy to be stored is electrical in form. Alternatively, where all of the energy is stored from hot water, hot water tubes can be substituted for the heating coil 14.
The heat transfer liquid 20 is moved rapidly over the top surface 22 of the salt 10, in a vortex pattern, and an emulsion layer 23 is formed. The salt in the emulsion layer 23 crystalizes and exothermally transfers to the liquid 20 the energy that was stored in the salt 10 by heating the salt 10 to above its latent heat of fusion. The salt which crystalizes then gravitates to the bottom of the container 12 to maintain the top surface 22 of the salt 10 in a liquid state.
This process of rapidly moving the heat transfer liquid 20 directly across the top surface of the salt 10 is also significant when the salt is one which both has a supercooled phase and can be converted from its supercooled phase by agitation. The agitation produced by the rapid movement of the heat transfer fluid causes such a salt to crystalize from its supercooled phase when the mere cooling of the salt 10 by contact with a relatively cooler heat transfer fluid by itself would not be sufficient to convert the salt 10 from its supercooled liquid state, and the introduction of a nucleation agent to effect such conversion would be necessary. The present invention is nevertheless operable, however, even with those salts having a supercooled state, as to which agitation does not effect conversion, whereby the introduction of a nucleation agent or some other means is required for conversion.
The top of the container 12 has an inlet 24 through which the liquid 20 is directed tangentially into the container 12 so as to flow in a free vortex pattern. The liquid 20 is moved over the top surface 22 of the salt 10 at such a velocity that the upper layer of the salt 10 is emulsified with the liquid 20 in a layer 23 to increase the heat transfer area. The top of the container 12 includes an outlet 26 in its top center for drawing out the liquid 20. The liquid 20 flows more rapidly at the center of the vortex, and thereby affords a higher heat transfer rate near the outlet 26. Also, intense centrifugal force near the center of the vortex separates any salt crystals from the liquid 20 and prevents such salt crystals from being drawn into the outlet 26, and thereby prevents the outlet 26 and the tubing 28 leading therefrom from becoming coated with and clogged by any such salt crystals.
The heated liquid 20 is transferred by tubing 28 to a heat exchanger 46. The heat exchanger 46 essentially includes a coil 50 and a fan 48 for removing the heat from the mineral oil by blowing air across the coil 50. A pump 30 is provided in the system for pumping the cooled liquid back through the container 12.
This process may be repeated by again heating the crystalized salt to a temperature above its latent heat of fusion.
Referring to FIG. 2, the salt 32 is stored in a cylindrical container 34. A heating coil 36 inside the container 34 and hot water tubes 38 mounted on the outside of the container wall 40 are provided for heating the salt 32 to store energy therein as described in connection with the embodiment shown in FIG. 1 discussed hereinabove.
The heat transfer liquid 42 (which is the primary heat transfer liquid) is stored within the container 34 in the space above the salt 32. A coolant (which is in effect, a secondary heat transfer fluid) is circulated through the liquid 42 without making direct contact therewith by means of tubing 44. The heated coolant is moved through the tubing 44 to a heat exchanger 46 where heat is removed from the coolant by blowing air with a fan 48 across a coil 50. A pump 52 is provided for circulating the coolant.
Still referring to the embodiment of FIG. 2, a propeller 54 is mounted in the top center of the container 34 for moving the liquid 42 over the top surface 56 of the salt 32 in an outward radial pattern. The outward radial pattern of the flow of the liquid maintains high temperatures at the wall 40 of the container 34 and thereby prevents salt crystals from building up on the wall 40. Any salt crystals having a tendency to form on the wall 40 or the tubing 44 will melt when heated. The propeller 54 is driven by a motor 58.
The liquid 42 is moved over the top surface of the salt 32 to form an emulsion with the salt in layer 43. The liquid 42 is heated by the exothermic crystallization of the salt 32 and the salt crystals so formed gravitate to the bottom of the container 34 to maintain the top surface 56 in a liquid state. This process may be repeated by again heating the crystalized salt to above its latent heat of fusion. The heat transfer area may be increased by increasing the size of the emulsion layer 43. Because the liquid 42 is enclosed in the container 34, a larger emulsion layer can be tolerated than in the embodiment shown in FIG. 1.
The present invention may also be practiced by linear movement of the heat transfer fluid over the top surface of the liquid state salt, such as with the systems partially shown in FIGS. 3 and 4.
In the system of FIG. 3, the heat transfer liquid 60 is moved from an inlet 62 on one side of the container 64 across the top surface 66 of the liquid salt 68 to an outlet 70 on the other side of the container 64. In other respects, this embodiment is the same as that shown in FIG. 1. An extremely high rate of linear flow is desired in order to create an emulsion in the top layer 71 of the salt 68 with the liquid 60 to increase the heat transfer area. Also, with a higher rate of flow the salt crystals that are formed are of smaller size, thereby providing greater heat release and also preventing an accumulation of salt crystals at the top surface 66.
In the system of FIG. 4 the heat transfer liquid 72 is moved within convection cells 74 formed in the top portion of the container 76, thereby creating a linear motion across the top surface 78 of the salt 80 to form an emulsion layer 82. A coolant that circulates through a heat exchanger (not shown) is moved through the liquid 72 without making contact therewith by means of tubing 84, as in the embodiment shown in FIG. 2. The heat flows in free convection currents through the liquid 72 within the container 76 and is conducted to the coolant through the tubing 84.
The process of storing energy by heating the salt and retrieving the energy by exothermic crystallization of the salt caused by moving the relatively cooler heat transfer liquid across the salt is the same in the embodiments of FIGS. 3 and 4 as in the embodiments of FIGS. 1 and 2.
In the above, the heat transfer liquid typically consists of liquid metal or metals of density less than that of the salt. For example, the salt may then consist of a metal halide, to provide a high temperature heat storage system. More specifically, the liquid metal may consist of lithium or sodium, or a mixture thereof, or other alkali metals, singly or in mixtures, and the salt may consist of a halide salt or a mixture of halide salts. The relative proportion of the salts in the mixture of same is selected to achieve a desired melting temperature of the salt melt. Mixtures of lithium fluoride, sodium fluoride and potassium fluoride are usable.
Referring to FIG. 5, a molten salt mixture of lithium fluoride and sodium fluoride is seen at 80 in the lower portion of vessel 81. A heat exchanger tube (or tubes) 83 extends in the melt for transferring heat to the melt. The fluid source of heat enters and leaves the exchanger at 84 and 85. The additive heat transfer liquid consists of molten lithium and sodium in upper region 86 above and at the sides of a vortex generator cone 87. The latter is shell-shaped, and is concave downwardly, extending across the region 86. A central impeller 88, motor driven at 89, rotates the cone 87. Liquid 86 is discharged radially outwardly by the impeller and flows downwardly over the cone, and under the edge 87a of the cone to entrain molten salt indicated by flow arrows 90. The mix of salt and molten metal forms an emulsion indicated at zone 91, within the shell-like cone. The emulsion circulates into the "eye" of the impeller at 92, for recirculation through the impeller and flow back down over the cone. The shell tends to maintain the emulsion zone 91 separate and apart from molten liquid in zone 86.
In this way, heat is transferred from the salt melt to the liquid metal in the emulsion, and heat is transferred from the liquid metal as via heat exchanger tubing 96 in region 86. Coolant flows through tubing 96 to remove heat from the system.
Salt crystallites form in the emulsion as a result of the heat transfer, and they gravitate downwardly in the melt, away from the emulsion. An inert gas seal at 98 enables initial introduction of inert gas into the vessel, nitrogen being an example.
A phase diagram of the lithium fluoride, sodium fluoride mixture appears in FIG. 6. If the lithium metal to sodium metal (coolant) ratio (by weights) is made the same as the chosen fraction of lithium fluoride to sodium fluoride (by weight), no replacement of one metal by the other will occur. The desired operating (melting) temperature is chosen by varying the fractional constituents in the salt mixture.
Accordingly, the salt is typically selected from the group that includes sodium fluoride, lithium fluoride and potassium fluoride; and the liquid metal is typically selected from the group that includes sodium, lithium and potassium.
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Energy is stored by heating a salt to a temperature above its latent heat of fusion to convert the salt to a liquid state. Heat is retrieved by moving a heat transfer fluid consisting of liquid metal or metals immiscible with the salt, and having a density less than that of the salt, over the top surface of the liquid salt at such a velocity that the upper layer of the salt is emulsified with the heat transfer fluid to crystallize the salt in the upper layer. Heat is thereby exothermally surrendered to the heat transfer fluid and the crystallized salt gravitates from said top surface, thereby maintaining the top surface in a liquid state. It is preferred to move the heat transfer fluid over the top surface of the salt in either a vortex pattern, or an outward radial pattern.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority on U.S. Patent Application Ser. No. 61/528,885, filed on Aug. 30, 2011, incorporated herein by reference.
FIELD OF THE APPLICATION
[0002] The present application generally relates to a connection system and method for releasably connecting a tool to a vehicle for subsequent hauling or driving, such as the connection of a plow to a vehicle.
BACKGROUND OF THE ART
[0003] It is often desired to releasably connect tools to vehicles to perform specific occasional tasks. For instance, plows, such as snowplows, may be used on a temporary basis on a vehicle. However, if the vehicle is a domestic vehicle such as a pick-up truck or an all-terrain vehicle, it may be desired to disconnect the plow after use, as the plow may be cumbersome.
[0004] Existing systems often require the user to move out of the vehicle to align the tool with the vehicle. The vehicle must then be driven forward to engage the tool to the vehicle, etc. The release of the tool from the vehicle may also be cumbersome, and may often require that the user step out of the vehicle and attend to the tool under the vehicle. It is, therefore, desirable to provide a connection system that simplifies the temporary connection of the vehicle tool to the vehicle.
SUMMARY OF THE APPLICATION
[0005] It is therefore an aim of the present disclosure to provide a connection system for vehicle tools that addresses issues associated with the prior art.
[0006] It is a further aim of the present disclosure to provide a method for releasably connecting a tool to a vehicle.
[0007] Therefore, in accordance with the present application, there is provided a connection system for a vehicle tool, comprising: a vehicle structure unit adapted to be secured to an underside of a vehicle; a tool connector unit adapted to be secured to a vehicle tool; a male and female connector system between the vehicle structure unit and the tool connector unit for the mating engagement therebetween; a latch unit latching at least one male connector of the connector system into a corresponding female connector for releasable engagement, the latch unit comprising at least one biasing element to bias the latch unit into the releasable engagement; and an interface connected to the latch unit for operating the latch unit in disengaging the male and female connector system.
[0008] Further in accordance with the present application, there is provided an assembly of a plow and a connection system, comprising: a plow; and a connection system comprising: a vehicle structure unit adapted to be secured to an underside of a vehicle; a tool connector unit secured to the plow; a male and female connector system between the vehicle structure unit and the tool connector unit for the mating engagement therebetween; a latch unit latching at least one male connector of the connector system into a corresponding female connector for releasable engagement, the latch unit comprising at least one biasing element to bias the latch unit into the releasable engagement; and an interface connected to the latch unit for operating the latch unit in disengaging the male and female connector system.
[0009] Still further in accordance with the present application, there is provided a method for connecting a vehicle tool to a vehicle, comprising: aligning a tool connector unit connected to the vehicle tool with a vehicle structure unit on the vehicle; manually raising the tool connector unit by handling an arm unit of the tool connector unit; moving the vehicle forward to cause the latching engagement of the tool connector unit with the vehicle structure unit; and releasing the arm unit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a perspective view of a connection system for a tool such as a plow;
[0011] FIG. 2 is an enlarged view of the connection system of FIG. 1 ;
[0012] FIG. 3 is a perspective view of the connection system of FIG. 1 , with latches in position for the disengagement of the vehicle tool;
[0013] FIG. 4 is a perspective view of the connection system of FIG. 1 , with a vehicle structure unit moved out of engagement with a tool connector unit;
[0014] FIG. 5 is a perspective view of the connection system of FIG. 1 , with a tool connector unit thereof in alignment with a vehicle structure unit thereof; and
[0015] FIG. 6 is an assembly view of components of the connection system for vehicle tool of FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] Referring to the drawings, and more particularly to FIGS. 1 and 2 , there is illustrated a connection system for a vehicle tool at 10 . The connection system for vehicle tool may be used with any appropriate type of vehicle, such as trucks, cars, all-terrain vehicles, etc. The vehicle tool may be any appropriate tool that is pushed (e.g., driven) or pulled (e.g., hauled) by the vehicle. For instance, the vehicle tool may be a plow, such as a snowplow.
[0017] The connection system 10 has a vehicle structure unit 12 that may become an integral or temporary part of the vehicle, and a tool connector unit 13 .
[0018] The vehicle structure unit 12 is the structural component of the connection system 10 and attaches to the vehicle or is integral with the vehicle.
[0019] The tool connector unit 13 attaches to the tool, and is releasably connectable to the vehicle structure unit 12 . The tool connector unit 13 is therefore the interface between the vehicle structure unit 12 and the vehicle tool.
[0020] In FIG. 1 , there is illustrated an example of a vehicle tool in plow 14 . The plow 14 is of the type that is pushed by a vehicle to plow away loose matter, such as snow, gravel, etc.
[0021] To provide context, the plow 14 is secured to the tool connector unit 13 by a pair of structural members 15 or any appropriate structural configuration. An interface 16 interrelates the plow 14 to the structural member 15 . The interface 16 may be a pivot mount by which the plow 14 is pivotally mounted to the structural member 15 . The pivot mount is one possible configuration among others for the connection between the plow 14 and the structural members 15 . For instance, there may be a rigid connection (i.e., no degree of freedom) between the structural members 15 and the tool. Moreover, it is observed from FIG. 1 that a biasing unit(s) may be used as well to ensure the plow 14 maintains a given orientation when possible. As mentioned previously, any appropriate vehicle tool may be used with the connection system 10 , and the description of the plow 14 given above is for illustrative purposes only.
[0022] Referring concurrently to FIGS. 1 and 2 , the vehicle structure unit 12 is shown in greater detail. The vehicle structure unit 12 consists of a body 20 . In an illustrated embodiment, the body 20 is a rigid plate having a top planar surface. However, any other appropriate shape for the body 20 is considered, for instance to customize the vehicle structure unit 12 to an underside of a vehicle. The vehicle structure unit 12 is illustrated as supporting four different U-bolts, i.e., U-clamps. Therefore, by way of the U-bolts 21 , the vehicle structure unit 12 may be secured to an undersurface of the vehicle. Accordingly, once U-bolts 21 secure the body 20 to the vehicle, the vehicle structure unit 12 is integral with the vehicle. The U-bolts 21 typically connect to the structural parts of the vehicle, such as the chassis. It is understood that any other appropriate configuration or connection means may be used to secured the vehicle structure unit 12 to the vehicle. For instance, the vehicle structure unit 12 may be bolted directly to the vehicle or welded directly thereto, among numerous other possible configurations.
[0023] Referring to FIGS. 2 and 4 , the vehicle structure unit 12 features a pair of brackets 22 (one of which is shown). The brackets 22 each have a portion that projects downwardly from the body 20 , upon which portion is a male connector 23 . The male connector 23 may be a pin, a bolt, or any other projecting component. The pin may be molded or cast directly with the bracket 22 , may be bolted thereto, welded thereto, etc. In any selected embodiment, the brackets 22 and the male connectors 23 of the vehicle structure unit 12 must have the necessary strength to sustain the forces applied thereon by the driving/hauling of the vehicle tool. The male connectors 23 may be opposed ends of a single rod, etc. The male connectors 23 may have a circular section as illustrated, or any other appropriate sectional shape.
[0024] Referring concurrently to FIGS. 1-3 , the tool connector unit 13 is shown having a structural base 30 . The structural base 30 is connected to the vehicle tool. In the illustrated embodiment, the structural base 30 is integral with the vehicle tool. More specifically, the structural base is a bar that is connected to the free ends of both the structural members 15 of the vehicle tool. Female connectors 31 are positioned at opposed ends of the bar and are thus part of the structural base 30 . The female connectors 31 are laterally oriented U-shaped plates, each defining a slot 32 oriented away from the tooling end of the vehicle tool.
[0025] A latch 33 is pivotally mounted to the structural base 30 . The latch 33 therefore moves between the position of FIG. 3 , in which the latch 33 is away from the slots 32 to allow entry and exit of the male connectors 23 . The other position of the latch 33 is shown at FIG. 2 , in which the latch 33 maintains the male connectors 23 captive therein. A push bar 34 may interrelate the latches 33 such that they move concurrently. Therefore, in an embodiment, the latches 33 may move concurrently in their pivoting motion relative to the structural base 30 . Other configurations are possible, for instance with the latches 33 moving independently from one another. The latches 33 are shaped and oriented to expose a contact surface or contact edge (i.e., a ramp surface or ramp edge, sliding surface/edge) to the incoming male connectors 23 . Hence, when the male connectors 23 contact the contact surfaces of the latches 33 , the latches 33 move away to the position of FIG. 3 .
[0026] A biasing unit 35 , partially visible in FIG. 3 , biases the latches 33 to the position of FIG. 2 , namely the position by which the slots 32 are closed off by the latches. The biasing unit 35 may be a helical spring, a leaf spring, or any other appropriate biasing component. Moreover, the tool connector unit 13 may feature more than one biasing unit 35 , for instance to increase biasing forces or if the latches 33 are independent.
[0027] An interface, in the form of an arm unit 36 , is integrally connected to the push bar 34 and may be used to displace the latch 33 away from the biased position of FIG. 2 . In the illustrated embodiment, the arm unit 36 features a telescopic arm 37 . The telescopic arm 37 projects laterally from the tool connector unit 13 . The telescopic arm 37 is manually handled by the user to operate the connection system 10 . The telescopic arm 37 is in a telescopic relation with a square-section tube 38 , although other sectional shapes are possible as well. The tube 38 is fixedly secured to the push bar 34 . As shown in FIG. 6 , a pin 39 may be used with appropriate holes in both the telescopic arm 37 and tube 38 , so as to adjust the length by which the telescopic arm 37 projects out of the housing 38 . While the telescopic arm 37 is inserted in the tube 38 in the illustrated embodiment, other configurations are also possible.
[0028] Now that the various components of the connection system 10 have been described, an installation of the vehicle tool to the vehicle is set forth.
[0029] Firstly, the vehicle structure unit 12 must be secured appropriately to the vehicle or must be integral with the vehicle. This is typically done, for instance, before the vehicle tool is used for the first time. The vehicle structure unit 12 may be permanently secured to the vehicle, or may be removed once the vehicle tool is no longer required, for instance after a season, in the event that the vehicle tool is of the seasonal-use type (e.g., snowplow). The tool connector unit 13 is connected to the vehicle tool for the method of installation of the tool to be performed.
[0030] The vehicle and the vehicle tool are then aligned with one another. In the illustrated example, FIG. 5 shows a suitable alignment, with the vehicle being illustrated by the vehicle structure unit 12 on the left-hand side of the page. The vehicle then moves towards the tool connector unit 13 , with a forward movement of the vehicle being in a direction generally collinear with a longitudinal axis of the structural members 15 . The vehicle is stopped when in close proximity to the tool connector unit 13 .
[0031] The telescopic arm 37 is arranged so as to project laterally beyond a side of the vehicle, such that it may be manually handled from the vehicle. The driver of the vehicle bends over to grasp the telescopic arm 37 and subsequently raises the tool connector unit 13 . It may be required that the vehicle roll over the telescopic arm 37 once aligned as described above. Alternatively, the telescopic arm 37 may be installed once the vehicle is in close proximity to the tool connector unit 13 . In the latter case, all necessary precautions must be taken to ensure that the installation is performed safely (e.g., vehicle turned off, park brake actuated, etc.). The illustrated arm 37 is on the right-hand side of the vehicle, and may thus be used with an all-terrain vehicle, etc. For standard left-driving side vehicles, the arm 37 may project on the left-hand side instead. Moreover, as some vehicles are higher above the ground (e.g., pick-up truck), the arm 37 may have an upwardly-projecting component to be readily grasped by the driver of the vehicle from the driver's seat.
[0032] In raising the tool connector unit 13 , its female connectors 31 are generally aligned with the male connectors 23 of the vehicle structure unit 12 . The vehicle is at that point driven forward further, whereby the male connectors 23 contact the latches 33 . The latches 33 therefore latch away from the position of FIG. 2 by this engaging action, making way for the male connectors 23 to fit inside the slots 32 . The biasing unit 35 then biases the push bar 34 and latches 33 back to the position of FIG. 2 , whereby the male connectors 23 are held captive in the female connectors 31 . At that point, the vehicle tool may be used. The tool connector unit 13 is connected to the vehicle structure unit 12 in the manner shown in FIG. 2 .
[0033] In order to release the tool from the vehicle, the user applies a force A on the arm unit 36 , as shown in FIG. 3 . In doing so, the latches 33 move out of the way of the slots 32 . The pivoting motion is illustrated by arrow B.
[0034] The vehicle is then moved in the opposite direction, as shown by arrows C in FIG. 4 . In moving away from the vehicle tool, the male connectors 23 move out of the slots 32 , and the tool connector unit 13 falls to the ground.
[0035] As shown in FIG. 5 , once the force on the arm unit 36 is released, the latches 33 are biased back to the latched position illustrated in FIG. 5 , but with the vehicle structure unit 12 separated therefrom.
[0036] It is pointed out that the latching mechanism may be part of the vehicle structure unit 12 instead of the tool connector unit 13 . In such a case, an alternate way to raise the tool connector unit 13 would be required, for the vertical alignment of the vehicle structure unit 12 with the tool connector unit 13 . For instance, the arm 37 could be connected to other parts of the structural base 30 .
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A connection system for a vehicle tool such as a plow, comprising: a vehicle structure unit adapted to be secured to an underside of a vehicle. A tool connector unit is adapted to be secured to a vehicle tool. A male and female connector system is between the vehicle structure unit and the tool connector unit for the mating engagement therebetween. A latch unit latches at least one male connector of the connector system into a corresponding female connector for releasable engagement, the latch unit comprising at least one biasing element to bias the latch unit into the releasable engagement. An interface connected to the latch unit for operating the latch unit in disengaging the male and female connector system.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to methods and compositions to impart coffee stain resistance to polyamide fibers such as those found in textile substrates, as well as to the treated fibers and substrates themselves. More particularly, the present invention relates to compositions useful in imparting coffee stain resistance to polyamide textile substrates, such as carpets, the compositions comprising either (i) a copolymer selected from the group consisting of a hydrolyzed aromatic-containing vinyl ether maleic anhydride copolymer, a half ester of an aromatic-containing vinyl ether maleic anhydride copolymer, and mixtures thereof, or (ii) an aromatic-containing acrylate copolymerized with an acid selected from the group consisting of acrylic acid and maleic acid.
2. The Prior Art
Polyamide textile substrates, such as carpeting and upholstery fabrics, may be permanently discolored or stained by certain colorants, like food or beverage dyes. It is known to use sulfonated aromatic formaldehyde condensates (a) in a yarn finish, during or after fiber quenching (U.S. Pat. No. 4 680 212), (b) in a dye bath (U.S. Pat. No. 4 501 591), or (c) incorporated into the fiber (U.S. Pat. No. 4 579 762, all for the purpose of improving stain resistance of carpet fiber. Use of fluorochemicals in combination with sulfonated aromatic formaldehyde condensates to improve stain and soil resistance is taught in U.S. Pat. No. 4 680 212. Commonly assigned U.S. application Ser. No. 101 652, filed Sept. 28, 1987 (International Publication No. WO 89/02949), discloses improved methods, utilizing application of sulfonated aromatic condensates, to enhance stain resistance of dyed nylon carpet fiber. These documents are all hereby incorporated by reference.
In the prior art the stain blocking performance of compositions is typically determined by testing for resistance to FD&C Red Dye 40, which is found in Cherry Kool-Aid® drink product, as well as in other beverages and foods. Those compositions which are effective in enhancing the stain resistance of the substrate to FD&C Red Dye 40 are then described as "stain blockers". Applicants have discovered, however, that not all "stain blockers" which are effective against staining by FD&C Red Dye 40 are effective in enhancing the stain resistance of the substrate to coffee.
The present invention was developed as a consequence of a need for a stain blocker which would be effective in resisting hot coffee stains, preferably in addition to resisting Red Dye 40 stains.
BRIEF DESCRIPTION OF THE INVENTION
This invention is a composition useful in imparting coffee stain resistance to polyamide textile substrates. The composition comprises a copolymer selected from the group consisting of a hydrolyzed aromatic-containing vinyl ether maleic anhydride copolymer, a half ester of an aromatic-containing vinyl ether maleic anhydride copolymer, and mixtures thereof. By the hydrolyzed copolymer, or hydrolysis product, is meant the hydrolyzed copolymer in which some, preferably less than about 25 to 50 percent, of the original anhydride units remain as anhydride. By the half ester is meant the esterification product of the copolymer with a lower alcohol, preferably a C1-C5 alcohol, most preferably isopropyl alcohol, in which some, preferably about 25 to 50 percent, of the original anhydride units remain as anhydride and in which the reacted anhydride units are monoesterified. The copolymer has a weight average molecular weight between about 1,200 and 23,000, preferably between about 1,200 and 15,000, more preferably between about 2,000 and 10,000 and most preferably between about 2,000 and 4,000 The weight average molecular weight is determined by Gel Permeation Chromatography (hereafter "GPC") by comparison with polystyrene standard using a set of Phenogel columns of the 10 micron particle size, covering a range of 50-500 angstroms pore diameter, 300 mm length, 7.8 mm I.D. and with tetrahydrofuran as eluent.
Preferred copolymers can be represented by the formula ##STR1## wherein m is 4 to 100, p is 0.5m to 0.7m, X is a moiety of an aromatic compound effective to improve stain resistance, R is alkyl or hydrogen and Z is either --0-- or --O--CH 2 --CH 2 --O--. Preferably m is 2 to 20, X is selected from the group consisting of phenyl, naphthyl, and a partially saturated naphthyl-like ring, and R is C 1 -C 5 . When X is selected from the group consisting of 5,6,7,8-tetrahydro-1-naphthyl and 5,6,7,8-tetrahydro-2-naphthyl, then Z is preferably --O--CH 2 --CH 2 --O-- and R is preferably C 1 --C 3 . When X is selected from the group consisting of 1-naphthyl and 2-naphthyl, and R is C 1 --C 5 , then Z is preferably --O--CH 2 --CH--2--O--. When X is phenyl, and R is C 1 --C 5 , Z can be either --O--CH 2 --CH.sub. 2 --O-- or --O--, preferably the latter.
The present invention is also a method of imparting improved coffee stain resistance to a polyamide textile substrate comprising treating the substrate with an effective amount of a copolymer selected from those set forth above, i.e., a hydrolyzed aromatic-containing vinyl ether maleic anhydride copolymer, a half ester of an aromatic-containing vinyl ether maleic anhydride copolymer, and mixtures thereof The preferred copolymers are also as set forth above The amount of the copolymer added to the substrate ranges from about 0.2 to 3.0, preferably 1.5 to 3.0 percent based on the weight of the substrate. When the substrate is treated with the half ester of phenyl vinyl ether maleic anhydride copolymer, the copolymer preferably is applied to the substrate in an aqueous solution at a temperature ranging from about 20° to 90° C., preferably 50° to 90° C., and having a pH ranging from about 2 to 9. The degree of coffee stain resistance imparted depends on the application pH. The optimum pH depends on the form the material appears to take when applied. If the material appears to be in a dispersion, then application pH can be about 2 to 5; if the material appears to be in solution, then application pH can be about 4 to 9, preferably 5 to 7, most preferably 5 to 6.
This invention is also a coffee stain-resistant polyamide textile substrate, preferably a nylon-6 substrate, having deposited thereon an effective amount of a composition which imparts coffee stain resistance to the substrate. The composition comprises a copolymer as set forth above. When the copolymer is either the half ester or the hydrolysis product of 2-(phenoxy) ethyl vinyl ether maleic anhydride copolymer or of phenyl vinyl ether maleic anhydride copolymer, the substrate has improved resistance to dye fading upon exposure to ozone and light, and does not yellow on exposure to UV light or oxides of nitrogen. When the copolymer is the half ester or the hydrolysis product of phenyl vinyl ether maleic anhydride copolymer, the substrate also has excellent resistance to staining by FD&C Red Dye 40.
In another embodiment, this invention is another composition useful in imparting coffee stain resistance to polyamide textile substrates. This composition comprises an aromatic-containing acrylate copolymerized with an acid selected from the group consisting of acrylic acid and maleic acid. The copolymer has a weight average molecular weight between about 2,000 and 15,000, determined by GPC as previously set forth.
Preferred copolymers for this embodiment can be represented by the formula ##STR2## wherein s is 2 to 50 and t is 2 to 50, X is a moiety of an aromatic compound effective to improve stain 15 resistance, and Z is either --O-- or --O--CH 2 --CH 2 --O--. Preferably, X is selected from the group consisting of phenyl, naphthyl, and a partially saturated naphthyl-like ring. When X is selected from the group consisting of 5,6,7,8-tetrahydro-1-naphthyl and 5,6,7,8-tetrahydro-2-naphthyl, then Z is preferably --O--CH 2 --CH 2 --O--. When X is selected from the group consisting of 1-naphthyl and 2-naphthyl, then Z is preferably --O--CH 2 --CH 2 --O--. When X is phenyl, Z can be either --O--CH 2 --CH 2 --O-- or --O--, preferably the latter.
This invention is also a method of imparting improved coffee stain resistance to a polyamide textile substrate comprising treating the substrate with an effective amount of a copolymer selected from those of the second embodiment above, i.e. an aromatic-containing acrylate copolymerized with an acid selected from the group consisting of acrylic acid and maleic acid. The preferred copolymers are as set forth. The amount of the copolymer added to the substrate ranges from about 0.2 to 3.0, preferably 1.5 to 3.0, percent based on the weight of the substrate.
This invention is also a coffee stain resistant polyamide textile substrate having deposited thereon an effective amount of a composition which imparts coffee stain resistance to the substrate. The composition comprises a copolymer of the second embodiment above. It is expected that the substrate will not yellow on exposure to light when the copolymer has the formula ##STR3## wherein s is 2 to 50 and t is 2 to 50, X is phenyl, and Z is either --O-- or --O--CH 2 --CH 2 --O--.
This invention is also a method to apply a polymer, preferably a stain blocker, to the surface of polyamide fibers comprising preparing an aqueous dispersion of charged microfine polymer beads and causing said beads to contact said fiber by electrostatic attraction to coat said fiber, then heating the coated fiber. The electrostatic attraction is the result of the phenomena of substances acquiring a surface electrical charge when contacted by a polar (e.g., aqueous) medium (see Shaw, Introduction to Colloid and Surface Chemistry, pp. 148-159 (3d ed. 1983)). It is preferred that the aqueous dispersion be prepared by dissolving the polymer into a water-soluble solvent, preferably an organic solvent such as acetone, tetrahydrofuran and/or an alcohol, most preferably acetone, followed by injecting the solution into water, whereby the polymer precipitates to form microfine beads which are smaller then about 2 microns. The solvent is then evaporated to leave a dispersion of microfine polymer beads in water. The dispersion has a pH in the range of about 2.0 to 7.0, preferably 2.0 to 3.0. The heating temperature is in the range 70° C. to 200° C., preferably 100° C. to 135° C.
The following terms are defined for use in this specification.
By polyamide is meant nylon 6, nylon 6,6 nylon 4, nylon 12 and the other polymers containing the ##STR4## structure along with the [CH 2 ] x chain. Nylon 6 and 6,6 are preferred.
By textile substrate is meant fiber or yarn which has been typically tufted, woven, or otherwise constructed into fabric suitable for final use in home furnishings, particularly as floor covering or upholstery fabric.
By fiber is meant continuous filament of a running or extremely long length, or cut or otherwise short fiber known as staple. Carpet yarn may be made of multiple continuous filaments or spun staple fiber, both typically pretextured for increased bulk.
DETAILED DESCRIPTION OF THE INVENTION
In the preferred embodiment coffee stain resistance is imparted to a nylon 6 textile substrate, by the hydrolysis product, the half ester, or mixtures thereof, of copolymers made from vinyl ethers and maleic anydride in which the vinyl ether contains an aromatic ring structure. These copolymers can be represented by the formula ##STR5## wherein m is 4 to 100, p is 0.5m to 0.7m, X is a moiety of an aromatic compound effective to improve stain resistance, R is alkyl or hydrogen and Z is either --O-- or --O--CH 2 --CH 2 --O--. X preferably is phenyl, naphthyl or a partially saturated naphthyl-like ring.
The most preferred copolymer is prepared from phenyl vinyl ether and maleic anhydride. These are typically 1:1 alternating copolymers. The hydrolysis product of this copolymer is preferred for resistance to FD&C Red Dye 40 staining, whereas the half ester product, preferably the half isopropyl ester product, of this copolymer is preferred for resistance to hot coffee staining, although each product provides protection against both types of staining. Substrates treated with these most preferred copolymers have the added advantages of not yellowing on exposure to UV light or oxides of nitrogen, and of resistance to dye fading upon exposure to ozone or light.
Alkali metal hydroxides, such as sodium, potassium, and lithium preferably the former, are suitable hydrolyzing agents for making the hydrolysis product. Alcohols, such as the C 1 -C 5 alcohols, preferably isopropyl alcohol, are suitable hydrolyzing agents for making the half ester product of the copolymer.
In the second less preferred embodiment of this invention, coffee stain resistance is imparted to a nylon 6 textile substrate by an aromatic-containing acrylate copolymerized with either acrylic acid or maleic acid. The more preferred copolymers, which can be random or block, made with maleic acid, can be represented by the formula ##STR6## wherein s is 2 to 50 and t is 2 to 50 (this is not necessarily an alternating copolymer), X is a moiety of an aromatic compound effective to improve stain resistance, and Z is either --O-- or --O--CH 2 --CH 2 --O--. X preferably is phenyl, naphthyl, or a partially saturated naphthyl-like ring.
The copolymers of all of the embodiments are readily soluble, even at high concentrations, in water at neutral to alkaline pH; increasing dilution is needed at pH below 6.
The copolymers of this invention can be used as such in treating polyamide textile substrates. They can be applied to dyed, and possibly undyed, polyamide textile substrates. They can be applied to such substrates in the absence or presence of polyfluoroorganic oil-, water-, and/or soil-repellent materials. In the alternative, such a polyfluoroorganic material can be applied to the textile substrate before or after application of the copolymers of this invention thereto. The copolymers can be applied to textile substrates in a variety of ways, e.g. during conventional beck and continuous dyeing procedures. The quantities of the polymers of this invention which are applied to the textile substrate are amounts effective in imparting coffee stain-resistance to the substrate. The amounts can be varied widely; in general, one can use between 0.2 and 3% by weight of them based on the weight of the textile substrate, preferably 1 to 3%, more preferably 1.5 to 3.0%. The copolymers can be applied, as is common in the art, at pHs ranging between 2 and 9.
The copolymers of this invention can also be applied in-place to polyamide carpeting which has already been installed in a dwelling place, office or other locale. They can be applied as a simple aqueous preparation at the levels described above, at temperature described, and at a pH between about 1 and 12, preferably between about 2 and 9. Heating after application is preferred but not necessary for performance. Steam treatment after application does not adversely affect performance.
Staining and test procedures utilized in the Examples were as follows.
TESTING PROTOCOLS
Unless noted otherwise, the fabric samples were a 3.4 g, 2.5 inch wide nylon 6 fabric (plain weave, 12-13 ends/inch x 11-12 picks/inch) woven from Allied Type 1189-7B39/2 ply Superba heatset [at 270° F. with presteam] yarn. The fabric was beck dyed into a 1/25 Standard Depth Neutral Grey Shade using C.I. Acid Orange 156, C.I. Acid Red 361 and C.I. Acid Blue 324. The samples were about 3 to 4 inches long.
A. COFFEE
A brew of coffee was prepared using 20g of Maxwell House Master Blend Auto Drip coffee per 500 mL of water. Thirty milliliters of this coffee solution at 71° C. was dropped from a 12 inch height onto a fabric samples. After one minute the coffee solution was drained and the stain was allowed to remain on the fabric for 4 hours. Then the fabric was rinsed with cold tap water.
1. The coffee stain resistance of early samples was measured by the following technique: A 0-10 scale was used to rate the stain protection, with a score of 0 for a stain similar to stain in a control (no protection) nylon-6 fabric, and a rating of 10 when the stain was not detectable. The rating was done by visual evaluation by the same panel of evaluators.
2. The coffee stain resistance of later samples was measured using a photovolt single filter colorimeter, as follows. The stain protection of the samples was evaluated using the red (R), green (G), and the blue (B) reflected light values measured with a photovolt single filter colorimeter. The RGB values from the stained, tested samples were referenced to those of a stained control and related in a quantitative form to an unstained fabric sample. The RGB data of each sample represented a color response vector in an RGB tridimensional space. The stain value of each sample was computed from the length of each response vector. The vector length was calculated as follows: Length (i) =SquareRoot (Square(R(i)) +Square(G(i)) +Square(B(i)) ) where i was the test sample. The stained control was the darkest sample and was represented by the shortest vector. The maximum length vector was derived from the RGB vector of the unstained sample. The stain protection performance of the same is then given by ##EQU1## The stain protection is reported in percent, for comparison with the unstained, untreated fabric sample (at 100%) and the stained control (at 0%).
B. FD&C RED DYE 40
1. Unsweetened cherry Kool-Aid® (0.14 oz) was dissolved in two quarts of water. Thirty milliliters of this solution was poured on a (2.5 inch piece of nylon-6 fabric weighing 3.4 g) from a 12 inch height. After one minute the Kool-Aid was drained and the stain was allowed to remain on the fabric for 4 hours. Then the stain was removed by rinsing the fabric with cold tap water. FD&C Red Dye 40 stain resistance for samples stained in this manner was measured on a 0-10 scale like Technique 1 for coffee above.
2. Unsweetened cherry Kool-Aid (0.14 oz) was dissolved in two quarts of water. Twenty milliliters of this solution were placed in a vial, and a 3.4 g blue grey nylon-6 flat fabric was immersed in this solution with agitation to achieve wetting of the fabric. The fabric was left in contact with this solution for 1.5 minutes and then it was removed and placed in a beaker. The remaining solution was combined with another 5 mL of Kool-Aid solution and it was poured onto the soaked flat fabric from a 12" height. After one minute, the Kool-Aid solution was drained, and the sample was allowed to stand for 4 hrs. At the end of this period the sample was rinsed with cold water and left to dry. FD&C Red Dye 40 stain resistance for samples stained by this procedure was measured using a photovolt single filter colorimeter, like Technique 2 for coffee, above.
Colorfastness to light (Yellowing) was measured in accordance with AATCC Test Method 16E-1987, at 40 fading units. D. Ozone fastness was measured in accordance with AATCC 129-1985.
E. N02 fastness was measured in accordance with AATCC 164-1987.
F. Application Methods
1. Solvent Application -
A known weight percent of the stain blocker oligomer per weight of fiber (typically 2-4%) was dissolved in 5-10 mL of tetrahydrofuran and diluted to 150 mL with trifluorotoluene. A nylon-6 fabric sample was immersed in half the amount of the above solution, and heated in a steam bath for 15 min. Then the sample was retrieved from the remaining liquid and dried with a hot (40° -90° C.) stream of nitrogen. The remainder of the liquid was mixed with the second half of oligomer solution and this was sprayed over the sample. The treated sample was then dried with a stream of nitrogen, and annealed for 15 min at 105° C.
2. Aqueous Application -
(a) The oligomeric stain blocker was dissolved in water at basic pH (e.g. 8-10) and then brought to acidic pH (2-7) with acetic or sulfamic acid. At acidic pH the stain blocker adsorbs onto nylon 6 with a rate of adsorption depending on the temperature and pH of the dispersion/solution.
(b) A 10% solution of the stain blocker in water can be made using NaOH (0.73 eq. NaOH per vinyl ether unit). This solution can be brought to a pH of between 5.5 and 6.5 and diluted with water typically to a 1.3% Stain Blocker solution. Nylon 6 flat fabric is then impregnated with said solution at 65° -75° C. for 1 to 2 min, to give, after squeezing the fabric between two rollers, a take up of 2.8% stain blocker per weight of fabric. The fabric is then annealed at 250° F. for 15 min.
(c) A dispersion is generated by spraying a solution of 1 g of copolymer in 50 mL of acetone into 50 mL of water. The acetone is evaporated to leave an aqueous dispersion of submicron beads. This dispersion is diluted to 1% with water at a pH of 2.0. One gram of nylon 6 fabric is soaked for about 20 minutes in 20 ml of this suspension at 45° C. and then annealed at 135° C. for 15 minutes.
PREPARATION OF STAIN BLOCKERS
Preparation of Saturated Naphthyl Derived Ring Systems by Hydrogenation:
The reduction of the naphthalene rings to yield 5,6,7,8 tetrahydronaphthalene derivatives was done by low pressure catalytic hydrogenation in methanol. The hydrogenations were carried out with the naphthol, naphthoxyethanol, or naphthyl ethyl derivatives. Except for 2-(2-naphthyl) ethanol, the reduction of the first ring was accomplished using 5% rhodium on carbon catalyst (Rh/C), 60 psi H 2 , 60° C., until complete reduction of the unsubstituted ring was observed by gas chromatography (GC). To hydrogenate the 5,6,7,8 position of 2-(2-naphthyl) ethanol it was necessary to use palladium on carbon catalyst (Pd/C), since rhodium is not active enough.
Preparation of Vinyl Ether Derived Stain Blockers
Except for phenyl vinyl ether, the vinyl ether monomers were prepared either by reaction of the appropriate alcohol with 2-chloroethyl vinyl ether or by transvinylation using palladium acetate phenanthroline catalyst. These methods are presented below. Phenyl vinyl ether was prepared according to the method of Mizuno et al., Synthesis, 1979, 688, by dehydrohalogenation of phenyl-2-bromoethyl ether with aqueous sodium hydroxide by utilizing the phase-transfer ability of tetra-n-butylammonium hydrogen sulfate. The reaction is exothermic and is completed within 1.5 hours at ambient temperature.
Preparation of 2-(2-Naphthoxy) Ethyl Vinyl Ether )via reaction with 2-chloroethyl vinyl ether)
Three pounds of 2-naphthol were placed in a three necked round bottom flask equipped with an overhead stirrer and a reflux condenser. One liter of dimethyl sulfoxide was used to dissolve the naphthol and to this solution was slowly added 0.8 lb. of NaOH, while keeping the temperature below 50° C. After the addition of NaOH was completed, 1.1 liters of 2-chloroethyl vinyl ether were added slowly while keeping the temperature at 60° C. The reaction mixture was heated at this temperature for 20 hours (the progress of the reaction was followed by GC). After cooling the reaction product was poured into a polyethylene decantation tank and water was added to separate the product. Toluene was added to dissolve the product, and the toluene phase was washed several times with enough 5% NaOH to remove any residual naphthol starting material. The toluene layer was dried with anhydrous Na 2 SO 4 filtered and the toluene was evaporated. The product was identified by GC. A product yield of approximately 85% based on the weight of the naphthol starting material was obtained with this procedure.
Preparation of (2-Naphthyl) Methyl Vinyl Ether (via transvinylation catalyst)
a. Preparation of Palladium Acetate Phenanthroline Catalyst
Pd(II) acetate, 3.36 g (0.01497 moles), was dissolved in 375 mL of benzene, and filtered through fluted filter paper giving a brown transparent solution. To this was added, dropwise, under nitrogen, a solution of 2.7 g (0.1498 moles) anhydrous 1,10-phenanthroline in 125 mL of benzene. A yellow precipitate resulted, which was filtered off and washed with benzene to obtain 4.7 g of a pale yellow solid.
b. Vinyl Ether Monomer Preparation
In a three necked round bottom flask equipped with a thermometer, condenser, and magnetic stirrer were added 16 g (0.1 moles) of 2-naphthalene methanol, 200 mL of butyl vinyl ether and 1.0 g of palladium (Pd(II)) acetate phenanthroline. The reaction mixture was stirred overnight while the reaction progress was followed by GC. When conversion was 85% or higher, the catalyst was removed with activated charcoal. After separating the catalyst by filtering, the butanol and the unreacted butyl vinyl ether were removed by distillation. The vinyl ether product was purified to 97%+ purity by column chromatography on silica gel using hexane/2% ethyl ether.
Vinyl Ether and Maleic Anhydride Copolymer
The copolymers were prepared in 1,2-dichloroethane, using VAZO 67, 2,2,'-azo-bis-(2 methylbutyronitrile) as initiator, and butanethiol or dodecanethiol as the chain transfer agent to control the degree of polymerization.
Preparation of 2-(2-Naphthoxy) Ethyl Vinyl Ether/Maleic Anhydride Copolymer
2-(2-naphthoxy) ethyl vinyl ether (20.0 g, 0.09524 moles), and maleic anhydride (9.33 g, 0.09524 moles) were dissolved in (155 mL) dichloroethane. The solution was placed in a three necked round bottom flask equipped with a thermometer, a condenser, and nitrogen inlet, and purged with nitrogen for half an hour. Then VAZO 67 (0.61 g, 0.003175 moles) and butanethiol (4.08 mL, 0.93799 moles) were added under nitrogen. The polymerization was carried out at 60° C. for 24 hrs or longer until complete monomer conversion. The polymer was isolated by precipitation in hexane.
Preparation of the Isopropyl Monester of 2-(2-Naphthoxy) Ethyl Vinyl Ether/Maleic Anhydride Copolymer
The anhydride copolymer was dissolved in the minimum amount of tetrahydrofuran. The solution was diluted with toluene, and then isopropanol. The solution was refluxed, until 50-75% of the monoester was formed as determined by infra red (IR) or by carbon 13 nuclear magnetic resonance ( 13 C NMR). The copolymer was recovered by precipitation. The average molecular weight of the copolymer was determined by gel permeation chromatography (GPC).
Acrylate Derived Stain Blockers
The acrylate monomers were prepared by the reaction of the corresponding alcohols with acryloyl chloride as described below.
Preparation of 2-(2-Naphthoxy) Ethanol
The reaction set-up consisted of a three necked round bottom flask, equipped with a thermometer, condenser and a mechanical stirrer, and a dropping funnel. 2-Naphthol, 100 g (0.6936 moles), was dissolved in 60 mL of dimethyl sulfoxide. Sodium hydroxide, 27.7 g (0.6936 moles), was carefully added to the solution. Then 2-chloroethanol, 61.4 g (0.7629 moles), was slowly added, keeping the reaction temperature at 80 C. The reaction was followed by GC. After 80% conversion was achieved, the reaction was worked-up by adding toluene and extracting the unreacted naphthol with 5% aqueous NaOH. The product was then recrystallized in ethanol or distilled under vacuum (70-80% yield).
Preparation of 2-(2-Naphthoxy) Ethyl Acrylate
In a round flask provided with an overhead stirrer, condenser, and addition funnel 2-(2-naphthoxy) ethanol, 40.0 g (0.2127 moles), was added and the system was swept with nitrogen for 15 minutes, then a dry tube was placed in the outlet of the condenser to prevent moisture from getting into the system. Acryloyl chloride, 21.1 g (0.2340 moles), was added dropwise, and the solution was stirred overnight. The solution was worked-up by extracting the HCl formed with water, evaporating the solvent and purifying the product by distillation (84% yield). Further purification by column chromatography was necessary.
The polymerization was carried out under nitrogen, using 1,2-dichloroethane as the solvent, VAZO 67 as the initiator, and butanethiol as a chain transfer agent to control the degree of polymerization. A typical polymerization is described below.
Homopolymerization of 2-(2-Naphthoxy) Ethyl Acrylate
The monomer, 3.0 g, was dissolved in 1,2 dichloroethane. The system was purged with nitrogen, and VAZO 67 , 30.6 mg (0.0002065 moles), and butanethiol, 0.53 mL (0.004942 moles), were added. The polymerization was carried out at 60° C. until total monomer conversion. The polymer was precipitated in hexane.
Preparation of 2-(2-Naphthoxy) Ethyl Acrylate/Maleic Diacid Copolymer
2-(2-Naphthoxy) ethyl acrylate (3.0 g, 0.01239 moles) and maleic anhydride (1.21 g, 0.01239 moles) were dissolved in 20.7 mL of dichloroethane. The solution was placed in a 100 mL three-necked round bottom flask equipped with a thermometer, condenser, stirring bar, and nitrogen inlet, and purged with nitrogen for half an hour. Then VAZO 67 (0.159 g, 0.000826 moles) and butanethiol (0.028 g, 0.000309 moles) were added under nitrogen. The polymerization was carried out at 60° C. for 24 hours until complete monomer conversion. The dichloroethane was then evaporated, a brown gummy solid was redissolved in tetrahydrofuran (15 mL) and added dropwise to 75 mL of ethanol to give once filtered, 1.86 g of a light brown solid. 1.20 g of this light brown solid, 20 mL of tetrahydrofuran, 3.0 mL H 2 O, and 0.10 g of p-toluene sulfonic acid were added to a 50 mL single necked round bottom flask and the reaction was run at 80° C. with stirring overnight. IR analysis then indicated that only about 20% of the anhydride remained, and the main peak came at 1700 CM -1 characteristic of a carboxylic acid group. The brownish solution was precipitated in 100 mL of hexane to give 1.5 g of a light brown solid (30-40% yield). The average molecular weight of the copolymer was determined by GPC.
EXAMPLE 1
With reference to Table 1, the copolymers listed were applied to a nylon 6 fabric sample by the solvent application method. These copolymers, which were each about 50-75% isopropyl monoester, had a number average molecular weight of about 5000-10,000. The fabric samples were tested for coffee stain resistance by Technique 1 set forth above, the 0-10 stain resistance by rating wherein 0 represents no protection and 10 represents complete protection. Data are presented in Table 1.
EXAMPLE 2
With reference to Table 2, the copolymers listed were applied to a nylon 6 fabric sample by the solvent application method. These copolymers, which were each 50-75% isopropyl monoester, had the number average molecular weights set forth in Table 2. The fabric samples were tested for coffee stain resistance by Technique 1 previously set forth. Data are presented in Table 2.
EXAMPLE 3
With reference to Table 4, the copolymers listed were applied to a nylon 6 fabric sample by the solvent application method. These copolymers, which were each 50-75% isopropyl monoester, had a number average molecular weight of about 5000-10,000. These fabric samples were then tested for lightfastness using AATCC method l6E-1987. Data are presented in Table 4.
EXAMPLE 4
With reference to Table 5, the copolymers listed were applied to a nylon 6 fabric sample via the solvent application method, modified as follows: the copolymer/trifluorotoluene solution was sprayed onto the sample to achieve about 3% of the copolymer based on the weight of the substrate. These copolymers, which were each about 50-75% isopropyl monoester, had a number average molecular weight of about 5,000-10,000. The fabric samples were tested for coffee stain resistance by Technique 2 set forth above, using a photovolt single filter colorimeter.
EXAMPLE 5
Best Mode
Fifteen grams of phenyl vinyl ether/ maleic isopropyl monoester copolymer were added to 119 g of water to make a slurry. Then 15.6 g of a 10% NaOH aqueous solution were added, and the mixture was heated to 75° C. for 20 min. The solution was then allowed to cool to room temperature. A 10 % w/w clear golden solution was obtained and the pH of this solution was around 6.0 to 6.5. This copolymer solution was diluted with water to a 1.32% w/v and the pH was adjusted to 5.8 with sulfamic acid. A grey nylon 6 flat fabric (3.4 g), was immersed in 50 g of the 1.32% weight by volume (w/v) aqueous copolymer solution at 70.C for 3 minutes. The flat fabric was wrung out to a 237 % weight pick-up, which resulted in a 3.1 % polymer add-on per weight of fiber (wof). The flat fabric was then heated at 220° -250° F. for 20 minutes.
A sufficient number of fabric samples were prepared to test separately for resistance to coffee staining, resistance to FD&C Red Dye 40 staining, lightfastness, ozone fastness and resistance to the action of oxides of nitrogen. Data are presented in Tables 6 and 7 (sample 22).
For comparison, untreated control samples were stained with coffee and cherry Kool-Aid, respectively. These control samples and a blank are presented in Table 6.
EXAMPLE 6 (COMPARATIVE)
Twelve and a half grams of deionized water were added to 20 g of a styrene maleic anhydride copolymer (commercially available from Aldrich Chem. Co., Catalog No. 20060-3, 1600 weight average molecular weight, white solid, 1:1 ratio styrene to maleic anhydride) in a 250 ml three-necked round bottom flask, and stirred with an overhead stirrer to make a white slurry. Then 22.5 g of a 30 % NaOH aqueous solution were added dropwise so as not to exceed 40° C. temperature in the flask. The flask was then heated to 70° C. and stirred for three hours. Then 11.6 g of deionized water were added to make a 30% concentrated solution. This solution was then allowed to cool to room temperature. A viscous, light yellow solution was obtained, and the pH of the solution was about 9.9. This copolymer solution was diluted with water to a 1.32% w/v and the pH was adjusted with acetic acid to 5. A blue-grey nylon-6 flat fabric (3.4 g, about 4 inches ×2.5 inches) was immersed in 50 g of 1.32% w/v aqueous copolymer solution at about 85° C. for 5 minutes. The solution container was shaken once every minute. The flat fabric was wrung out to achieve about a 2.9 % polymer add-on per weight of fabric. The sample was dried at about 200F. for 25 minutes, without rinsing first since this adversely affected performance. A sufficient number of samples were prepared to test for coffee stain protection and FD&C Red Dye 40° stain protection using a photovolt single filter colorimeter. Data are presented in Table 6.
EXAMPLE 7
5.4 g phenyl vinyl ether/maleic anhydride were added to 13.2 g of water (in a 250 mL 3-necked round bottom flask) to make a slurry. Then 8.44 g of a 20% NaOH aqueous solution were added, and the mixture was heated to 75° C. for 2.5 hours with stirring by overhead stirrer. The solution was then allowed to cool to room temperature. A viscous, orange solution was obtained with a pH of about 9. This copolymer solution was diluted with water to a 1.32 % w/v, and the pH was adjusted to 5 using a 5 % acetic acid/water solution. Fabric samples were made as in Example 5 except that the polymer add-on per weight of fiber was about 3 %. Samples were tested for stain resistance (%) to coffee and FD&C Red Dye 40, respectively, using a photovolt single filter colorimeter. Data are presented in Table 6 (Sample 24).
EXAMPLE 8
Example 7 was repeated, except that the pH was adjusted to 5.8. Data are presented in Table 6 (Sample 25).
EXAMPLE 9
0.1 g of phenyl vinyl ether/maleic isopropyl monoester (number average molecular weight 4500) stain blocker was dissolved in 5 mL of 1 % NaOH solution to make a 2% polymer in water solution, which was then diluted to 0.2% polymer in water. This diluted solution was then sprayed, using a thin layer chromatography (TLC) sprayer onto 500 mL of water at pH 2.0 (sulfamic acid), under constant stirring at 40 C while keeping the overall pH at 2.0. This created a dispersion of the polymer in water. 2.5 g of a nylon-6 fabric were immersed in the polymer dispersion at 40° C. for 2 hours. The dispersion was not completely exhausted. The coated fabric was dried in air and annealed at 120° C. for 30 minutes. Coffee stain test, Technique 1, gave a rating of 8.
EXAMPLE 10
A solution of 1 gram of phenyl vinyl ether/ maleic isopropyl monoester copolymer in 50 mL of acetone was sprayed into 50 mL of water. The acetone was evaporated to leave an aqueous dispersion of submicron beads. This dispersion was diluted to 1% with water at pH 2. One gram of nylon-6 fabric was soaked in 20 mL of this suspension at 45° C. for 20 minutes and then annealed at 135° C. for 15 minutes. The resulting fabric sample showed good protection against coffee staining according to Technique 1.
EXAMPLES 11-12
Example 7 was repeated in Example 11 with the following modifications: The copolymer solution in which the fabric was immersed was at 75° C. rather than 70° C., and the flat fabric was heated at 90° C. for 20 minutes. The fabric was tested for stain resistance (%) to FD&C Red Dye 40 using a photovolt single filter colorimeter--protection was 99.3%.
Example 12 was a repeat of Example 11 except that the fabric was allowed to air dry at room temperature, about 25° C., i.e., there was not heating step. Protection level was 92.0%.
This set of examples demonstrates that the hydrolysis product of phenyl vinyl ether/maleic anhydride copolymer can be applied to an installed carpet to yield excellent protection against FD&C Red Dye 40 stains. The product can be applied by soaking the installed carpet with the product followed by air drying of the carpet. There is no need to provide extra heat in drying the carpet or as an added treatment to achieve good stain protection.
DISCUSSION
Applicants have found that coffee stain protection can be achieved when the vinyl ether monomer of the vinyl ether/maleic anhydride copolymer contains an aromatic ring (phenoxy, naphthyl or a partially saturated naphthyl-like ring). With reference to Table 1, it can be seen that straight chain hydrocarbons (Samples 3 and 2) provide little to no protection, but when the side chains include an aromatic ring system (Samples 4-6, 8-9, 11), there is good protection.
Applicants have also found that the aromatic ring of the copolymer must be bound to an oxygen as part of the chain connecting the ring to the polymer backbone. See samples 22-25 in Table 6 which demonstrate the superior coffee stain resistance of Samples 22,24 and 25 versus Sample 23. Also see Table 5, Samples 4 and 21.
The importance of an oxygen being part of the chain binding the aromatic ring of the copolymer to the polymer backbone is also seen with FD&C Red Dye 40 Stains. See Table 6 wherein Comparative Sample 23 does not have such an oxygen and has inferior performance to both of Samples 22 and 24 of the present invention.
Coffee stain protection was tested with coffee at a temperature of 71° C., i.e., with hot coffee. The samples in Table 3 demonstrate that having a glass transition temperature and/or a melt temperature greater than 71° C. is not required of the copolymer in order to achieve hot coffee stain protection.
While vinyl ether/maleic anhydride copolymers are considered the best mode of practicing this invention, it was also found that acrylate/maleic anhydride copolymers offer coffee stain protection; homoacrylates, however, did not protect against coffee stains. See Table 2. And although the protection offered by the copolymer of Sample 17 is only 4, this sample is included as part of the present invention since it was not an optimized structure; the monomers' ratio could probably be varied to provide improved performance.
The naphthoxy containing copolymers yellowed upon exposure to ultra violet (UV) light even when the oxygen in the naphthoxy or 5,6,7,8-tetrahydro-2-naphthoxy ring of the above mentioned copolymers was etherified. See Table 4. A phenoxy ring linked from the phenoxy oxygen (phenyl-0-) to the vinyl ether oxygen (0-CH=CH2 by a CH2CH2 group : (phenyl-0-CH2CH2-OCH=CH2) gave stain protection against coffee, although much lower than the protection given by the same naphthoxy arrangement (compare Samples 9 and 4 in Tables 1 and 4); however it had the advantage that it did not yellow. This was surprising because the 5,6,7,8 tetrahydro-2-naphthoxy ethyl vinyl ether/maleic isopropyl monoester (Sample 6, Table 4), which could be considered an etherified dialkyl substituted phenoxy derivative, did yellow upon exposure to UV light.
A preferred stain blocker was obtained when a phenyl ring was linked directly to the vinyl ether oxygen. This arrangement with the oxygen from the phenoxy ring being the vinyl ether oxygen, gave the best combination of coffee stain protection with no yellowing upon exposure to UV light or oxides of nitrogen. See Tables 4, 5, 6 and 7.
The half ester, namely the half isopropyl ester of the vinyl ether/maleic anhydride copolymers gave better coffee stain protection than the hydrolysis product (see Table 6). This is in contrast with FD&C Red Dye 40 protection where both the half ester and the hydrolysis product of the anhydride copolymer gave excellent protection. Furthermore, each can be applied to achieve this protection as easily as soaking the carpet in an aqueous solution thereof, steaming the carpet if desired, and allowing to air dry.
It is possible that optimum performance against both types of stains may be obtained with a combination of the half ester and the hydrolysis product.
Effect of Molecular Weight on Performance
Using the compound of the invention, 2-(1-naphthoxy) ethyl vinyl ether/maleic isopropyl monoester copolymer, (50-75% monoester), of the following molecular weights, stain protection was evaluated as shown:
______________________________________Mol. Wt. × 10.sup.3 Stain Protection*______________________________________less than 4.5 7 4.5 9-10 7.9 8-9 23 7-8______________________________________ *by Technique 1 for Coffee Stains, above.
It is believed that the other compounds of this invention will show very similar results.
TABLE 1______________________________________ Coffee StainSample Copolymer Protection______________________________________1 Control 02 Decyl vinyl ether/Maleic 0(comparative) anhydride3 Docosyl vinyl ether/Maleic 4-5(comparative) isopropyl monoester4 2-(2-Naphthoxy) ethyl vinyl 9-10 ether/Maleic isopropyl monoester5 2-(1-Naphthoxy) ethyl vinyl 9-10 ether/Maleic isopropyl monoester6 2-(5,6,7,8-Tetrahydro-2- 8-9 naphthoxy) ethyl vinyl ether/Maleic isopropyl monoester7 2-(2-Decahydro naphthoxy) 2(comparative) ethyl vinyl ether/Maleic isopropyl monoester8 Phenyl vinyl ether/Maleic 9-10 isopropyl monoester9 2-(Phenoxy) ethyl vinyl 8-9 ether/Maleic isopropyl monoester10 2-(4-Cyclohexyl phenoxy) 6-5 ethyl vinyl ether/Maleic isopropyl monoester11 2-(2-Naphthyl) ethyl vinyl 7-8 ether/Maleic isopropyl monoester12 (2-Naphthyl) methyl vinyl 0(comparative) ether/Maleic isopropyl monoester______________________________________
TABLE 2______________________________________ Coffee Stain Mol. Pro-Sample Copolymer Wt. tection______________________________________13 2-(2-Naphthoxy) ethyl vinyl 4.8 × 10.sup.3 9-10 ether/Maleic isopropyl monoester14 Poly 2-(2-Naphthoxy) ethyl 2.9 × 10.sup.3 2(comparative) acrylate15 Poly 2-(2-Naphthoxy) ethyl 7.7 × 10.sup.3 2(comparative) acrylate16 Poly 2-(2-Naphthoxy) ethyl 14 × 10.sup.3 2(comparative) acrylate17 2-(2-Naphthoxy) ethyl 6 × 10.sup.3 4 acrylate/Acrylic acid18 2-(2-Naphthoxy) ethyl 6 × 10.sup.3 7-8 acrylate/Maleic acid______________________________________
TABLE 3______________________________________ CoffeeSam- Stainple Copolymer T.sub.g.sup.1 (°C.) T.sub.m.sup.2 (°C.) Protection______________________________________6 2-(5,6,7,8, 98 -- 8-9Tetrahydro-2-naphthoxy) ethylvinyl ether/Maleicisopropyl monoester4 2-(2-Naphthoxy) ethyl 50 -- 9-10vinyl ether/Maleicisopropyl monoester10 2-(4-Cyclohexyl- 60 126 6-5phenoxy) ethyl vinylether/Maleic isopropylmonoester______________________________________ .sup.1 Glass transition temperature. .sup.2 Melt temperature.
TABLE 4______________________________________ Yellowing (40Samples Copolymer AATCC Fading Units)______________________________________8 Phenyl vinyl ether/Maleic No yellowing isopropyl monoester9 2-(Phenoxy) ethyl vinyl No yellowing ether/Maleic isopropyl monoester4 2-(2-Naphthoxy) ethyl vinyl Yellowing ether/Maleic isopropyl monoester11 2-(2-Naphthyl) ethyl vinyl Yellowing ether/Maleic isopropyl monoester6 2-(5,6,7,8-Tetrahydro-2- Yellowing naphthoxy) ethyl vinyl ether/Maleic isopropyl monoester19 2-(4-Methyl-2-naphthoxy) Yellowing ethyl vinyl ether/Maleic isopropyl monoester20 2-(5,6,7,8-Tetrahydro-2- Yellowing naphthyl) ethyl vinyl ether/Maleic isopropyl monoester______________________________________
TABLE 5______________________________________ Coffee Stain Protection (%) Technique 2 DetergentSample Copolymer Water Rinse Rinse*______________________________________4 2-(2-Naphthoxy ethyl 55.8 74.3 vinyl ether)/Maleic isopropyl monoester21 2-(1-Naphthyl ethyl 33.5 -- vinyl ether)/Maleic isopropyl monoester8 Phenyl vinyl ether/Maleic 64.2 89.4 isopropyl monoester9 Phenoxy ethyl vinyl ether/ 54.2 -- Maleic isopropyl monoester______________________________________ *5 minute wash with AllIn-One detergent solution (7.5 g/l) at 60° C.
TABLE 6______________________________________ Coffee Stain FD & C Red Protection (%) Dye No. Water Detergent 40 Protec-Sample Copolymer Rinse.sup.1 Rinse.sup.2 tion (%)______________________________________Blank.sup.3 -- 100 -- 100Coffee -- 0 -- --StainedControlCherry -- -- -- 0Kool-AidStainedControl22 Phenyl vinyl 69 90 93 ether/Maleic isopropyl monoester 23* Styrene/Maleic 18.3 -- 77.9 acid.sup.424 Phenyl vinyl 32.7 -- 99.3 ether/Maleic acid.sup.525 Phenyl vinyl 21.1 -- -- ether/Maleic acid.sup.6______________________________________ *Comparative .sup.1 As set forth in Coffee Testing Protocol. .sup.2 Five minute wash with Allin-one detergent solution 7.5 g/l at 60° C. .sup.3 The blank was an untreated, unstained sample. It is given a value of 100% for protection since it is what a sample with 100% protection would look like. .sup.4 Hydrolysis product of the anhydride copolymer, number average molecular weight about 1600. .sup.5 Hydrolysis product of the anhydride copolymer, aqueous application at pH 5. .sup.6 Hydrolysis product of the anhydride copolymer, aqueous application at pH 5.8.
TABLE 7______________________________________ Gray Scale Rating* Oxides of Ozone Nitrogen Lightfastness.sup.1 Fastness.sup.3 FastnessSample Copolymer (40 SFU.sup.2) (3 cycles) (1 cycle).sup.4______________________________________Control -- 3 1 322 Phenyl vinyl 4 3-4 3 ether/Maleic isopropyl monoester______________________________________ .sup.1 AATCC 16E1987. .sup.2 AATCC Standard fading unit. .sup.3 AATCC 1291985. .sup.4 AATCC 1641987. *AATC Evaluation Procedure 1
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A method to impart coffee stain resistance to polyamide fibers such as those found in textile substrates (e.g., carpets). The method includes preparing an aqueous dispersion of charged microfine beads of either (i) a copolymer selected from the group consisting of a hydrolyzed aromatic-containing vinyl ether maleic anhydride copolymer, a half ester of an aromatic-containing vinyl ether maleic anhydride copolymer, and mixtures thereof, or (ii) an aromatic-containing acrylate copolymerized with an acid selected from the group consisting of acrylic acid and maleic acid, immersing the polyamide fiber in the aqueous dispersion so that the beads contact and coat the fiber via an electrostatic attraction. The aqueous dispersion is prepared by dissolving the polymer into a water-soluble solvent to form a solution, injecting the solution into water, and evaporating the solvent.
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BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The present invention relates to an improved manufacturing semiconductor device, and, in particular, to a method and apparatus for depositing dielectrics on a semiconductor substrate. Still more particularly, the present invention relates to a method and apparatus for depositing and processing low dielectric aerogel films on a semiconductor substrate.
[0003] 2. Description of the Related Art
[0004] Semiconductor devices are widely used in integrated circuits to create microprocessors and other devices for use in products, such as computers, cellular phones, televisions, and automobiles. These integrated circuits typically contain transistors on a single silicon chip to perform various functions and to store data.
[0005] Integrated circuits have continued to shrink in size and increase in complexity with each new generation of devices. As a result, integrated circuits increasingly require very close spacing of interconnect lines. Many integrated circuit designs now include multiple levels of metalization to interconnect the various circuits on the device. The closer spacing of these interconnect lines increases capacitance between adjacent lines. As a consequence, as the device geometry shrinks and densities increase capacitance interference or cross talk between adjacent lines becomes an increasing problem (cross talk is the same as capacitive coupling). It is desirable to shrink the size of the integrated circuits. One reason for decreasing the size is this cross talk effects both limits of achievable speed and degrades the noise margin used to ensure proper operation of the device.
[0006] One way to diminish the power consumption and cross talk effects in integrated circuits is to decrease the dielectric constant of the insulator or dielectric separating the conductors in the lines. The most common semiconductor dielectric is silicon dioxide, which has a dielectric constant (k) of about 3.9. In contrast, air has a dielectric constant of just over 1.0. As a result, it becomes more desirable to use lower dielectric materials to offset this problem.
[0007] Many of the materials used for producing ultra-low-k dielectric insulators for use in integrated circuits require very specific processing constraints, which are not easily achievable. For example, dielectric layers having porous structure have been employed because it has been recognized that porous dielectric layers having a porosity of generally greater than 50% and in many cases greater than 75% may provide a low dielectric constant insulation for decreasing unwanted capacitive coupling in semiconductor devices. Manufacture of these dielectrics, however, have been difficult because of problems associated with shrinkage during drying of dielectrics. Therefore, it would be advantageous to have an improved method and apparatus for depositing a low-k dielectric material on a semiconductor substrate.
SUMMARY OF THE INVENTION
[0008] The present invention provides a method and apparatus for forming a dielectric layer. A silica precursor solution is deposited onto the surface of a substrate. This solution is spread over the surface of the substrate by spinning the substrate. Thereafter, a catalyst is introduced into the substrate by introducing the catalyst through a filter that causes the catalyst to deposit uniformly on the solution and be distributed homogeneously within the silica precursor solution. The solution is aged and dried using a carrier gas in which the carrier gas is used to place a positive pressure on the solvent within the pores.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The novel features believed characteristic of the invention are set forth in the appended claims. The invention itself however, as well as a preferred mode of use, further objects and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
[0010] FIGS. 1 A- 1 B are cross-sections of a semiconductor substrate with a dielectric, depicted in accordance with a preferred embodiment of the present invention;
[0011] [0011]FIG. 2 is a dielectric processing apparatus depicted in accordance with a preferred embodiment of the present invention; and
[0012] [0012]FIG. 3 is a flowchart of a process used to create aerogels depicted in accordance with a preferred embodiment of the present invention.
DETAILED DESCRIPTION
[0013] The processes, steps, and structures described below do not form a complete process flow for manufacturing integrated circuits. The present invention can be practiced in conjunction with integrated circuit fabrication techniques currently used in the art, and only so much of the commonly practiced process steps are included as necessary for an understanding of the present invention. The figures represent cross sections of a portion of an integrated circuit during fabrication and are not drawn to scale, but instead are drawn so as to illustrate important features of the invention.
[0014] With reference now to FIGS. 1 A- 1 B, cross-sections of a semiconductor substrate with a dielectric, is depicted in accordance with a preferred embodiment of the present invention. In this example, substrate 100 is a silicon substrate including conductors 102 and 104 . These conductors are typically separated by a gap 106 of a predetermined width, typically a fraction of a micron. The width and height ratios illustrated in FIGS. 1A and 1B are not to scale. In FIG. 1A, substrate 100 has a precursor silica layer 108 in a wet or liquid form. Precursor silica layer 108 in this example is a tetraethylorthosilicate (TEOS) layer. Although the depicted example employs the use of TEOS, other types of silica precursors may be used in accordance with the preferred embodiment of the present invention. For example, a tetramethylorthosilicate (TMOS) is an example of another silica precursor solution that may be used to form a dielectric layer in accordance with the preferred embodiment of the present invention.
[0015] These dielectric layers that are formed from precursor silica layer 108 include a number of pores when processed. In FIG. 1B, film 110 includes pores 112 - 120 , also referred to as capillaries. Acid catalyzed hydrolysis causes the polymer to form chains of silica with alcohol contained (i.e., ethanol) within pores 112 - 120 . In drying precursor silica layer 108 , the present invention provides an apparatus to control the drying of TEOS layer 108 to maintain the capillary pressure within the pores to prevent the pores from collapsing.
[0016] The equation for this process in the depicted example is as follows: nSi(OR) 4 →n(SiO 2 .)+ROH. The TEOS stock may take the form of an Si(OR) 4 where R is an ethanol. TEOS layer 108 is deposited on substrate 100 to form an aerogel dielectric layer. The TEOS is a precursor solution for forming aerogel. This aerogel film also may be placed on other substrates other than semiconductor substrates. For example, without limitation, the substrate may be that for a miniaturized chemical sensor, thermal isolation structures, and thermal isolation layers, including thermal isolation structures of infrared detectors.
[0017] Substrate 100 may include common substrates for semiconductor devices, such as silicon, germanium, and gallium arsenide. After precursor silica layer 108 has been deposited onto substrate 100 , the solvent is evaporated from precursor silica layer 108 to form film 110 .
[0018] The present invention provides a method and apparatus for creating a low-k dielectric material. As used herein, a low-k dielectric is a material with a dielectric constant less than 2 . A catalyst is introduced into the chamber through a distribution mechanism to aid the formation of the porous silica dielectric layer. A catalyst, such as, for example, anhydrous HF may be introduced into the chamber through a distribution mechanism that allows for uniform distribution of the HF gas across the substrate prior to drying of the substrate. The present invention employs an apparatus that provides for controlling the pressure as well as the gasses or vapors introduced into the system. A closed cup system is provided to control the pressure of a gas, such as nitrogen and water vapor, during the creation of a low-k dielectric on a substrate. In this example, nitrogen acts as a carrier gas. Of course, other types of carrier gases may be used depending on the available gases and other processing parameters. The amount of nitrogen may be adjusted with respect to the amount of water vapor to maintain capillary pressure within the capillary and pores formed in the dielectric. A higher nitrogen to vapor ratio is employed as the film dries in accordance with a preferred embodiment of the present invention.
[0019] The pores created by the highly branched polymers behave as capillaries filled with a solvent byproduct, such as ethanol from the TEOS. As part of the process of creating an aerogel, it is desirable to minimize capillary forces while drying the film to prevent the pores from collapsing. An aerogel is a porous dielectric material that is 90% air within the dielectric structure. The processes of the present invention include injecting a gas mixture, such as nitrogen and water vapor, or some other solvent vapor, to control the vapor pressure during the drying phase. The nitrogen gas flow into the chamber may be increased while other gasses are decreased to allow the film to dry while retaining its porosity. Although the depicted examples include the use of nitrogen as a carrier gas, other carrier gases may be used in accordance with a preferred embodiment of the present invention.
[0020] With reference now to FIG. 2, a dielectric processing apparatus is depicted in accordance with a preferred embodiment of the present invention. Closed cup apparatus 200 includes a housing 202 with chamber 204 in which a substrate may be placed through gate or window 206 . A chuck 208 is located within chamber 204 on which a substrate 210 is shown. In the depicted example, substrate 210 is a silicon semiconductor wafer. Of course, substrate 210 may be any substrate on which a dielectric, such as that of the present invention, is to be deposited and processed. Chuck 208 is connected to spindle 212 , which is also coupled to motor 214 . Motor 214 causes chuck 208 to spin in direction 216 . In the depicted examples, the spin rate may be from about 1500 revolutions per minute (rpm) to about 5000 rpm depending on the desired film thickness. The spin may be performed from about 5 to about 10 seconds to form the film on the wafer.
[0021] A material dispense line 218 is present, which is used to dispense a TEOS solution onto wafer 210 . A vapor line 220 provides various gases or vapors to dispense head 222 for introduction to chamber 204 via mesh vapor distribution unit 224 . In this example, vapor line 220 is used to provide the catalyst or the carrier gas in accordance with the preferred embodiment of the present invention. Mesh vapor distribution unit 224 provides for an even distribution of the catalyst onto the surface of the substrate, and for a consequent homogeneous distribution of the catalyst within the silica precursor solution.
[0022] Substrate 210 is transported to chuck 208 through a variety of tracks through gate 206 , after which the chamber closes. The pressure within chamber 204 is controlled by introducing various vapors or gases through dispense head 222 into housing 202 of chamber 204 . In accordance with a preferred embodiment of the present invention, a vapor introduced into chamber 204 is a mixture of nitrogen gas and water vapor in which nitrogen is the carrier gas. This vapor is distributed uniformly by using mesh vapor distribution unit 224 . In the depicted example, the mesh may be that of Teflon. Teflon is a registered trademark of BI duPont de Nemouris and company. Teflon is an example of a polytetrafluoroethylene (PTFE), which is inert to virtually all chemicals and considered a slippery material. Further, the silicon precursor solution to be dispensed onto wafer 210 typically requires the addition of a catalyst, such as, dilute hydrofluoric acid (HF) or ammonium fluoride before the TEOS solution has hydrolyzed. These additions may be required to provide a catalyst to form the silicon matrix of an aerogel. In accordance with a preferred embodiment of the present invention, these catalysts are introduced into the TEOS solution through mesh vapor distribution unit 222 . A homogeneous distribution of these catalysts within the silicon precursor solution is provided by mesh vapor distribution unit 222 .
[0023] This homogeneous distribution within the silica precursor solution results in a more uniformed dielectric layer being manufactured in accordance with the preferred embodiment of the present invention. In such an instance, anhydrous HF may be sent through vapor line 220 into dispense head 222 and mesh vapor distribution unit 224 into cavity 204 . Other catalysts that can be used include, for example, Ammonium fluoride, HCL, and HNO 3 . Ammonium fluoride is a base catalyst, while HCL and HNO 3 is an acid catalyst. Of course, other base and acid catalyst may be employed. In this instance, the vapor line 220 should be compatible with the solvents being used.
[0024] The drying portion of the process is important to the nanostructure within the film developed on wafer 210 . A nanostructure is a physical structure on an atomic level; how atoms are organized to form crystalline or amorphous material in this case. In the depicted examples, the aerogel was illustrated as being formed from a silica precursor solution. Aerogels may be created from a number of different types of materials. For example, organic sol-gels and other silica gels may be used to create an aerogel. Organic sol-gels include resorcihol-formaldehyde and melamine-formaldehyde. Other silica gels include hydrosilsesquioxane, as well as silica-titania complexes. In this example, the nanostructure retains porosity. The nanostructure may be controlled by adjusting the amount of water vapor and nitrogen into the chamber. A higher nitrogen to water vapor ratio may be introduced as the film dries. Similarly, the nitrogen line also may be temperature controlled to allow temperature adjustment within chamber 204 of housing 202 . Closed cup apparatus 200 may be implemented using available spin on glass processing equipment with a few modifications. For example, closed cup apparatus 200 may be modified or designed to include mesh vapor distribution unit 224 .
[0025] The formation of the aerogel in closed cup apparatus 200 is desired to be such that the dielectric properties are preserved. In particular, the dielectric constant should be minimized while increasing the porosity of an aerogel layer. As a TEOS stock solution is catalyzed, the silicon in the TEOS begins to polymerize forming long branched molecules. Dilute HF may be titrated into the TEOS as a catalyst for this process. The uniformity of the dielectric film is dependent upon how the branching takes place when the HF is introduced into the system.
[0026] With closed cup apparatus 200 of the present invention, an anhydrous HF gas is injected through mesh vapor distribution unit 224 , which is designed to evenly distribute the HF gas across the wafer. As a result, the properties of the dielectric film formed are more uniform. These properties include, for example, the density and the dielectric constant of the film. In addition, this process also improves the adhesion of the dielectric film formed because less stress will occur with a homogeneous nanostructure.
[0027] With reference now to FIG. 3, a flowchart of a process used to create aerogels is depicted in accordance with a preferred embodiment of the present invention. The process begins by stabilizing the vapor pressure within the processing chamber (step 300 ). Thereafter, the stock material is deposited onto the substrate (step 302 ). The stock material in the depicted example is a stock TEOS solution. This stock solution may be an organic solution, such as a polyamide or an inorganic stock solution, such as a TEOS solution. This material is dispensed onto the substrate wafer under the stabilized vapor pressure in the processing chamber. Thereafter, the material is spun (step 304 ). The spinning that takes place is similar to that used for spin on glass.
[0028] Next, the material is aged and dried (step 306 ). This aging and drying may include typical steps used to age and dry aerogels. Thereafter, the substrate is annealed (step 308 ). The annealing is used for thermal stabilization. Typically, low-k dielectric materials require an annealing step for thermal stabilization. This particular step does not take place within the chamber. Instead, the substrate may be sent to a hotplate or oven used for baking films and semiconductors. The substrate would exit the chamber after the age and dry cycle in step 306 has completed and be transported for an annealing process.
[0029] Different gas flow settings, temperature, and process times may be used in closed cup apparatus 200 to achieve the desired dielectric film properties. A typical range for the vapor pressure (P v /P o ) that will maintain optimal pore size is 0.7 to 0.95. This correlates to the capillary pressure 40 Mpa to 100 Mpa. The pressure may vary with the solvent vapor, which is introduced into the gas mixture. Others solvents may be used in the solvent vapor include, for example, water, methanol, IPA, and formaldehyde.
[0030] The spin on and drying part of the process typically will occur within a time period of two minutes in accordance with a preferred embodiment of the present invention. The nominal dielectric constant of such a film will have a dielectric constant value of k<1.7. Typical low-k materials range from about 2.0 to about 3.0.
[0031] The following is an example of the materials, steps, and processing parameters used to create a dielectric layer in accordance with a preferred embodiment of the present invention: mix 1 mol of TEOS, about 4 to about 20 mols of water containing dilute catalyst (i.e., 0.2% HF). The catalyst introduced into the TEOS is introduced through a vapor distribution unit, such as, mesh vapor distribution unit 224 of FIG. 2 for a period of time of about 5 second in this example. After mixing these ingredients the hydrolysis begins to increase as the pH changes in response to the introduction of the catalyst. No additional additives are needed to change the viscosity. The gelation changes the viscosity as hydrolysis takes place in this example. Storage conditions for these materials prior to mixing should be at about 15° C. to about 20° C. to maintain the stability of the solution until it is used. Temperature changes to the solutions are not required for depositing the solution for use on a wafer.
[0032] The wafer then would be spun at a speed of about 1500 revolutions per minute RPM) to 5000 RPM, depending on the film thickness for about 5-10 seconds. The processing parameters during spin on of the solution would be at ambient pressure temperatures and pressures.
[0033] During and after deposition and spinning, a nitrogen gas and water vapor mixture is introduced into the processing chamber at a pressure of 40-100 pascals (Mpa) with this pressure being reduced to ambient pressure during the drying phase, after the pressure has been maintained with nitrogen only the solvents are no longer being used to minimize capillary force.
[0034] The description of the preferred embodiment of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. Aerogels may be created from a number of materials. For example, organic sol-gels include resorcinol-formaldehyde and melamine-formaldehyde. Other silica gels include hydrosilsesquioxane, as well as silica-titania complexes. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
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A method and apparatus for forming a dielectric layer. A dielectric precursor solution is deposited onto a surface of a substrate. The substrate is spun to spread the dielectric precursor solution over the surface of the substrate. A catalyst is introduced through a filter, wherein the filter causes a substantially homogenous distribution of the catalyst within the substrate, wherein a dielectric layer forms containing pores and wherein a solvent is contained in the pores. The solution is dried to form the dielectric layer using a carrier gas after introducing the catalyst, wherein the carrier gas places a positive pressure within the pores while removing the solvent to form a low-k dielectric layer.
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FIELD OF THE INVENTION
The present invention relates to new peptides, a method for the preparation of said peptides and a pharmaceutical preparation containing said peptides. The peptides according to the present invention are excellent as immunomodulating agents.
BACKGROUND OF THE INVENTION
There has been a longfelt need for new safe immunomodulatory agents in the treatment of many different diseases including malignant diseases, autoimmune diseases and asthma/allergy. Present immunomodulatory agents such as Cyclosporin A and steroids, are very potent immunosuppressive agents but also present severe side effects in a dose dependent manner. New immunomodulatory agents with higher specificity for the immune system, showing less side effects will be of great benefit in the treatment of diseases with a pathological immune response as an important component in the disease process.
PRIOR ART
Signalling between cells are to a major extent mediated by oligo- or polypeptide principles, including cytokines, neuropeptides and hormones. One possible way such a signal can be transmitted may involve oxidoreductase activity mediated by thiol-disulfide interaction of cysteine residues. This type of action can induce conformational changes of proteins which ultimately may result in a signal to the cell nuclei. Thus redox systems, based on oxidised or reduced cysteines, play important roles in initiating, maintaining and/or downregulating inflammatory responses. Redox systems that are characterized today are the thioredoxin (TR)/thioredoxin reductase (TRR) system (Holmgren et al, 1989, J.Biol.Chem, 264, 13963) and similar systems like the glutaredoxin/glutathione reductase (Bushweller et al., 1992, Biochemistry, 31, 9288) and the protein disulfide isomerase (PDI) systems (Noiva and Lennarz, 1992, J.Biol.Chem., 267, 3553). The TR/TRR system and related redox systems are potent regulators of different known immunological and inflammatory parameters, like IL-2R α-chain expression (Espinoz-Adelgado et al, 1992, J.Immunol., 149, 2961), modulation of expression of IFN-γ activity (Deiss and Kimchi, 1991, Science, 252, 117), differentiation and effector function of lymphocytes (Yodoi and Uchiyama, 1992, Immunol. Today 13, 405-411), regulation of eosinophil effector functions (Balcewics et al, 1991, J. Immunol., 147, 2170), activation of glucocorticoid receptor (Grippo et al, 1985, J.Biol.Chem. 260, 93-97) and modulation of immune response during pregnancy (Clarke et al, 1991, J.Reprod.Fert., 93, 525).
The active site of TR includes a sequence with a -Cys-Gly-Pro-Cys- motif. Selected virus proteins, e.g. gene products coded from X regions of human T-cell leukaemia viruses (Shimotohno et al, 1985, P.N.A.S. 82, 302-306) and human immunoregulatory proteins may have cysteine-containing sequences which are homologous to such a -Cys-Gly-Pro-Cys- motif. We have considered that these proteins may either express oxidoreductase activity or can be substrates for such an activity or possibly act as inhibitors of such an activity.
Previously peptides based on the cysteine-rich TR active site sequence mentioned above have been produced and shown to exhibit biological activities similar to the native protein Another example of a cysteine-containing peptide with thioredoxin-like activity was obtained from hFSH-β-(81-95) (Grasso et al, 1991, Molecular and Cellular Endocrinology 78, 163).
Analogs of thymic humoral factor γ2 (ThF-γ2) for use as immunomodulatory agents in pharmaceutical compositions are described in WO, A1, 9501182 (12.01.95). This document discloses two cyclic analogs; Leu-Glu-Cys-Gly-Pro-Cys-Phe-Leu (SEQ ID NO: 34) and Leu-Cys-Ala-Gly-Pro-Cys-Phe-Leu (SEQ ID NO: 35);, which are excluded from the present invention. However, this document does not reveal the active importance of cysteine-containing sequences.
We have prepared peptides with cysteine-containing motifs, selected from virus structural proteins e.g. retroviral transmembraneous protein p15E, and human proteins involved in regulation of inflammnation, e.g. TGF-β. Peptides were then modified to get optimal immuno-regulatory properties.
OUTLINE OF THE INVENTION
We have now surprisingly found a novel group of peptides which are excellent as immunomodulators. The peptides according to the present invention comprise 4-15 amino acids and can be described by the general formula (I):
A-X-Y-Cys-Z-B (I)
wherein
X is selected from Gly, Ala, Ile, Asp, Thr, Ser, Arg or Trp;
Y is selected from Pro, pipecolic acid (hereinafter called Pec) or Ile:
Z is selected from Ile, Phe, Pro, Ala, Tyr or Gly;
A is H, a protecting group, an amino acid in either L- or D-form with or without protected sidechain-functionality and/or N-terminal protection or an amino acid sequence with or without protected sidechain-functionalities and/or N-terminal protection;
B is OH, NH 2 , a protecting group, an amino acid in either L- or D-form with or without protected sidechain-functionality and ending with a C-terminal amide, a free carboxyl or a protecting group or an amino acid sequence with or without protected sidechain-functionalities and ending with a C-terminal amide, a free carboxyl or a protecting group; and provided that the following sequences are excluded from the formula (I):
Leu-Glu-Cys-Gly-Pro-Cys-Phe-Leu (SEQ ID NO: 34),
Leu-Cys-Ala-Gly-Pro-Cys-Phe-Leu (SEQ ID NO: 35),
Tyr-Ile-Pro-Cys-Phe-Pro-Ser-Ser-Leu-Lys-Arg-Leu-Leu-Ile (SEQ ID NO: 36),
Tyr-Ile-Pro-Cys-Phe-Pro-Ser-Ser-Leu-Lys-Arg-Leu-Ile (SEQ ID NO: 37),
Ser-Gly-Pro-Cys-Pro-Lys-Asp-Gly-Gln-Pro-Ser (SEQ ID NO: 38) and
Thr-Pro-Pro-Thr-Pro-Cys-Pro-Ser (SEQ ID NO: 39).
The length of A and B can vary, as long as the criteria concerning length and possible amino acids or other substituents are fulfilled.
The amino acids according to the present invention can be both naturally occurring amino acids and non-naturally, synthetic amino acids or amino acid analogues.
Examples of protecting groups for A are a variety of carbamates and amides of which the following protecting groups are preferred: acetyl (Ac), 9-fluorenylmethyl carbamate (Fmoc), 1-methyl-1-(4-biphenylyl)ethyl carbamate (Bpoc), trityl (Trt), allyl carbamate (Alloc) and t-butyl carbamate (Boc).
Especially preferred protecting groups for A are acetyl (Ac), 9-fluorenylmethyl carbamate (Fmoc) and t-butyl carbamate (Boc).
Examples of protecting groups for B are a variety of esters such as C 1 -C 6 alkyl, allyl, adamantyl, benzyl, and t-butyl.
Also within the scope of the present invention are homodimers according to the formulae (II), (III) and (IV) ##STR1## i.e. homodimers of the peptides of the formula (I) according to the invention.
Also within the scope of the present invention are pharmaceutically acceptable salts of peptides of the formulae (I), (II), (III) and (IV).
Peptides of the formula (I) containing several cysteine residues may exist both in an oxidized and in a reduced form. The oxidized form may contain intramolecular disulfide bonds resulting in oxidized monomers or intermolecular disulfides resulting in both head to head and head to tail dimers of the peptides of formula (I).
Preferred peptides according to the present invention are peptides of the formulae (I), (II), (III) and (IV) wherein
X is Gly, Y is Pro and Z is Ile;
X is Gly, Y is Pro and Z is Gly;
X is Ala, Y is Pro and Z is Ala;
X is Ile, Y is Pro and Z is Tyr;
X is Ala, Y is Pro and Z is Ile;
X is Arg, Y is Pro and Z is Ile;
X is Ile, Y is Pro and Z is Ile;
X is Asp, Y is Pro and Z is Ile;
X is Trp, Y is Pro and Z is Ile;
X is Trp, Y is Pro and Z is Gly;
X is Gly, Y is Ile and Z is Ile;
X is Gly, Y is Pec and Z is Ile;
X is Thr, Y is Pro and Z is Tyr;
X is Thr, Y is Pec and Z is Phe;
X is Ala, Y is Pro and Z is Phe;
X is Ser, Y is Pro and Z is Phe;
X is Gly, Y is Pro and Z is Pro; or
X is Gly, Y is Pro and Z is Tyr;
wherein A and B can be varied as defined above; and
provided that the following sequence is excluded from the formulae (I), (II), (III) and (IV): Ser-Gly-Pro-Cys-Pro-Lys-Asp-Gly-Gln-Pro-Ser (SEQ ID NO: 38).
Preferred peptides according to the invention are
H-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 1);
Fmoc-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 1);
H-Gly-Pro-Cys-Gly-OH (SEQ ID NO: 2);
H-Ala-Pro-Cys-Ala-OH (SEQ ID NO: 3);
H-Ile-Pro-Cys-Tyr-OH (SEQ ID NO: 4);
H-Trp-Pro-Cys-Gly-OH (SEQ ID NO: 32);
H-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 5);
H-Gly-Pro-Cys-Ile-Leu-Asn-NH 2 (SEQ ID NO: 6);
H-Gly-Pro-Cys-Ile-Leu-Asn-Arg-OH (SEQ ID NO: 7);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 8);
H-Leu-Leu-D-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 8);
H-Leu-Leu-Phe-Ala-Pro-Cys-Ile-OH (SEQ ID NO: 9);
H-Leu-Leu-Phe-Arg-Pro-Cys-Ile-OH (SEQ ID NO: 10);
H-Leu-Leu-Phe-Ile-Pro-Cys-Ile-OH (SEQ ID NO: 11);
H-Leu-Leu-Phe-Asp-Pro-Cys-Ile-OH (SEQ ID NO: 12);
H-Leu-Leu-Phe-Trp-Pro-Cys-Ile-OH (SEQ ID NO: 13);
H-Leu-Leu-Phe-Gly-Ile-Cys-Ile-OH (SEQ ID NO: 14);
H-Leu-Leu-Phe-Gly-Pec-Cys-Ile-OH (SEQ ID NO: 15);
H-Ala-Val-Trp-Thr-Pro-Cys-Tyr-OH (SEQ ID NO: 33);
H-Tyr-Phe-Tyr-Thr-Pec-Cys-Phe-OH (SEQ ID NO: 16);
H-Phe-Val-Met-Ala-Pro-Cys-Phe-OH (SEQ ID NO: 17);
H-Leu-Leu-Tyr-Ser-Pro-Cys-Phe-OH (SEQ ID NO: 18);
H-Ile-Ser-Gly-Pro-Cys-Pro-Lys-OH (SEQ ID NO: 19);
H-Phe-Leu-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 20);
H-Leu-Phe-Gly-Pro-Cys-Ile-Leu-NH 2 (SEQ ID NO: 21);
H-Glu-Lys-Gly-Pro-Cys-Tyr-Arg-OH (SEQ ID NO: 22);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-OH (SEQ ID NO: 23);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-NH 2 (SEQ ID NO: 24);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-OAllyl (SEQ ID NO: 23);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-NH 2 (SEQ ID NO: 25);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg-OH (SEQ ID NO: 26);
H-Phe-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-NH 2 (SEQ ID NO: 27);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg-Leu-Met-Glu-NH 2 (SEQ ID NO: 28);
H-Phe-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg-Leu-Met-Glu-NH 2 (SEQ ID NO: 29);
Fmoc-Phe-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg-Leu-Met-Glu-NH 2 (SEQ ID NO: 29);
H-Phe-Cys-Leu-Gly-Pro-Cys-Pro-OH (SEQ ID NO: 30); ##STR2##
Especially preferred peptides according to the invention are peptides of the formulae (I), (II), (III) and (IV) wherein
X is Gly, Y is Pro and Z is Ile;
X is Ala, Y is Pro and Z is Ala;
X is Ala, Y is Pro and Z is Ile;
X is Asp, Y is Pro and Z is Ile;
X is Gly, Y is Ile and Z is Ile;
X is Gly, Y is Pec and Z is Ile;
X is Ser, Y is Pro and Z is Phe; or
X is Gly, Y is Pro and Z is Pro;
wherein A and B can be varied as defined above; and
provided that the following sequence is excluded from the formulae (I), (II), (III) and (IV): Ser-Gly-Pro-Cys-Pro-Lys-Asp-Gly-Gln-Pro-Ser (SEQ ID NO: 38).
Especially preferred peptides according to the invention are the peptides
H-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 1);
H-Ala-Pro-Cys-Ala-OH (SEQ ID NO: 3);
H-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 5);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 8);
H-Leu-Leu-Phe-Ala-Pro-Cys-Ile-OH (SEQ ID NO: 9);
H-Leu-Leu-Phe-Asp-Pro-Cys-Ile-OH (SEQ ID NO: 12);
H-Leu-Leu-Phe-Gly-Ile-Cys-Ile-OH (SEQ ID NO: 14);
H-Leu-Leu-Phe-Gly-Pec-Cys-Ile-OH (SEQ ID NO: 15);
H-Leu-Leu-Tyr-Ser-Pro-Cys-Phe-OH (SEQ ID NO: 18);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-OH (SEQ ID NO: 23); ##STR3##
The most preferred peptides according to the invention are peptides of the formulae (I), (II), (III) and (IV) wherein
X is Gly, Y is Pro and Z is Ile,
X is Ala, Y is Pro and Z is Ile;
X is Asp, Y is Pro and Z is Ile;
X is Ser, Y is Pro and Z is Phe; or
X is Gly, Y is Pro and Z is Pro;
wherein A and B can be varied as defined above; and
provided that the following sequence is excluded from the formulae (I), (II), (III) and (IV): Ser-Gly-Pro-Cys-Pro-Lys-Asp-Gly-Gln-Pro-Ser (SEQ ID NO: 38).
The most preferred peptides according to the invention are the peptides
H-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 1);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 8);
H-Leu-Leu-Phe-Ala-Pro-Cys-Ile-OH (SEQ ID NO: 9);
H-Leu-Leu-Phe-Asp-Pro-Cys-Ile-OH (SEQ ID NO: 12);
H-Leu-Leu-Tyr-Ser-Pro-Cys-Phe-OH (SEQ ID NO: 18);
H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-OH (SEQ ID NO: 23); ##STR4##
We have now surprisingly found that peptides of the formulae (I), (II), (III) and (IV) are excellent as immunomodulators, thus having either immunostimulating or immunoinhibitory effect. The invention thus provides peptides with advantageous properties for the treatment of diseases where an anergy of the immune response or an aberrant immune response or an ineffective host defence can be suspected. Such diseases include chronic bronchitis, where a reduction of the rate of exacerbations has previously been reported with immune response modifiers such as Biostim (Radermecker, M. et al. Int. J. Immunopharmac. 10, 913-917, 1988, Scheffer, J. et al. Arzneim Forsch/Drug Res: 41, 815-820, 1991), Ribomunyl and BronchoVaxom (Paupe, J. Respiration 58, 150-154, 1991) as well as with N-acetylcysteine (See Bergstrand, H. et al J. Free Radic. Biol. Med. 2, 119-127, 1986).
Such diseases also include certain forms of malignant diseases. Thus, numerous research institutes round the world aim at finding ways of stimulating the immune response in patients with various forms of malignant diseases and numerous reviews in the literature deal with this approach (Stevenson, F. K. FASEB J 5: 2250-2257, 1991; Melief, C. J. M. Advances in Cancer Research 58: 143-75, 1992, Chen, J. et al., Immunology Today 14:10, 483-86, 1993). To mention one example patients with intracranial tumours (gliomas) exhibit a profound decrease in immunity possibly due to a defect in the secretion of IL-2 as well as the expression of IL-2 receptors in T cells from these patients (Roszman, T. et al. Immunology Today 12, 370-374, 1991). Moreover, a significant adjuvant effect in immunotherapy of melanoma and colon carcinoma has been documented for the immunostimulator Levamisole (Van Wauwe, J. and Janssen, P. A. J: Int J. Immunopharmac 13, 3-9, 1991) and immunotherapy with IL-2 in vivo or treatment of patients lymphokine activated killer cells with IL-2 ex vivo has caused the regression of cancer in selected patients (Rosenberg, S. A. Immunology Today 9, 58-62, 1988). The malignant diseases where the peptides of the formulae (I), (II), (III) and (IV) can be expected to have advantageous effects include tumours of mesenchymal origin such as sarcomas like fibrosarcoma, myxosarcoma, liposarcoma, chondrosarcoma, osteogenic sarcoma or chordosarcoma, sarcomas like angiosarcoma, endotheliosarcoma, lymphangiosarcoma, synoviosarcoma or mesotheliosarcoma, leukemias and lymphomas like granulocytic leukemia, monocytic leukemia, lymphocytic leukemia, malignant lymphoma, plasmocytoma, reticulum cell sarcoma or Hodgkins disease, sarcomas like leiomysarcoma or rhabdomysarcoma, tumours of epithelial origin (Carcinomas) like squamous cell carcinoma, basal cell carcinoma, sweat gland carcinoma, sebaceous gland carcinoma, adenocarcinoma, papillary carcinoma, papillary adenocarcinoma, cystadenocarcinoma, medullary carcinoma, undifferentiated carcinoma, bronchogenic carcinoma, melanoma, renal cell carcinoma, hepatoma-liver cell carcinoma, bile duct carcinoma-cholangiocarcinoma, papillary carcinoma, transitional cell carcinoma, squamous cell carcinoma, choriocarcinoma, semonoma or embryonal carcinoma, tumours of the central nervous system like glioma, meningoma, medulloblastoma, schwannoma or ependymoma.
Moreover, the peptides according to the present invention also have advantageous properties for the treatment of chronic infections such as herpes, aphtous stomatitis and minimal change syndrome where clinical improvement has previously been reported by treatment with an immunostimulator such as Levamisole as well as other chronic inflammatory diseases in the urinary tract or in ear, nose or throut, which benefit from treatment with immunostimulators such as Biostim, Broncho-Vaxom and Ribomunyl, or at HIV infection or AIDS.
Moreover, an impairment, a defect or an imbalance of the immune response has also been postulated to exist at atopic diseases such as atopic dermatitis, rhinitis and asthma (Katz, D. H. Immunology Rewiews 41, 77-108, 1977). Since theoretical considerations suggest that stimulation of an immune response would possibly be the best way of restoring imbalances and autoimmunity (Varela, F. J. and Coutinho, A. Immunology Today 12, 159-166, 1991), the peptides can also be expected to have advantageous properties for the treatment of asthma, rhinitis, atopic dermatitis and autoimmune diseases like non-obese diabetes, systemic lupus erythematosus, sclerodermia, Sjogren's syndrome, dermatomyositis or multiple sclerosis, rheumatoid arthritis and possibly psoriasis.
Moreover, the peptides according to the present invention, due to their immune modulating properties, may have advantageous properties as adjuvants in various forms of vaccine preparations. Due to their immune modulating properties, the peptides can also be expected to have favourable properties in inhibiting rejection of organs/transplants.
Finally, the peptides according to the present invention can be expected to have advantageous properties in the treatment of artheriosclerosis, whether or not they will influence a putative inflammatory process in this condition (Hansson. G. K. et al. Proc. Nat. Acad. Sci. USA 88, 10530, 1991).
The peptides according to the present invention are particulary suitable for treatment of malignancies such as melanoma, mammary carcinoma, gastrointestinal carcinoma, glioma, bladder carcinoma and squamous cell carcinoma of the neck and head region; infections such as chronic bronchitis, hepatitis, post-infectious anergy and aquired immune deficiencies such as AIDS; posttraumatic immunological anergy; and purported autoimmune diseases such as rheumatoid arthritis, multiple sclerosis, artheriosclerosis and psoriasis.
Preparation
The peptides according to the present invention may be prepared using the standard solid phase sequential coupling technique utilizing an automatic peptide synthesizer (see for example: Jones, J. The Chemical Synthesis of Peptides, pp 132-156, first edition, Oxford University Press, 1991 and R. Epton (ed) Innovation and Perspectives in Solid Phase Synthesis, SPCC (UK) Ltd, 1990). The preparation starts form the C-terminal amino acid which can be obtained grafted to a methylbenzhydrylamine, benzhydrylamine or chloromethylated resin or other suitable solid support. The other amino acids are grafted step by step, after having protected the side chains thereof. In this coupling method the α-amino groups of the amino acids are protected either with Fmoc or t-Boc methodology.
Protective groups for the side chains of amino acids are well known in the art. The whole protected peptide is released either from the chloromethylated resin by ammoniolysis to obtain the protected amide, or from the methylbenzhydrylamine or benzhydrylamine resins by acidolysis.
Peptides according to the invention may also be prepared using solution methods, by either stepwise or fragment condensations (see for example: Jones, J. The Chemical Synthesis of Peptides, pp 115-131, first edition, Oxford University Press, 1991). An appropriately alpha aminoprotected amino acid is coupled to an appropriately alpha carboxyl protected amino acid (such protection may not be required depending on the coupling method chosen) using diimides, symmetrical or unsymmetrical anhydrides, or other coupling reagents or techniques known to those skilled in the art. These techniques may be either chemical or enzymatic. The alpha amino and/or alpha carboxyl protecting groups are removed and the next suitably protected amino acid or block of amino acids are coupled to extend the growing peptide. Various combinations of protecting groups and of chemical and/or enzymatic techniques and assembly strategies can be used in each synthesis.
The dimers (peptides of the formulae (II), (III) and (IV)) and peptides containing intramolecular disulfide bonds between cysteine residues may be prepared via general oxidation techniques described by Andreu et al in Methods in Molecular Biology, Peptide Synthesis Protocols vol 35 (Humana Press Inc., Totowa, N.J., 1994) and Ruiz-Gayo et al, 1988, Tetrahedron Letters, 29, 3845-3848, as well as in other reference works known to those skilled in the art. Low-resolution mass spectra and accurate mass determinations were recorded on an Autospec-Q, Fisons Analytical, double focusing sector instrument equiped with a LSIMS interface.
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be described in more detail with the following examples which are not to be construed as limiting the invention.
EXAMPLE 1
Synthesis of H-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 1)
A resin (0.37 g, 0.22 mequiv/g, 81 μmol) consisting of a crosslinked polystyrene backbone grafted with polyethyleneglycol chains, functionalized with the linker p-hydroxymethylphenoxyacetic acid (Sheppard and Williams, 1982, Int. J. Peptide Protein Res., 20, 451-454) and Fmoc-Ile, from Rapp Polymere (Germany) was used for the synthesis. N.sup.α -Fmoc amino acids were from Bachem (Switzerland), and Cys was protected with a triphenylmethyl (Trt) group. DMF was distilled before being used.
The N.sup.α -Fmoc amino acids were coupled to the peptide-resin as 7-aza-1-benzotriazolyl (HOAt) esters (Carpino, 1993, J. Am. Chem. Soc. 115, 4397-4398). These were prepared, in situ, in the peptide synthesizer from the appropriate N.sup.α -Fmoc amino acid (0.32 mmol) and HOAt (65 mg, 0.48 mmol) by addition of DMF (0.5 ml) and a solution of 1,3-diisopropyl-carbodiimide in DMF (0.39 M, 0.8 ml, 0.312 mmol). After 45 min bromophenol blue (Flegel and Sheppard, 1990, J. Chem. Soc., Chem. Commun. 536-538) in DMF (0.15mM, 0.4 ml) was added to the HOAt ester by the synthesizer, and the resulting solution was recirculated through the column. The acylation was monitored (Flegel and Sheppard, 1990, J. Chem. Soc., Chem. Commun. 536-538) using the absorbance of bromophenol blue at 600 nm, and when the coupling was complete the peptide-resin was automatically washed with DMF. Coupling times for different N.sup.α -Fmoc amino acids were approximately 30 min. N.sup.α -Fmoc deprotection of the peptide resin was performed by a flow of 20% piperidine in DMF through the column for 12.5 min, and was monitored (Dryland and Sheppard, 1986, J. Chem. Soc. Perkin Trans. I, 125-137) using the absorbance of the dibenzofulvene-piperidine adduct at 350 nm. After completion of the N.sup.α -Fmoc deprotection the peptide-resin was again washed automatically with DMF.
After completion of the synthesis and cleavage of the N-terminal N.sup.α -Fmoc group, the resin was washed with dichloromethane (5×5 ml) and dried under vacuum. The peptide (40 μmol) was then cleaved from the resin (200 mg), and the amino acid side chains were deprotected, by treatment with trifluoroacetic acid-water-thioanisole-ethanedithiol (87.5:5 5:5:2.5, 20 ml) for 2 h, followed by filtration. Acetic acid (20 ml) was added to the filtrate, the solution was concentrated, and acetic acid (20 ml) was added again before the solution was concentrated. The residue was dissolved in acetic acid-water (4:1, 25 ml) and the solution was freeze dried. The residue was triturated with ether (10 ml) which gave a solid, crude peptide (21 mg) after drying under vacuum.
The peptide was analyzed on a Beckman System Gold HPLC using a Kromasil C-8 column (1000 Å, 4.6×250 mm) and a linear gradient of 0-80% of B in A over 60 min with a flow rate of 1.5 ml/min and detection at 214 nm (solvent systems A: 0.1% aqueous trifluoroacetic acid and B: 0.1% trifluoroacetic acid in acetonitrile). Purification of the crude peptide (21 mg) was performed with the same HPLC system on a 20×250 mm Kromasil C-8 column with a flow rate of 11 ml/min and gave pure a product (8.5 mg, 55%). FAB-MS: 389 (MH + ).
The compound is also listed in table 1.
EXAMPLES 2-33
The peptides according to examples 2-33 were prepared using the same protocol as in example 1.
The compounds are listed in table 1.
EXAMPLE 34 ##STR5##
A solution of the monomer (1.5 mg/ml, in 50 nM phosphate buffer, pH=7.2) containing 5 ppm copper(II)-sulphate was stirred at room temperature for 20 hours. The solution was lyophilized and redissolved in water/acetonitrile (80/20) and purified by reverse phase HPLC using a VYDAC C-18 column (5 μm, 4×250 mm). An aqueous solution containing 0.1% trifluoroacetic acid and 5% acetonitrile was used as a mobile phase. The concentration of acetonitrile was increased linearly to 60% over a time scale of 25 min. The flow rate was 1.5 ml/min and the components were detected with UV at 220 nm. Fractions were collected manually and checked with FAB-MS. Repeated injections were pooled to give a solution of the product which was lyophilized. FAB-MS: 1521 (MH + ).
The compound is listed in table 1.
EXAMPLES 35-37
The peptides according to examples 35-37 were prepared using the same protocol as in example 34.
The compounds are listed in table 1.
EXAMPLE 38
The peptide according to example 38 was prepared using the same protocol as in example 1.
The compound is listed in table 1.
EXAMPLE 39
The peptide according to example 39 was prepared using the same protocol as in example 34-37.
The compounds are listed in table 1.
EXAMPLES 40-41
The peptides according to examples 40-41 were prepared using the same protocol as in example 1.
The compounds are listed in table 1.
EXAMPLE 42 ##STR6##
To prepare the parallel (head to head) homodimer a single peptide chain with an Acm (acetamidomethyl) protecting group on one of the cysteines and with the other cysteine unprotected (H-Phe-Cys-Leu-Gly-Pro-Cys(Acm)-Pro-OH) was synthesized using the same protocol as in example 1. The monomer was dimerized through oxidation of the free cysteines using the same protocol as in example 2. The second disulfide bond was accomplished using the protocol of Ruiz-Gayo (Ruiz-Gayo et al, 1988, Tetrahedron Letters, 29, 3845-3848) in which a onepot deprotection and oxidation of the Acm protected cysteine with iodine in 80% aqueous acetic acid resulted in a crude product which was purified on HPLC.
The compound is listed in table 1.
EXAMPLE 43 ##STR7##
To prepare the antiparallel (head to tail) homodimer the general procedure of Ruiz-Gayo was used (Ruiz-Gayo et al, 1988, Tetrahedron Letters, 29, 3845-3848). Two single peptide chains each with an Acm (acetamidomethyl) protecting group on one of the cysteines and with the other cysteine unprotected (H-Phe-Cys-Leu-Gly-Pro-Cys(Acm)-Pro-OH and H-Phe-Cys(Acm)-Leu-Gly-Pro-Cys-Pro-OH) was synthesized using the same protocol as in example 1. The unprotected cysteines on one of the monomers was activated with dithiopyridine resulting in the S-pyridyl derivative H-Phe-Cys(SPyr)-Leu-Gly-Pro-Cys(Acm)-Pro-OH. This derivative was reacted with the second peptide chain resulting in the first disulfide. The second disulfidebond was accomplished using the same protocol as in example 42 with iodine in 80% aqueous acetic acid which, after purification on HPLC, resulted in the final product.
The compound is listed in table 1.
The following Table 1 lists compounds according to the invention and their identification by FAB-MS spectra.
TABLE 1______________________________________Ex. No. Peptide MH.sup.+ (m/z)______________________________________1 H-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 1) 3892 Fmoc-Gly-Pro-Cys-IIe-OH (SEQ ID NO: 1) 6113 H-Gly-Pro-Cys-Gly-OH (SEQ ID NO: 2) 3334 H-Ala-Pro-Cys-Ala-OH (SEQ ID NO: 3) 3615 H-Ile-Pro-Cys-Tyr-OH (SEQ ID NO: 4) 4956 H-Trp-Pro-Cys-Gly-OH (SEQ ID NO: 32) 4627 H-Phe-Gly-Pro-Cys-Ile-OH (SEQ ID NO: 5) 5378 H-Gly-Pro-Cys-Ile-Leu-Asn-NH.sub.2 calcd: 615.329 (SEQ ID NO: 6) (Exact miss) found: 615.3299 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-OH calcd: 762.422 (SEQ ID NO: 8) (Exact mass) found: 762.41910 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-OH 762 (SEQ ID NO:8)11 H-Leu-Leu-Phe-Ala-Pro-Cys-Ile-OH calcd: 776.438 (SEQ ID NO: 9) (Exact mass) found: 776.43812 H-Leu-Leu-Phe-Arg-Pro-Cys-Ile-OH 861 (SEQ ID NO: 10)13 H-Leu-Leu-Phe-Ile-Pro-Cys-Ile-OH 808 (SEQ ID NO: 11)14 H-Leu-Leu-Phe-Asp-Pro-Cys-Ile-OH 819 (SEQ ID NO: 12)15 H-Leu-Leu-Phe-Trp-Pro-Cys-Ile-OH 891 (SEQ ID NO: 13)16 H-Leu-Leu-Phe-Gly-IIe-Cys-Ile-OH 778 (SEQ ID NO: 14)17 H-Leu-Leu-Phe-Gly-Pec-Cys-Ile-OH calcd: 776.438 (SEQ ID NO: 15) (Exact mass) found: 776.43918 H-Ala-Val-Trp-Thr-Pro-Cys-Tyr-OH 839 (SEQ ID NO: 33)19 H-Tyr-Phe-Tyr-Thr-Pec-Cys-Phe-OH 954 (SEQ ID NO: 16)20 H-Phe-Val-Met-Ala-Pro-Cys-Phe-OH 814 (SEQ ID NO: 17)21 H-Leu-Leu-Tyr-Ser-Pro-Cys-Phe-OH 842 (SEQ ID NO: 18)22 H-Ile-Ser-Gly-Pro-Cys-Pro-Lys-OH calcd: 701.384 (SEQ ID NO: 19) (Exact mass) found: 701.38623 H-Phe-Leu-Phe-Gly-Pro-Cys-Ile-OH 796 (SEQ ID NO: 20)24 H-Leu-Phe-Gly-Pro-Cys-Ile-Leu-NH.sub.2 calcd: 761.438 (SEQ ID NO: 21) (Exact mass) found: 761.43725 H-Glu-Lys-Gly-Pro-Cys-Tyr-Arg-OH 852 (SEQ ID NO: 22)26 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-OH 875 (SEQ ID NO: 23)27 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-NH.sub.2 878 (SEQ ID NO: 24)28 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-OAllyl 915.5 (SEQ ID NO: 23)29 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-NH.sub.2 988 (SEQ ID NO: 25)30 H-Phe-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-NH.sub.2 calcd: (SEQ ID NO: 27) 1022.550 (Exact mass) found: 1022.55131 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg- 1517 Leu-Met-Glu-NH.sub.2 (SEQ ID NO: 28)32 H-Phe-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg- 1552 Leu-Met-Glu-NH.sub.2 (SEQ ID NO: 29)33 Fmoc-Phe-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn- 1776 Arg-Leu-Met-Glu-NH.sub.2 (SEQ ID NO: 29)34 ##STR8## 1521 (homodimer of SEQ ID NO: 8)35 ##STR9## 1682 (homodimer of SEQ ID NO: 18)36 ##STR10## 775 (homodimer of SEQ ID NO: 1)37 ##STR11## 3101 Arg-Leu-Met-Glu-NH.sub.2 Arg-Leu-Met-Glu-NH.sub.2 (homodimer of SEQ ID NO: 29)38 H-Phe-Cys-Leu-Gly-Pro-Cys-Pro-OH 736 (SEQ ID NO: 30)39 ##STR12## 734 (SEQ ID NO: 31)40 H-Gly-Pro-Cys-Ile-Leu-Asn-Arg-OH 772 (SEQ ID NO: 7)41 H-Leu-Leu-Phe-Gly-Pro-Cys-Ile-Leu-Asn-Arg- 1146 OH (SEQ ID NO: 26)42 ##STR13## 1467.7 (head to head homodimer of SEQ ID NO: 30)43 ##STR14## 1468 (head to tail homodimer of SEQ ID NO: 30)______________________________________
Pharmaceutical Preparations
The peptides according to the invention may be administered orally, nasally, rectally, intravenously or by inhalation.
The dosage will depend on the route of administration, the severity of the disease, age and weight of the patient and other factors normally considered by the attending physician, when determining the individual regimen and dosage level as the most appropriate for a particular patient.
The pharmaceutical preparations comprising the peptides according to the invention may conveniently be tablets, pills, capsules, syrups, powders or granules for oral administration sterile parenteral solutions or suspensions for parenteral administration or suppositories for rectal administration.
For the preparation of pharmaceutical preparations containing a peptide according to the present invention in the form of dosage units for oral administration, the active peptide may be admixed with an adjuvant or a carrier, e.g. lactose, saccharose, sorbitol, mannitol, starches such as potato starch, corn starch or amylopectin, cellulose derivatives, a binder such as gelatine or polyvinylpyrrolidone, and a lubricant such as magnesium stearate, calcium stearate, polyethylene glycol, waxes, paraffin, and the like, and then compressed into tablets. If coated tablets are required, the cores, prepared as described above, may be coated with a concentrated sugar solution which may contain e.g. gum arabic, gelatine, talcum, titanium dioxide, and the like. Alternatively, the tablet may be coated with a polymer known to the man skilled in the art, dissolved in a readily volatile organic solvent or mixture of organic solvents. Dyestuffs may be added to these coatings in order to readily distinguish between tablets containing different active substances or different amounts of the active peptides.
For the preparation of soft gelatine capsules, the active substance may be admixed with e.g. a vegetable oil or polyethylene glycol. Hard gelatine capsules may contain granules of the active substance using either the above mentioned excipients for tablets, e.g. lactose, saccharose, sorbitol , mannitol, starches (e.g. potato starch, corn starch or amylopectin), cellulose derivatives or gelatine. Also liquids or semisolids of the drug may be filled into hard gelatine capsules.
Dosage units for rectal application may be solutions or suspensions, or may be prepared in the form of suppositories comprising the active substance in admixture with a neutral fatty base, or gelatin rectal capsules comprising the active substance in admixture with vegetable oil or paraffin oil.
Liquid preparations for oral application may be in the form of syrups or suspensions, for example solutions containing a peptide as herein described as the active substance, the balance being sugar and a mixture of ethanol, water, glycerol and propylene glycol. Optionally such liquid preparations may contain colouring agents, flavouring agents, saccharine and carboxymethylcellulose as a thickening agent or other excipients known to the skilled man in art.
Solutions for parenteral applications by injection may be prepared in an aqueous solution of a water-soluble pharmaceutically acceptable salt of the active substance. These solutions may also contain stabilizing agents and/or buffering agents and may involve the use of surface acting agents to improve solubility. They may conveniently be provided in various dosage unit ampoules.
The compounds according to the invention may be formulated in pressurised metered dose inhalers or dry powder inhalers for oral or nasal inhalation or in liquid formulations for nebulisation. The active substance is micronised or otherwise processed to a particle size suitable for inhalation therapy (mass median diameter <4 μm).
For pressurised metered dose inhalers the micronized substance is suspended in a liquefied propellant or a mixture of liquefied propellants which also can act as solvents and filled into a container which is equipped with a metering valve.
The propellants used may be hydrofluoroalkanes (HFAs) of different compositions. The most frequent used HFAs are tetrafluoroethane (propellant 134a) and heptafluoropropane (propellant 227).
Low concentrations of surfactants such as sorbitan trioleate, lecithin, oleic acid or other suitable substances may be used to improve the physical stability of the preparation. Ethanol or other solvents may be used to increase the solubility of the substances in the propellants.
The active substance may also be delivered through a portable inhaler device suitable for dry powder inhalation. The active substance may be used alone or be combined with a suitable carrier substance such as lactose, mannitol or glucose. Other additives may also be included in the powder formulation by various reasons, such as to increase the stability. The inhaler may be a single dose inhaler with one predispensed dose or a multi dose inhaler in which the dose is created by a metering unit within the inhaler or is delivered from an assembly of predispensed doses.
Biological Studies
The ability of the peptides according to the invention to modulate immune responses can be illustrated by its efficacy in the animal delayed type hypersensitivity (DTH) test in mice.
Both male and female Balb/c mice, obtained from Bomholtsgaard (Denmark), were used with a weight of 18-20 gram.
4-Ethoxymethylene-2-phenyloxazolin-5-one (OXA) (England) and served as the antigen in this test.
The mice were sensitized, Day 0, by epicutaneous application of 150 μl of an absolute ethanol-acetone (3:1) solution containing 3% OXA on the shaved abdomen. Treatment with the peptide or vehicle (0.9% NaCl) was initiated by oral feeding immediately after sensitization an continued once daily until Day 6. Seven days (Day 6) after the sensitization, both ears of all mice were challenged on both sides by topical application of 20 μl 1% OXA dissolved in peanut oil. Ear thickness was measured prior to and 24 or 48 hours after challenge using an Oditest spring calliper. Challenges and measurements were performed under light pentobarbital anaesthesia.
The intensity of the DTH reactions was expressed according to the formula: T t24/48 -T t0 μm units, where t0, t24 and t48 represent the ear thickness before and 24 or 48 hours after challenge respectively, in individual tests (T). The result were expressed as the mean ±S.E.M. The level of significance between means of the groups was obtained by Student's two-tailed t-test. The immunomodulating effect of the peptide is reflected in a significant difference in the increase or decrease in ear thickness as compared to the control.
DISCUSSION
The present invention describes peptides that can be expected to have favorable effects for the treatment of various diseases, affecting the immune system including diseases where an anergy of the immune response, an aberrant immune response or peripheral tolerance to pathogenes or an ineffective host defence by other reasons can be suspected. These type of drugs have an urgent need on the market, instead of or as a complement to present more toxic drugs, for the treatment of many diseases.
______________________________________Abbreviations______________________________________Pec pipecolic acidAc acetylFmoc 9-fluorenylmethyl carbamateBpoc 1-methyl-1-(4-biphenylyl)ethyl carbamateTrt tritylAlloc allyl carbamateBoc t-butyl carbamateFAB-MS fast atom bombardment mass spectrometryDTH delayed type hypersensitivityOXA 4-ethoxymethylene-2-phenyloxazolin-5-oneAcm acetamidomethyl______________________________________
__________________________________________________________________________# SEQUENCE LISTING- (1) GENERAL INFORMATION:- (iii) NUMBER OF SEQUENCES: 39- (2) INFORMATION FOR SEQ ID NO:1:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 4 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:1:- Gly Pro Cys Ile 1- (2) INFORMATION FOR SEQ ID NO:2:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 4 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:2:- Gly Pro Cys Gly 1- (2) INFORMATION FOR SEQ ID NO:3:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 4 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:3:- Ala Pro Cys Ala 1- (2) INFORMATION FOR SEQ ID NO:4:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 4 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:4:- Ile Pro Cys Tyr 1- (2) INFORMATION FOR SEQ ID NO:5:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 5 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:5:- Phe Gly Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:6:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 6 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 6...6#where Xaa at position 6 is "Asn-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:6:- Gly Pro Cys Ile Leu Xaa 1 5- (2) INFORMATION FOR SEQ ID NO:7:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:7:- Gly Pro Cys Ile Leu Asn Arg 1 5- (2) INFORMATION FOR SEQ ID NO:8:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:8:- Leu Leu Phe Gly Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:9:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:9:- Leu Leu Phe Ala Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:10:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:10:- Leu Leu Phe Arg Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:11:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:11:- Leu Leu Phe Ile Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:12:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:12:- Leu Leu Phe Asp Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:13:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:13:- Leu Leu Phe Trp Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:14:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:14:- Leu Leu Phe Gly Ile Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:15:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 5...5#where Xaa at position 5 is "pipecolic acid"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:15:- Leu Leu Phe Gly Xaa Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:16:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 5...5#where Xaa at position 5 is "pipecolic acid"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:16:- Tyr Phe Tyr Thr Xaa Cys Phe 1 5- (2) INFORMATION FOR SEQ ID NO:17:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:17:- Phe Val Met Ala Pro Cys Phe 1 5- (2) INFORMATION FOR SEQ ID NO:18:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:18:- Leu Leu Tyr Ser Pro Cys Phe 1 5- (2) INFORMATION FOR SEQ ID NO:19:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:19:- Ile Ser Gly Pro Cys Pro Lys 1 5- (2) INFORMATION FOR SEQ ID NO:20:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:20:- Phe Leu Phe Gly Pro Cys Ile 1 5- (2) INFORMATION FOR SEQ ID NO:21:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 7...7#where Xaa at position 7 is "Leu-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:21:- Leu Phe Gly Pro Cys Ile Xaa 1 5- (2) INFORMATION FOR SEQ ID NO:22:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:22:- Glu Lys Gly Pro Cys Tyr Arg 1 5- (2) INFORMATION FOR SEQ ID NO:23:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 8 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:23:- Leu Leu Phe Gly Pro Cys Ile Leu 1 5- (2) INFORMATION FOR SEQ ID NO:24:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 8 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 8...8#where Xaa at position 8 is "Leu-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:24:- Leu Leu Phe Gly Pro Cys Ile Xaa 1 5- (2) INFORMATION FOR SEQ ID NO:25:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 9...9#where Xaa at position 9 is "Asn-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:25:- Leu Leu Phe Gly Pro Cys Ile Leu Xaa 1 5- (2) INFORMATION FOR SEQ ID NO:26:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 10 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:26:- Leu Leu Phe Gly Pro Cys Ile Leu Asn Arg# 10- (2) INFORMATION FOR SEQ ID NO:27:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 9 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 9...9#where Xaa at position 9 is "Asn-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:27:- Phe Leu Phe Gly Pro Cys Ile Leu Xaa 1 5- (2) INFORMATION FOR SEQ ID NO:28:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 13 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 13...13#where Xaa at position 13 is "Glu-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:28:- Leu Leu Phe Gly Pro Cys Ile Leu Asn Arg Le - #u Met Xaa# 10- (2) INFORMATION FOR SEQ ID NO:29:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 13 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (ix) FEATURE: (A) NAME/KEY: Other (B) LOCATION: 13...13#where Xaa at position 13 is "Glu-NH2"- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:29:- Phe Leu Phe Gly Pro Cys Ile Leu Asn Arg Le - #u Met Xaa# 10- (2) INFORMATION FOR SEQ ID NO:30:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:30:- Phe Cys Leu Gly Pro Cys Pro 1 5- (2) INFORMATION FOR SEQ ID NO:31:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:31:- Phe Cys Leu Gly Pro Cys Pro 1 5- (2) INFORMATION FOR SEQ ID NO:32:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 4 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:32:- Trp Pro Cys Gly 1- (2) INFORMATION FOR SEQ ID NO:33:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 7 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:33:- Ala Val Trp Thr Pro Cys Tyr 1 5- (2) INFORMATION FOR SEQ ID NO:34:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 8 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:34:- Leu Glu Cys Gly Pro Cys Phe Leu 1 5- (2) INFORMATION FOR SEQ ID NO:35:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 8 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:35:- Leu Cys Ala Gly Pro Cys Phe Leu 1 5- (2) INFORMATION FOR SEQ ID NO:36:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 14 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:36:- Tyr Ile Pro Cys Phe Pro Ser Ser Leu Lys Ar - #g Leu Leu Ile# 10- (2) INFORMATION FOR SEQ ID NO:37:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 13 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:37:- Tyr Ile Pro Cys Phe Pro Ser Ser Leu Lys Ar - #g Leu Ile# 10- (2) INFORMATION FOR SEQ ID NO:38:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 11 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:38:- Ser Gly Pro Cys Pro Lys Asp Gly Gln Pro Se - #r# 10- (2) INFORMATION FOR SEQ ID NO:39:- (i) SEQUENCE CHARACTERISTICS:#acids (A) LENGTH: 8 amino (B) TYPE: amino acid (D) TOPOLOGY: linear- (ii) MOLECULE TYPE: peptide- (xi) SEQUENCE DESCRIPTION: SEQ ID NO:39:- Thr Pro Pro Thr Pro Cys Pro Ser 1 5__________________________________________________________________________
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Novel homodimers that include cysteine-containing peptides having 4-15 amino acid residues can be administered to modulate the immune response in an animal.
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FIELD OF THE INVENTION
The present invention relates generally to software. More specifically, web service generation is described.
BACKGROUND OF THE INVENTION
Complex software systems are often implemented using applications and platforms from a variety of vendors. In many cases, applications may be shared among various locations, hosts, machines, clients, and other system resources using web services. Web services generally rely upon the use of common protocols or formats such as Web Services Description Language (“WSDL”) to enable applications to be used between disparate platforms from multiple vendors. Platforms may include operating systems, software systems, or other foundation layer software that enables the sharing of data among various applications using formats such as XML. However, there are problems when implementing web services and ensuring a common web service may be integrated for use with different platforms.
Web services are built using common protocols (e.g., WSDL) and often requires significant developer time and labor. Integrating web services to function with different platforms often requires substantial, manual access and modification of source code associated with a particular platform or web service. Adding functionality to an existing web service is also problematic in that source code access and modifications are required. The process of adding functionality to a web service or generating a web service with additional functionality requires manual modification, deletion, or addition of source code in order to build the web service.
When building a web service, a client, host, or other machine or system resource will call an existing web service to retrieve a set of definitions to “learn” how to build the web service. Before, during, and after the call, only the functionality that is defined by the web service can be used by the client. New or different functionality can not be implemented without manually modifying the underlying application source code on the web service.
Thus, what is needed is a solution for extending a web service without changing the implementation of the original web service.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments of the invention are disclosed in the following detailed description and the accompanying drawings:
FIG. 1 illustrates an exemplary system for web service generation;
FIG. 2 illustrates an exemplary web service wrapping tool;
FIG. 3 illustrates an exemplary web service;
FIG. 4 illustrates an exemplary process for web service generation;
FIG. 5 illustrates an exemplary process for introspecting an original web service;
FIG. 6 illustrates an exemplary process for building a web service; and
FIG. 7 is a block diagram illustrating an exemplary computer system suitable for web service generation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention can be implemented in numerous ways, including as a process, an apparatus, a system, a composition of matter, a computer readable medium such as a computer readable storage medium or a computer network wherein program instructions are sent over optical or electronic communication links. In this specification, these implementations, or any other form that the invention may take, may be referred to as techniques. In general, the order of the steps of disclosed processes may be altered within the scope of the invention.
A detailed description of one or more embodiments of the invention is provided below along with accompanying figures that illustrate the principles of the invention. The invention is described in connection with such embodiments, but the invention is not limited to any embodiment. The scope of the invention is limited only by the claims and the invention encompasses numerous alternatives, modifications and equivalents. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the invention. These details are provided for the purpose of example and the invention may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the invention has not been described in detail so that the invention is not unnecessarily obscured.
Generating a web service to enable the addition of functionality before, or after an original web service call is described. Layering functionality or software applications on software platforms developed by disparate vendors is an important and valuable objective. Through the use of a web services wrapping tool, functionality may be automatically added to existing web services without requiring manual access or modification of existing source code associated with native web services.
FIG. 1 illustrates an exemplary system for web service generation. Included in system 100 are client 102 , original web service 104 , web service wrapping tool 106 , and web service 108 . In other examples, more or fewer components may be included with system 100 . Here, client 102 calls original web service 104 , requesting a particular web service, which may be implemented as an application or program. Client 102 may also be referred to as an endpoint, which may be implemented using a computer, server, or other end user device. Web service 108 may be built by web service wrapping tool 106 and used by client 102 . Web service 108 may also be referred to as a superset web service in some examples. Superset web services may include functionality provided by native or original web service 104 plus additional functionality added by web service wrapping tool 106 . As an example, web service wrapping tool 106 adds or “wraps” additional or layered functionality onto original web service 104 , providing metadata that enables the additional functionality to be integrated with an original web service interface. This enables a user to continue to work with a familiar user interface such as that provided by original web service 104 , but with additional functionality provided by web service wrapping tool 106 .
In some examples, calls may be made from client 102 to web service 108 using a web service switch (not shown), which provides for code-compatibility between client 102 and web service 108 . In this example, original web service 104 may be introspected by web service wrapping tool 106 to determine a set of definitions that may be used to establish original web service 104 . For example, client 102 requests to establish original web service 104 , which may be a word processing, financial, document management, or other type of software-based system. Client 102 calls web service 108 , which is passed to original web service 104 . When a call is initiated, web service wrapping tool 106 also introspects original web service 104 to build web service 108 , as described below in connection with FIGS. 4-6 . In some examples, web service 108 and original web service 106 may be hosted, installed, and maintained from a single location or multiple locations. In other examples, original web service 104 may be hosted at multiple locations that are able to establish a web service with client 102 . Multiple clients may also call, establish, and use web service 108 . Web service wrapping tool 106 is described in further detail below in connection with FIG. 2 .
FIG. 2 illustrates an exemplary web service wrapping tool. Here, web service wrapping tool 106 includes interpreter 202 , generator 204 , template library 206 , and web service builder 208 . In other examples, more or fewer components may be used. In this example, web service wrapping tool 106 introspects original web service 104 when client 102 calls web service 108 . Interpreter 202 introspects original web service 104 to request and receive information. As an example, information may include common formatting protocols and languages (e.g., WSDL) and a definition or set of definitions that provides details on building original web service 104 . Upon receipt of definitions and other information from original web service 104 (“WSDL data”), web service wrapping tool 106 builds web service 108 .
Functionality is added to web service 108 by web service wrapping tool 106 using WSDL data from original web service 104 and templates 206 . As an example, generator 204 may be used to generate templates. Templates may be automatically or user-defined. Users (e.g., developers, architects, administrators, and other personnel with access to system 100 resources) may develop additional functionality to layer on native web services such as original web service 104 without accessing or modifying associated source code. Instead, web service wrapping tool enables layered functionality to be added to native web services, creating a superset of web services that are made available to client 102 . Once generated, templates are stored in template library 208 , from which a superset of functionality may be built and implemented into web service 108 . In other examples, more or fewer components may be used to implement web service wrapping tool 106 . Web service 108 is described in greater detail below in connection with FIG. 3 .
FIG. 3 illustrates an exemplary web service. As an example, web service 108 includes original web service interface 302 , functionality superset 304 , and wrapping layer 306 . In other examples, more or fewer components may be used to implement web service 108 . Here, web service 108 is built using web service wrapping tool 106 . Included with web service 108 is metadata which allows an original user interface associated with original web service 104 to be used, but enables access to the superset of functionality built by web service wrapping tool 106 and templates 206 . Original web service interface 302 provides, in some examples, a familiar interface to client 102 for web service 108 , but layered functionality is integrated and enabled for use by web service wrapping tool 106 . The superset of functionality is implemented by functionality superset 304 , which is also integrated into web service 108 by wrapping layer 306 . Wrapping layer 306 integrates functionality superset 304 into web service 108 . In other examples, multiple wrapping layers may be used to additional functionality in functionality superset 304 and web service 108 .
FIG. 4 illustrates an exemplary process for web service generation. As an example, web service wrapping tool 106 introspects original web service 104 ( 402 ). In this example, introspection into original web service 104 provides a set of definitions (e.g., WSDL) that enable web service wrapping tool 106 to determine what templates to use and how to generate web service 108 . In other examples, a token is obtained, which enables a session call to original web service 104 . Definitions indicated by original web service 104 are imported by web service wrapping tool 106 ( 404 ). Once imported, web service wrapping tool 108 builds web service 108 ( 406 ).
FIG. 5 illustrates an exemplary process for introspecting an original web service. Web service wrapping tool 106 selects original web service 104 ( 502 ). After selecting original web service 104 , web service wrapping tool 106 points to a particular address indicated by original web service 104 ( 504 ). An address may be a name space or other location from which definitions may be imported by web service wrapping tool 106 . Web service wrapping tool 106 retrieves a set of definitions for the selected service, which may be based on a common formatting language (e.g., WSDL) ( 506 ).
FIG. 6 illustrates an exemplary process for building a web service. Here, web service wrapping tool 106 retrieves templates stored in template library 206 ( FIG. 2 ), which may be used to define functionality for web service 108 ( 602 ). Using templates and earlier-retrieved definitions associated with original web service 104 , web service wrapping tool 106 layers additional functionality on original web service 104 ( 604 ). A user interface associated with original web service 104 is exposed to client 102 ( 606 ). In this example, the original user interface associated with web service 108 may be modified to support the additional or layered functionality added to original web service 104 .
Disparate multiple vendor-developed platforms using a common web service may be modified to implement web service generation, as described above. As an example, the following module illustrates how parameters may be modified to provide for web service generation integration. In some examples, adding a pointer to a particular name space directs web service wrapping tool to namespace for retrieving definitions to build web service 108 with added functionality.
FIG. 7 is a block diagram illustrating an exemplary computer system suitable for web service generation. In some examples, computer system 700 may be used to implement the above-described techniques. Computer system 700 includes a bus 702 or other communication mechanism for communicating information, which interconnects subsystems and devices, such as processor 704 , system memory 706 (e.g., RAM), storage device 708 (e.g., ROM), disk drive 710 (e.g., magnetic or optical), communication interface 712 (e.g., modem or Ethernet card), display 714 (e.g., CRT or LCD), input device 716 (e.g., keyboard), and cursor control 718 (e.g., mouse or trackball).
According to one embodiment of the invention, computer system 700 performs specific operations by processor 704 executing one or more sequences of one or more instructions contained in system memory 706 . Such instructions may be read into system memory 706 from another computer readable medium, such as static storage device 708 or disk drive 710 . In alternative embodiments, hard-wired circuitry may be used in place of or in combination with software instructions to implement the invention.
The term “computer readable medium” refers to any medium that participates in providing instructions to processor 704 for execution. Such a medium may take many forms, including but not limited to, non-volatile media, volatile media, and transmission media. Non-volatile media includes, for example, optical or magnetic disks, such as disk drive 710 . Volatile media includes dynamic memory, such as system memory 706 . Transmission media includes coaxial cables, copper wire, and fiber optics, including wires that comprise bus 702 . Transmission media can also take the form of acoustic or light waves, such as those generated during radio wave and infrared data communications.
Common forms of computer readable media includes, for example, floppy disk, flexible disk, hard disk, magnetic tape, any other magnetic medium, CD-ROM, any other optical medium, punch cards, paper tape, any other physical medium with patterns of holes, RAM, PROM, EPROM, FLASH-EPROM, any other memory chip or cartridge, carrier wave, or any other medium from which a computer can read.
In an embodiment of the invention, execution of the sequences of instructions to practice the invention is performed by a single computer system 700 . According to other embodiments of the invention, two or more computer systems 700 coupled by communication link 720 (e.g., LAN, PSTN, or wireless network) may perform the sequence of instructions to practice the invention in coordination with one another. Computer system 700 may transmit and receive messages, data, and instructions, including program, i.e., application code, through communication link 720 and communication interface 712 . Received program code may be executed by processor 704 as it is received, and/or stored in disk drive 710 , or other non-volatile storage for later execution.
Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed embodiments are illustrative and not restrictive.
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Web service generation is described, including introspecting an original web service, importing a definition associated with the original web service from an address, and building the web service using the definition and a template associated with the definition. A web service wrapping tool is also described, including an interpreter configured to introspect a first web service to retrieve a definition from an address, a generator configured to generate a class for the web service using the definition and a template, and a builder configured to build a second web service using the class generated by the generator. Also described is a system for generating a web service, including a template defining the web service, an interpreter configured to receive and interpret an address to determine a definition associated with the web service, and a generator configured to generate the web service using the definition and the template.
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FIELD OF THE INVENTION
This application relates to devices used in search and rescue of vessels and persons in distress, especially in a marine environment. More particularly, the present application provides a high-intensity pattern of light which incorporates both a radially symmetrical and omni directional/beam electrically-powered, LED light emitting electronic visual distress signaling device (eVDSD) incorporating a GPS transmitter that can interface with the internet using a cell phone adaptor to enable mobile handheld smartphone application (apps) devices to alert and locate vessels and persons in distress. This device can be used as a replacement for pyrotechnic flares utilized in search and rescue of vessels and persons in distress, especially in a marine environment.
BACKGROUND OF THE INVENTION
A vast assortment of signaling lights, including search and rescue devices for the use on vessels in distress, have been used for many years. The use of pyrotechnic flares has been in the past the most commonly used for distress signal devices. Pyrotechnic flares are exceptionally dangerous because they can easily burn the people using them, they can start the vessels on fire if there is a fuel leak and they can even burn under water creating additional problems. Moreover, one cannot overemphasize the potential environmental disaster of flare disposal. Over the next three years it is estimated that approximately 30 million flares will be disposed of improperly or illegally.
The Coast Guard's Research, Development, Test and Evaluation (RDT&E) program is working on more than 80 projects that support Coast Guard requirements across all mission areas. The RDT&E program is comprised of the Office of RDT&E at Coast Guard Headquarters in Washington, D.C., and the Research and Development Center (RDC) at New London, Conn. The RDC is the Coast Guard's sole facility performing applied RDT&E experimentation and demonstrations.
The RDT&E program pursues technologies that provide incremental improvements as well as those with the greatest potential to strategically transform the way the Coast Guard does business.
The RDT&E program leverages partnerships with academia, other government agencies and private industry, to proactively anticipate and research solutions to future technological challenges.
Search and Rescue Distress Notification Methods and Alternatives by the United States Coast Guard reviewed pyrotechnic flares that are commonly used by mariners to signal distress. Flares have drawbacks and present significant storage and disposal problems. The RDC was sought to determine appropriate criteria to evaluate light emitting diode (LED) or other light signals as potential maritime distress signals.
The project team selected a group of LED, flashtube (strobe) and incandescent-based devices to obtain photometric data. An understanding of the physical and perceptual aspects of these devices allowed the project team to select a subset of devices for further evaluation.
Following the lab tests, the project team designed and conducted two field demonstrations. The first demonstration assessed individual devices to determine the most effective signal characteristics based on detectable range, ability to attract attention and ability to distinguish the signal against background lighting. A second demonstration used a subset of the devices to compare the most effective characteristics, head-to-head. Finally, a separate evaluation looked at device ergonomics to help understand the physical aspects of the devices that would make them easier to use.
This project was to determine suitability of potential alternatives to pyrotechnic visual distress signals by.
Evaluating the effectiveness of presently available LED (and other) devices as Visual Distress Signal Devices.
Reviewing functional requirements for visual distress signals.
Investigating and reporting on device characteristics and evaluating them against existing pyrotechnic standards.
Investigating and reporting on “experimental” or “developmental” technologies and evaluating them against pyrotechnic standards.
Determining the most effective light-signal characteristics for alternative Visual Distress Signal Devices.
Additionally, this project will produce recommendations for future non-pyrotechnic requirements and applications. Recommendations will address the feasibility of whether non-pyrotechnic devices could replace pyrotechnics as alert, locate and/or marker devices. Alert and locate specifications for the signal lights differ in the varying peak intensity and the focal height of the LED emitted light, which can be altered by manually adjusting the distance between the LED and the optics.
Numerous innovations for the Visual Distress Signal Device have been provided in the prior art that are described as follows. Even though these innovations may be suitable for the specific individual purposes to which they address, they differ from the present design as hereinafter contrasted.
The following is a summary of those prior art patents most relevant to this application at hand, as well as a description outlining the difference between the features of the Visual Distress Signal Device and the prior art.
U.S. Pat. No. 7,153,002 of Jin Jong Kim describes a lens for light emitting diode (LED) light sources which allows light emitted from an LED light source to exit the lens in a direction perpendicular to a vertical center axis of the lens. The lens of the present invention includes an inner space which is defined in a lens body having both a bottom surface and an upper reflective surface, so that light passing through the inner space is partially reflected by total internal reflection on a portion (selective transmission surface, inner reflective surface, inside reflective surface) of a boundary surface between the inner space and the lens body. Thus, light emitted from an LED light source efficiently exits the lens through a side surface. Accordingly, the lens of the present invention is used in efficient display and illumination of optical systems.
This patent describes a light emitting diode (LED) light sources which allows light emitted from an LED light source to exit the lens in a direction perpendicular to a vertical center axis of the lens used in display and illumination optical systems. This lens does not have the same internal structure and it only describes LED light source exiting the lens in a direction perpendicular to a vertical center axis of the lens. It does not address the value of a portion of the light to be directed vertically or describe the other unique features of the Visual Distress Signal Device.
U.S. Pat. No. 6,679,621 of Robert S. West et al. describes a lens that comprises a bottom surface, a reflecting surface, a first refracting surface obliquely angled with respect to a central axis of the lens, and a second refracting surface extending as a smooth curve from the bottom surface to the first refracting surface. Light entering the lens through the bottom surface and directly incident on the reflecting surface is reflected from the reflecting surface to the first refracting surface and refracted by the first refracting surface to exit the lens in a direction substantially perpendicular to the central axis of the lens. Light entering the lens through the bottom surface and directly incident on the second refracting surface is refracted by the second refracting surface to exit the lens in a direction substantially perpendicular to the central axis of the lens. The lens may be advantageously employed with LEDs, for example, to provide side-emitting light-emitting devices. A lens cap attachable to a lens is also provided.
This patent describes a side-emitting light-emitting lens that does not have the same internal structure and again does not address the value of a portion of the light to be directed vertically or describe the other unique features of the Visual Distress Signal Device.
U.S. Pat. No. 6,607,286 of Robert S. West et al. describes a lens mounted to a light emitting diode package internally redirects light within the lens so that a majority of light is emitted from the lens approximately perpendicular to a package axis of the light emitting diode package. In one embodiment, the light emitted by the light emitting diode package is refracted by a saw tooth portion of the lens and reflected by a total internal reflection portion of the lens.
This patent describes another side-emitting light-emitting lens that does not have the same internal structure and again does not address the value of a portion of the light to be directed vertically or describe the other unique features of the Visual Distress Signal Device.
U.S. Pat. No. 6,598,998 of Robert S. West et al. describes a lens mounted to a light emitting diode package internally redirects light within the lens so that a majority of light is emitted from the lens approximately perpendicular to a package axis of the light emitting diode package. In one embodiment, the light emitted by the light emitting diode package is refracted by a saw tooth portion of the lens and reflected by a total internal reflection portion of the lens.
This patent describes another side-emitting light-emitting lens that does not have the same internal structure and again does not address the value of a portion of the light to be directed vertically or describe the other unique features of the Visual Distress Signal Device.
U.S. Pat. No. 2,492,837 of Eugene Briggs describes an electronically operated signal lights and more particularly to a portable light of the flashing type adapted for emergency or signal use.
This patent describes a self-contained portable flashing light of the gaseous discharge type energized by a battery that has not been designed to be used in a marine environment and does not float in the water.
U.S. Pat. No. 5,034,847 of John E. Brain describes a portable light beacon for use on life rafts and the like that has a long life due to a flashing light allowing the battery to recharge and a water sensing switch that once wet remains on. The light beacon comprises a portable battery power source in a water proof container, a flashing light with watertight electrical connections between the flashing light and the power source, and a fluid sensing switch comprising a fluid absorbent composition positioned between two terminals with circuitry to activate the flashing light when an electrical conductive fluid has been absorbed by the fluid absorbent composition to provide an electrical path between the two terminals.
This patent describes a hand held light beacon for use on life rafts and the like that has a long life due to a flashing light but does not have the lens capability of horizontal or vertical light directing and has not been designed to float vertically or be tied by a lanyard lifted to the top of a mast.
U.S. Pat. No. 7,182,479 of John f. Flood et al. describes a portable, hand-held, electrically powered, high intensity directed light beam generating device for use as a replacement for a pyrotechnic flare for search and rescue, especially in a marine environment. The light intensity is generated by a xenon strobe flash tube in a covered, mirror reflective housing that allows for a directional beam of light of less than 6 steradians. The limited radiation light direction provides a safe optical solution for the user to prevent eye damage while increasing the beam intensity and range. The light and illumination section surrounding the strobe flash tube includes thermally conductive paths for the heat generated by the flash tube to be transmitted to the outside of the housing.
This patent describes a hand held electrically powered, high intensity directed light beam generating device but does not have the unique lens capability nor does it float in the water and if you let go of it would sink.
U.S. Pat. No. 7,703,950 of Jurgen E. Ewert et al. describes a side-emitting lens for use with an LED lamp provides a distribution of emitted light that is substantially normal to an axis of symmetry of the lens; the light can also be symmetrical with respect to a plane normal to the lens axis. The lens has a cavity in which the LED lamp can reside, having a cavity refracting surface with a central section and a stepped cavity sidewall. The lens also has a base external refracting surface surrounding the cavity, an internal reflecting surface spaced apart from the cavity, and a side surface; these surfaces redirect light that enters the lens through the cavity refracting surface. For many applications, the lens axis is vertical in service and the lens is configured to provide a narrow distribution of light in the horizontal plane.
This patent describes only a side-emitting lens for an LED lamp having a base section with a cavity defined by a cavity refracting surface with a substantially planar central section, which is substantially normal to the central lens axis, and a stepped cavity sidewall having a series of sidewall refracting surfaces, and a base external refracting surface symmetrically disposed about the central lens axis and spaced apart from said stepped cavity sidewall. The Visual Distress Signal Device lens does not have the stepped cavity sidewall but has a concave inner surface while having drain capability of the conical upper cavity. The application additionally provides the complete structure of the Visual Distress Signal Device and its unique floating capabilities.
U.S. Pat. No. 8,702,256 of Hans Poul Alkaer relates to an emergency light device for marine use comprising a housing accommodating an electronic circuit, at least one transparent dome, and a first and a second housing member, said electronic circuit comprising at least one light emitting diode provided in the one transparent dome, an electrical power supply comprising at least one battery of the AA, AAA or AAAA type, and at least one operating switch, said emergency light characterized in that the housing has a width which is substantially larger than the height, preferably the width is at least double or triple the height.
This patent describes a light for a life jacket that would sink if it were dropped in the water and does not provides the complete structure of the Visual Distress Signal Device and its unique floating capabilities.
U.S. Pat. No. 6,805,467 of Edward A. Wolf describes a portable emergency light for long range detection by flight and marine search and rescue personnel which utilizes a battery-powered laser array mounted and sealed within a waterproof housing to increase the effective intensity of a specific class laser. The laser array includes a plurality of laser light generators mounted together to project substantially along a common optical axis producing a signaling light. The search and rescue light may include a rotatable head for directing the signaling lights along a 360 degree plane and a three-dimensional gimbal which maintains the light beams in a level horizontal position so that the signaling lights may be easily projected along the entire horizon relative to the user. Each laser light generator is within US Government safety standards for the specific class laser despite the increased power of the signal. The laser array can be used with optical alignment lenses to form a desired highly visible light pattern.
This patent describes an emergency laser array signal light that utilizes a battery-powered laser array mounted and sealed within a waterproof housing to increase the effective intensity of a specific class laser but does not have any floating capability.
In this respect, before explaining at least one embodiment of the Visual Distress Signal Device in detail it is to be understood that the design is not limited in its application to the details of construction and to the arrangement, of the components set forth in the following description or illustrated in the drawings. The Visual Distress Signal Device is capable of other embodiments and of being practiced and carried out in various ways. In addition, 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.
SUMMARY OF THE INVENTION
The principle advantage of the Visual Distress Signal Device is to be used to locate marine vessels and or persons in distress, with a high-intensity portable LED signaling light that is compliant within current and future published governmental regulations for devices utilized in search and rescue operations.
Another advantage of this Visual Distress Signal Device to provide a LED signaling device that eliminates the use of pyrotechnic flares especially in marine environment.
Another advantage of this Visual Distress Signal Device is that the primary light source is not only directed in a horizontal plane, for radial symmetry, but a portion is directed vertically through a transitional angle of divergence between horizontal and vertical planes.
Another advantage of the Visual Distress Signal Device is that it has one or more intermittent LED lights that can be provided in varying colors and can replicate one or more preprogrammed approved distress signal flash sequences such as an SOS signal or other defined flash patterns.
Another advantage of the Visual Distress Signal Device is changes to the vertical position of the LED changes the aiming direction of the beam from both the first and second parts of the lens. This allows the peak intensity of the lens to be varied as needed for specific applications. Raising the position of the LED within the lens will lower the beam angle from the first section of the lens and raise the beam angle from the second total internal reflection (TIR) section of the lens. So this allows the total beam angle to be widened or split into 2 beams if desired. This is particularly helpful in switching from the alert to the locate signal status during a search and rescue operation.
Another advantage of this Visual Distress Signal Device to provide a LED signaling device that eliminates the problems of storage and disposal of old or damaged pyrotechnic flares.
Another advantage of the Visual Distress Signal Device is to provide a very high-intensity portable light signaling device that is safe for the user in any environment.
Another advantage of the Visual Distress Signal Device is that it will float in an upright position.
Another advantage of the Visual Distress Signal Device is that in a lower compartment it can house either a die marker, a Coast Guard approved distress flag or a non-pyrotechnic smoke generating device.
Another advantage of the Visual Distress Signal Device is that the conical central element of the lens has a means to drain water that collects in the center.
Yet another advantage of the Visual Distress Signal Device is being portable, floatable and can be hoisted aloft for optimal visual range and effectiveness and also be tethered to the vessel, a life raft or person in the water. Additionally, with the flag or dye marker removed from the chamber housing same, a pole or boat hook can be inserted into the empty chamber to elevate the device. In this regard, the lower chamber is sized for display in a standard cup holders or fishing rod holders commonly found on most boats.
The Visual Distress Signal Device provides a high-intensity, radially symmetrical, omni directional beam electrically-powered, LED light generating signal locating device for use as a replacement of pyrotechnic flares.
The Visual Distress Signal Device has a lens with a conical upper reflective cavity with the capability to drain any moisture out to the side by the means of one or more vertical slits or one or more slanting drain holes at the bottom of the conical cavity. The device also incorporates a snap on lower section to house either a die marker, or an internationally recognized distress signaling flag used to aid search and rescue personnel or a non-pyrotechnic smoke generating device. The LED's timing and control of the pulsating flashes is electronically controlled by electrical circuitry that will use a programmable microprocessor.
The marine application includes a waterproof housing with sealing O-rings employing an exterior magnet on the optical lens cap which will be rotated for activation of the LED light reed switch without compromising the housing structure.
The light intensity distribution generated by the Visual Distress Signal Device is greater than 75 candelas in the horizontal plane and greater than 15 candelas along the vertical axis. The light is generated by one or more pulsating light emitting diodes (LEDs) and is distributed by three distinct sections of an optical lens. Light entering the first section of the lens is refracted through the outer lens surface into the horizontal plane. Light entering the second section of the lens is refracted toward a total internal reflection (TIR) feature, which then reflects light toward the horizontal plane. Light entering the third section of the lens, directly above the LED, is allowed to pass through the inner and outer surfaces relatively unaffected, thus maintaining its original direction toward the vertical axis. The unit is powered by one or more batteries, preferably lithium or alkaline batteries.
A feature of the Visual Distress Signal Device is that changes to the vertical position of the LED changes the aiming direction of the beam from both the first and second parts of the lens. This allows the peak intensity of the lens to be varied as needed for specific applications. Raising the position of the LED within the lens will lower the beam angle from the first section of the lens and raise the beam angle from the second total internal reflection (TIR) section of the lens. So this allows the total beam angle to be widened or split into 2 beams if desired.
The operational instructions for the Visual Distress Signal Device are:
Snap the lower compartment to the upper housing. Insert batteries in battery holder board assembly. Place supplied EDPM O-ring seals in grooves below thread group on upper housing. Insert complete battery holder board assembly in opening of upper assembly. Lower into place, rotate to align board for proper switch operation position. Thread optical lens cap on upper housing clockwise until it bottoms out. Magnet will line up with the word “ON” and the device will be operating. Rotate lens cap counterclockwise to the word “OFF” Your device is now at the ready. A third setting for “TEST” is also anticipated, as well as a battery strength signal switch, for when the light is tested and the batteries checked with turning on the light.
When the magnetically activated reed switch is first turned on to power the circuit pass element, in this example the MOSFET Q 1 is turned on. The current through the LED and inductor ramps up until the current through the current sensor element matches the reference. Then pass element, in this example a MOSFET Q 1 is turned off and an inductor L 1 continues to supply the current through zener D 3 until its stored energy is exhausted. After some delay, the MOSFET Q 1 is turned on again and the cycle repeats. This cycle repeats during the time the light source is intended to be on and effectively generates the maximum light with the most efficient use of the battery power. Various patterns can be constructed by turning this cycle on and off. For example an S-O-S pattern for a marine beacon. Other color combinations are anticipated, such as cyan-cyan-cyan, red/orange-red/orange-red/orange and numerous other combinations of these colors, chosen from all wavelengths of the visible light spectrum, with white LED emitted light mixed in.
The foregoing has outlined rather broadly the more pertinent and important features of the present Visual Distress Signal Device in order that the detailed description of the application that follows may be better understood so that the present contribution to the art may be more fully appreciated. Additional features of the design will be described hereinafter which form the subject of the claims of this disclosure. It should be appreciated by those skilled in the art that the conception and the disclosed specific embodiment may be readily utilized as a basis for modifying or designing other structures and methods for carrying out the same purposes of the present design. It should also be realized by those skilled in the art that such equivalent constructions and methods do not depart from the spirit and scope of this application as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the Visual Distress Signal Device and together with the detailed description, serve to explain the principles of this application.
FIG. 1 depicts a perspective of the Visual Distress Signal Device with the protective lens cap and bottom drain cap.
FIG. 2 depicts a perspective of the Visual Distress Signal Device.
FIG. 3 depicts a top view of the Visual Distress Signal Device.
FIG. 4 depicts a cross section of the Visual Distress Signal Device illustrating the transparent lens, the location of the battery tray/circuit board perch assembly within the water tight outer housing and the snap on storage compartment that can house a Coast Guard approved distress flag or dye marker or a non-pyrotechnic smoke generating device.
FIG. 5 depicts a perspective view of the battery tray/circuit board perch assembly.
FIG. 6 depicts a cross section through the upper portion of the lens defining the transparent and reflective surfaces and the drain slots.
FIG. 7 depicts a cross section through the upper portion of the lens defining the transparent and reflective surfaces and the drain holes.
FIG. 8 depicts a side view of the circuit board with a single LED.
FIG. 9 depicts a top view of the circuit board with a single LED.
FIG. 10 depicts a top view of the circuit board with one or more (in this case) three LED's, where the placement of the multiple LED's is crucial for optimal operation of the Visual Distress Signal Light.
FIG. 11 depicts an exploded perspective view of the Visual Distress Signal Device illustrating locating slots for the battery tray/circuit board perch assembly in the rim of the water tight outer housing and the mating tabs on the sides of the circuit board.
FIG. 12 depicts a schematic with a single LED.
FIG. 13 depicts a similar schematic with multiple LED's.
FIG. 14 depicts a similar schematic with multiple LED's and an embedded transmitter.
FIG. 15 depicts a communications flow diagram of an additional controller in communication with a global positioning system (GPS) transmitter utilizing Internet connectivity or a WiFi module and a radio module, with a light source controller present.
FIG. 16 depicts a communications flow diagram of an additional controller in communication with a GPS transmitter utilizing Internet connectivity or WiFi module and a radio module.
FIG. 17 depicts a communication system wherein a GPS device can interface with the Internet using a cell phone transmitter adaptor and mobile application software to provide a Visual Distress Signal Device unit which includes a PCB having an integrated electronic beacon with capability for GPS, cell phone, WiFi and Internet connectivity through a common server.
FIG. 18 depicts a communication system wherein a GPS device can interface with a radio transmitter to provide a Visual Distress Signal Device unit which includes a PCB having an integrated electronic beacon with capability for GPS, cell phone, WiFi and Internet connectivity through a common server.
FIG. 19 depicts an alternate embodiment electronic version of the reed switch in the form of an SM353LT electronic switch, which is activated by a magnetic field.
For a fuller understanding of the nature and advantages of the Visual Distress Signal Device, reference should be had to the following detailed description taken in conjunction with the accompanying drawings which are incorporated in and form a part of this specification, illustrate embodiments of the design and together with the description, serve to explain the principles of this application.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein similar parts of the Visual Distress Signal Device 10 A and 10 B are identified by like reference numerals, there is seen in FIG. 1 a perspective of the Visual Distress Signal Device 10 A with the protective lens cover 12 and a bottom cap 14 with drain orifices 15 . This view illustrates the transparent lens 16 with the magnet protrusion 18 and the on and off positioning indicators 22 and 24 on the bulbous top portion 26 of the water tight light housing 28 above the cylindrical grip portion 30 with nonslip ribs 32 . The removable snap-on lower compartment 34 has orifices 41 on the top surface to allow air to escape or water to get in to maintain the vertical positioning of the device. The Visual Distress Signal Device is specifically configured and designed to float with the same characteristics with or without the lower chamber attached. Thus, the lower chamber is optional.
FIG. 2 depicts a perspective of the Visual Distress Signal Device 10 A illustrating the location of the upper lanyard attachment orifice 42 attached to the bulbous top portion 26 , the cylindrical grip portion 30 having nonslip ribs 32 and the snap on storage compartment 34 with the distress flag lanyard orifice 43 on the lower edge.
FIG. 3 depicts a top view of the Visual Distress Signal Device 10 A illustrating the conical upper surface 46 of the transparent lens 16 with the magnet protrusion 18 . The ON and OFF positioning indicators 22 and 24 are on the bulbous top portion 26 of the water tight light housing 28 .
FIG. 4 depicts a cross section of the Visual Distress Signal Device 10 A illustrating the transparent lens 16 , with the two O-ring seals 47 , and the location of the battery tray/circuit board perch assembly 48 within the water tight light housing 28 . The bottom of the battery tray/circuit board perch assembly 48 is incased with a soft cushioning material 29 within the cylindrical grip portion 30 . The water line 45 is shown along the bulbous top portion 26 of the water tight light housing 28 . The battery tray/circuit board perch assembly 48 is shown with the battery compartment 49 and the extended perch legs 50 with the electronic reed switch 51 attached. The extended perch legs 50 are connected to the circuit board mounting plate 52 . The snap-on storage compartment 34 shown with a flag lanyard orifice 43 , can house a Coast Guard approved distress flag 36 , a dye marker pack 38 or a non-pyrotechnic smoke generating device 40 .
FIG. 5 a perspective view of the battery tray/circuit board perch assembly 48 illustrating the battery compartment 49 and the extended perch legs 50 with the electronic reed switch 51 attached is shown connected to the circuit board mounting plate 52 . The circuit board mounting plate 52 has on the upper surface two banana plugs 54 , two alignment pins 56 and two snap-on couplings 58 .
FIG. 6 depicts a cross section through the upper section of the transparent lens 16 defining the drain slots 66 and the general positioning of the ray patterns 60 , 62 and 64 vertically and three hundred and sixty degrees through the transparent lens 16 from the LED light 65 . The inner lens surface 68 directs light onto the upper internal reflection surface 70 of the conical segment 72 , forming the light in a ray pattern 60 toward the horizon. The rays are not all perfectly parallel due to the faceted outer surface to add a bit of spread to the beam to help improve the tolerance due to manufacturing variations. The ray pattern 62 is directed through the inner concave surface 74 and in a horizontal direction through the outer convex surface 76 of the transparent lens 16 while the ray pattern 64 is directed at approximately fifteen degrees through the two flat surfaces 78 and 80 in the transparent lens 16 in a vertical direction. This image is from a real ray trace of a polar array of collimated beams put through the transparent lens 16 .
FIG. 7 depicts a cross section through the upper section of the transparent lens 16 defining the light ray patterns 60 , 62 and 64 and reflection surface 70 of the conical segment 72 . The alternate embodiment of the transparent lens 16 will have a plurality of drain holes 84 slanting to the lower circumference of the conical segment 72 to drain water from the conical segment 72 .
FIG. 8 depicts a side view of the circuit board 88 with a single LED light 65 .
FIG. 9 depicts a top view of the circuit board 88 with a single LED light 65 with the large alignment tab 90 and the small alignment tab 92 . Four holes in the circuit board 88 align to secure the circuit board 88 to the circuit board mounting plate. Electrical connectivity is made from the battery pack to the circuit board with two banana pins. Alignment tabs 90 and 92 on the board 88 allow the board 88 to be indexed to the upper watertight housing 28 .
FIG. 10 depicts a top view of the circuit board 88 with a three LED's lights 65 and the large alignment tab 90 and the small alignment tab 92 .
FIG. 11 depicts an exploded perspective view of the Visual Distress Signal Device 10 A illustrating the large alignment slot 94 and small alignment slot 96 for the positioning of the battery tray/circuit board perch assembly 48 (shown in FIG. 4 ). The slots are in the outer rim 98 of the water tight light housing 28 for the mating of the large alignment tab 90 and the small alignment tab 92 on the circuit board 88 in relation to the electronic reed switch 51 (shown in FIG. 4 ).
FIG. 12 depicts a schematic for Visual Distress Signal Device 10 A with a single LED (D 4 ), that details that the circuit is controlled by a microcontroller or processor (U 1 ) that is controlled by software. The circuit is energized by a power source supplied to Bat+ and Bat−. The circuit has inputs TP 1 through TP 4 that enable “In circuit programming”. The power source is controlled by reed switch (S 1 ). R 1 acts to limit the inrush current going to the storage capacitor (C 2 ). Reverse power source protection is provided by (D 1 ). Since the power source can be variable, the zener (D 2 ) regulates the voltage supplying power to the microcontroller (U 1 ). Frequency control is provided by a crystal (X 1 ) in this example, but can be provided by any frequency regulating device. The output of the microprocessor controls a pass element, in this example a MOSFET (Q 1 ), which is driven by a MOSFET Driver (U 2 ). This pass element allows current to flow through a light emitting source, in this example an LED (D 4 ), an inductor (L 1 ), and a current sense element, in this example, a resistor (R 5 ). When Q 1 is turned on, the current builds up a magnetic field in the inductor (L 1 ) storing energy. When Q 1 is turned off, inductor (L 1 ) supplies current through D 3 , continuing to power the LED (D 4 ), until the field in inductor (L 1 ) collapses.
The microcontroller senses the current, in this example by using an internal comparator (ACMP+ and ACMP−) to compare the voltage across R 5 that represents the current, to a voltage supplied by a reference, in this example a voltage provided by a voltage divider R 3 and R 4 . This controls the peak current. Points “A” and “B” are for wiring an alternate electronic switch to the reed switch shown and described above (see FIG. 19 ).
FIG. 13 depicts a schematic for Visual Distress Signal Device 10 B with similar characteristics except having the option of having multiple LED lights 65 .
Referring now to FIG. 14 , there is shown a similar schematic for Visual Distress Signal Device 10 C with multiple LED's and an embedded beacon transmitter. A circuit controlled by a microcontroller or processor (U 1 ) that is controlled by software. The circuit is energized by a power source supplied to Bat+ and Bat−. The circuit has inputs TP 1 through TP 4 that enable “In circuit programming”. The power source is controlled by a switch. In this example, this is a reed switch (S 1 ). R 1 acts to limit the inrush current going to the storage capacitor (C 2 ). Reverse power source protection is provided by (D 1 ). Since the power source can be variable, the zener (D 2 ) regulates the voltage supplying power to the microcontroller (U 1 ). Frequency control is provided by a crystal (X 1 ) in this example, but can be provided by any frequency regulating device. The output of the microprocessor controls a pass element, in this example a MOSFET (Q 1 ), which is driven by a MOSFET Driver (U 2 ). This pass element allows current to flow through a light emitting source, in this example an LED (D 4 ), an inductor (L 1 ), and a current sense element, in this example, a resistor (R 5 ).
The light source can be a single element like an LED or multiple elements represented by “Dn” and placed in series illustrated by the dotted line trace. When Q 1 is turned on, the current builds up a magnetic field in the inductor (L 1 ) storing energy. When Q 1 is turned off, L 1 supplies current through D 3 , continuing to power the LED until the field in L 1 collapses. The microcontroller senses the current, in this example by using an internal comparator (ACMP+ and ACMP−) to compare the voltage across R 5 that represents the current, to a voltage supplied by a reference, in this example a voltage provided by a voltage divider R 3 and R 4 . This controls the peak current.
Another embodiment would have multiple additional drivers and light sources, represented by the example additional circuit in the dotted box within for Visual Distress Signal Device 10 C as shown in FIG. 14 . This allows lighting separate light sources in different patterns and at different times.
The Algorithm for Visual Distress Signal Device 10 C would function as follows: the switch is first turned on to power the circuit. Then Q 1 is turned on. The current through the LED and inductor ramps up until the current through the current sense element matches the reference. Then Q 1 is turned off and L 1 continues to supply the current through D 3 until its stored energy is exhausted. After some delay, Q 1 is turned on again and the cycle repeats. This cycle repeats during the time the light source is intended to be on. Various patterns can be constructed by turning this cycle on and off. For example an S O S pattern for a marine beacon.
An additional embodiment would provide additional drivers allowing multiple circuits to use this algorithm independently.
FIG. 15 depicts a communications flow diagram 100 of an additional controller in communication with a WiFi module and a radio module, with a light source controller present. An additional controller 102 is in communication with a WiFi module 104 , and a radio module 106 . A light source controller 108 is also present.
FIG. 16 depicts a communications flow diagram 110 of an additional controller in communication with a WiFi module and a radio module. An additional controller 112 is in communication with a WiFi module 114 , and a radio module 116 .
The alert system functions as follows: either an additional micro-controller or an enhanced version of the micro-controller that blinks the light source can be used to interface with an alert system. It can be interfaced with a WiFi Module such as a Freescale TWR-WIFI-AR4100 or a Radio Module such as a Maxim SKY77555 or a conventional transmitter circuit to transmit the information. The WiFi module could be setup as a WiFi hotspot with a web-page displaying an alert. Anyone in range looking for this hotspot would see the alert for example in a cellphone application. It could display the name of the vessel and the location for example. See FIGS. 15 and 16 .
Another embodiment would allow the application to contact a server which monitors the GPS coordinates of its users. Users within an appropriate distance would be notified by text, email, or phone or any combination of these. See FIGS. 15 and 16 .
A third embodiment would use a radio module to send out the alert or contact the Coast Guard. See FIGS. 15 and 16 .
Any combination of these could be used together. See FIGS. 15 and 16 .
FIG. 17 depicts a communication system 120 wherein a GPS device can interface with the Internet using a cell phone transmitter adaptor with mobile application software 122 to provide a connected Visual Distress Signal Device unit 126 on board a vessel 124 . The cell phone transmitter adaptor with mobile application software 122 connected Visual Distress Signal Device unit 126 includes a PCB having an integrated electronic beacon with capability for GPS, cell phone, WiFi and Internet connectivity through a common server 130 in communication with cell phone towers 128 and 132 .
For enabling an Internet link, a unit with a GPS can interface with the Internet using a cell phone adaptor such as the ones available from most cell phone companies to connect to a laptop (see FIG. 17 ). The information describing the location and vessel identification can be sent to a server on the Internet. The server can compare the location of the vessel in distress with the database of locations of other vessels in the area. This database can be derived from the cell phones of users of the software application in the area. This software application would periodically transmit the location of the user's phone. The server would alert the vessels in the area by sending a text an alert in the software application on the phone, a text message, a phone call, an email, or some combination of them.
FIG. 18 depicts a communication system 140 wherein a GPS device can interface with the Internet using a radio transmitter 144 to provide a connected Visual Distress Signal Device unit 146 on board a vessel 124 . The radio transmitter 144 connected to the Visual Distress Signal Device unit 146 on board a vessel 124 , includes a PCB having an integrated electronic beacon with capability for GPS, cell phone, WiFi and Internet connectivity through a common server 130 in communication with radio tower 142 and cell phone tower 132 .
For enabling a radio link, a unit with a GPS can interface with the Internet using a radio transmitter (see FIG. 18 ). The information describing the location and vessel identification can be sent to a server on the Internet. The server can compare the location of the vessel in distress with the database of locations of other vessels in the area. This database can be derived from the cell phones of users of the software application in the area. This software application would periodically transmit the location of the user's phone. The server would alert the vessels in the area by sending a text an alert in the software mobile application on the phone, a text message, a phone call, an email, or some combination of them.
Another embodiment of the alert system anticipates a cellphone application. This application would present a web page to enter the vessel's information. The GPS present in the cellphone would pass the location information to the application. Periodically, this information would be sent by the cellphone via the internet to a central server. This would allow a program on the server to know the location of all of the cellphones using the application. A person on the vessel could activate the alert function of the application. The cellphone would send the alert to the server which would compare the location of the cellphone that issued the alert and the location of the other cell phones in the area. The server would relay the alert the alert to all of the cellphones using the application within a given radius of the cellphone that issued the alert.
Referring now to FIG. 19 there is illustrated an electronic version of the reed switch in the form of a SM353LT electronic switch which is activated by a magnetic field. This electronic version of the reed switch is wired to the schematic shown in FIG. 12 by way of the “A” point to the circuit ground, and the “B” to the circuit (see the “A” and the “B” points clearly shown in FIG. 12 ). The SM353LT is an off the shelf available electronic switch activated by a magnetic field. In an alternate embodiment, using the SM353LT, the magnet that would control the reed switch would instead control the SM353LT. D 5 is a zener diode and regulates the voltage across U 3 . R 6 limits the current to U 3 and to the zener. U 3 turns on when subjected to a magnetic field. This turns on Q 2 through R 7 , a current limiting resistor. The rest of the circuit works as in the previous version.
The Visual Distress Signal Device 10 A, 10 B and 10 C shown in the drawings and described in detail herein disclose arrangements of elements of particular construction and configuration for illustrating preferred embodiments of structure and method of operation of the present application. It is to be understood, however, that elements of different construction and configuration and other arrangements thereof, other than those illustrated and described may be employed for providing a Visual Distress Signal Device 10 in accordance with the spirit of this disclosure, and such changes, alternations and modifications as would occur to those skilled in the art are considered to be within the scope of this design as broadly defined in the appended claims.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
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The present invention is directed to a Visual Distress Signal Device that will float vertically and provides a high-intensity pattern of light which incorporates both a radially symmetrical and omni directional/beam electrically-powered, LED light emitting electronic visual distress signaling device (eVDSD) incorporating a GPS transmitter that can interface with the internet using a cell phone adaptor to enable mobile handheld smartphone application (apps) devices to alert and locate vessels and persons in distress. This device can be used as a replacement for pyrotechnic flares utilized in search and rescue of vessels and persons in distress, especially in a marine environment.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a linear actuator.
[0003] 2. Description of the Related Art
[0004] [0004]FIG. 3 is a schematic cross sectional view of a conventional linear actuator. The linear actuator of FIG. 3 comprises a stator assembly 10 , a rotor assembly 20 , a rear end cap 30 , an output shaft 40 , and a front end cap 50 .
[0005] The stator assembly 10 is composed of two stator units, one of which is structured such that two stator yokes 13 a , 13 b shaped into a ring oppose each other so as to sandwich therebetween a bobbin 12 having a winding 11 provided therearound, and the other of which is structured such that two stator yokes 16 a , 16 b shaped into a ring oppose each other so as to sandwich therebetween a bobbin 15 having a winding 14 provided therearound. The two stator units structured as above are coaxially stacked on each other forming a hollow-cylinder looking like a doughnut. The stator yokes 13 a , 13 b each have an array of pole teeth and are coupled to each other with their respective pole teeth intermeshing with each other. In the same way, the stator yokes 16 a , 16 b each have an array of pole teeth and are coupled to each other with their respective pole teeth intermeshing with each other. The pole teeth constitute the inner circumference of the stator assembly 10 . The windings 11 , 14 are responsible for exciting the pole teeth. The stator yokes 13 a , 13 b , and 16 a , 16 b , and the bobbins 12 , 15 are integrally fixed together by resin injection-molding.
[0006] The rotor assembly 20 is housed in the stator assembly 10 . The rotor assembly 20 is composed of a rotor magnet 21 , and a resin segment 22 , and is shaped into a hollow-cylinder. The rotor magnet 21 has a plurality of magnetic poles, and constitutes the outer circumference of the rotor assembly 20 thus opposing the pole teeth of the stator assembly 10 with a predetermined gap therebetween. The resin segment 22 is shaped tube-like, and disposed inside the rotor magnet 21 , and a female screw 23 is fixedly attached inside the resin segment 22 .
[0007] The rear end cap 30 is disposed at the rear end face of the stator assembly 10 so as to cover the hollow of the stator assembly 10 . The rear end cap 30 has a cavity 31 at its inner side facing the rotor assembly 20 and has a rear ball bearing 32 fitted into a circular recess formed coaxially with the cavity 31 . The ball bearing 32 supports rotatably the rear end portion of the rotor assembly 20 .
[0008] The output shaft 40 is shaped round in its cross section, has a male screw 41 formed at its rear end portion, has a stopper pin 24 disposed at its frontward portion, and has its rearward portion inserted through the rotor assembly 20 . The male screw 41 engages threadedly with the female screw 23 of the rotor assembly 20 , whereby the output shaft 40 travels in the axial direction linearly without turning or with less than one turn when the rotor assembly 20 rotates. In this connection, the stopper pin 24 prohibits or restricts rotation of the output shaft 40 within one turn.
[0009] The front end cap 50 is attached to the front end of the stator assembly 10 so as to cover the hollow of the stator assembly 10 housing the rotor assembly 20 . The front end cap 50 has a round center hole 51 , and the output shaft 40 is inserted through the center hole 51 so as to have its front end portion sticking out from the front end cap 50 . The front end cap 50 has a circular recess 52 coaxial with the center hole 51 , and has a groove 53 extending parallel to the length of the output shaft 40 . The recess 52 receives a front ball bearing 54 fitted thereinto, which rotatably supports the front end portion of the rotor assembly 20 . The aforementioned stopper pin 24 is lodged in and guided by the groove 53 so as to prohibit or restrict rotation of the output shaft 40 , and to restrict the frontward travel amount of the output shaft 40 , and, in some cases, the rearward travel amount thereof as well.
[0010] In the above described linear actuator of FIG. 3, when current is caused to flow in the windings 11 , 14 , the pole teeth of the stator assembly 10 are excited thereby rotating the rotor assembly 20 due to magnetism of the rotor magnet 21 having magnetic poles. When the rotor assembly 20 rotates, the rotational movement of the rotor assembly 20 is converted into linear movement of the output shaft 40 by means of the female screw 23 of the rotor assembly 20 threadedly engaging with the male screw 41 of the output shaft 40 . The output shaft 40 travels in a reciprocating manner within the length of the groove 53 in response to the rotational direction of the rotor assembly 20 . The output shaft 40 stops and reverses its movement when the rotor assembly 20 stops and reverses its rotation.
[0011] The linear actuator above described may encounter troubles incurred when the output shaft 40 stops its movement, that is, when the rotor assembly 20 is caused to stop its rotation. The male screw 41 of the output shaft 40 has a predetermined length defined by its proximal end portion 41 a , and in some linear actuators in which the rearward travel amount of the output shaft 40 is restricted by the proximal end portion 41 a , the rotor assembly 20 is caused to stop its rotation when the proximal end portions 41 a of the male screw 41 touches the female screw 23 . In this case, the thread of the female screw 23 may possibly bite into the proximal end portion 41 a depending on the magnitude of inertial force of the rotation of the rotor assembly 20 at the time of touching, which, depending on the degree of the biting, can cause a critical problem that the rotor assembly 20 will not start off its rotation in the reversed direction therefore failing to move the output shaft 40 . On the other hand, if the length of the male screw 41 is increased to keep off the screw biting problem, the output shaft 40 is caused to stop its rearward movement when the stopper pin 24 touches the front end of the rotor assembly 20 or the inner ring of the front ball bearing 54 . In this case, since the touching area of the stopper pin 24 therewith is positioned outside the pitch diameter of the female and male screws 23 , 41 , an extra torque is required for the rotor assembly 20 to duly start its rotation in the reversed direction thus, in the worst case, making it possibly happen that the rotor assembly 20 will not start off its rotation.
[0012] A linear actuator to address the above problems is disclosed in Unexamined Japanese Patent Application KOKAI Publication No. H06-335228 and will be explained below based on reference numbers in FIG. 3. The linear actuator disclosed therein has a pointed stopper disposed at the center of the cavity 31 of the rear end cap 30 . In the linear actuator, the output shaft 40 is caused to stop its rearward movement when the rear end surface of the output shaft 40 touches the pointed stopper. This structure eliminates the two problems described above, specifically one is that the thread of the female screw 23 bites into the proximal end portion 41 a of the male screw 41 , and the other is that an increased torque is required for the rotor assembly 20 to duly start off its rotation in the reversed direction. However, since the stopper has a pointed head, the head of the stopper can possibly be readily worn away or damaged due to the rear end surface of the output shaft 40 repeatedly touching the head. If the head of the stopper is worn away or damaged, the output shaft 40 cannot be stopped precisely at a place originally determined thus failing to perform an accurate control.
SUMMARY OF THE INVENTION
[0013] The present invention has been made in light of the above problems, and it is an object of the present invention to provide a linear actuator, in which the rearward movement of an output shaft can be surely and accurately stopped without undergoing malfunction.
[0014] In order to achieve the object, according to one aspect of the present invention, a linear actuator comprises a stator assembly, a rotor assembly, an output shaft, a stopper pin, and a stopper member, wherein: the stator assembly is shaped into a cylinder defining a hollow, and includes a plurality of windings, and a plurality of stator yokes each having an array of pole teeth which constitute an inner circumference of the stator assembly, and which are excited by the windings; the rotor assembly is shaped into a hollow-cylinder, is rotatably housed in the hollow of the stator assembly, and includes a ring-shaped magnet which has a plurality of magnetic poles, constitutes an outer circumference of the rotor assembly, and which opposes the pole teeth of the stator assembly with a predetermined distance therebetween, and a female screw disposed at an inner circumference of the rotor assembly; the output shaft is inserted through the rotor assembly, and has a male screw which is formed at a rearward portion thereof, and which engages threadedly with the female screw of the rotor assembly; the stopper pin is fixedly disposed at a frontward portion of the output shaft, and controls axially the mode and amount of movement of the output shaft initiated by rotation of the rotor assembly; and the stopper member is disposed fixedly with respect to the stator assembly, and stops the axial movement of the output shaft without making it happen that the stopper pin which moves with the output shaft touches the rotor assembly.
[0015] Consequently, the female screw does not touch the proximal end portion of the male screw therefore eliminating the aforementioned screw biting problem, and the stopper pin does not touch any portion of the rotor assembly therefore not requiring any extra torque for restarting the rotation of the rotor assembly. Also, the stopper member does not have any pointed portion therefore exhibiting little wear and keeping from damage, eventually resulting in a stable and accurate positioning control of the output shaft.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The above object and other advantages of the present invention will become more apparent by describing in detail the preferred embodiments of the present invention with reference to the attached drawings in which:
[0017] [0017]FIG. 1 is a schematic cross sectional view of a linear actuator according to a first embodiment of the present invention;
[0018] [0018]FIG. 2 is a schematic cross sectional view of a linear actuator according to a second embodiment of the present invention; and
[0019] [0019]FIG. 3 is a schematic cross sectional view of a conventional linear actuator.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] (First Embodiment)
[0021] A linear actuator according to a first embodiment of the present invention will hereinafter be described with reference to FIG. 1. A linear actuator of FIG. 1 generally comprises a stator assembly 60 , a rotor assembly 70 , an output shaft 80 , a rear end cap 90 ; a front end protrusion 100 ; and a front end cap 110 .
[0022] The stator assembly 60 is composed of two stator units 63 , 66 , one 63 of which is structured such that two stator yokes 63 a , 63 b shaped into a ring oppose each other so as to sandwich therebetween a bobbin 62 having a winding 61 provided therearound, and the other 66 of which is structured such that two stator yokes 66 a , 66 b shaped into a ring oppose each other so as to sandwich therebetween a bobbin 65 having a winding 64 provided therearound, and the two stator units 63 , 66 structured as above are coaxially stacked on each other forming a hollow-cylinder looking like a doughnut. The two stator yokes 63 a , 63 b of the stator unit 63 each have an array of pole teeth and are coupled to each other with their respective pole teeth intermeshing with each other. In the same way, the two stator yokes 66 a , 66 b of the stator unit 66 each have an array of pole teeth and are coupled to each other with their respective pole teeth intermeshing with each other. And, respective pole teeth of the two stator units 63 , 66 are appropriately shifted from each other for two-phase driving. The pole teeth constitute the inner circumference of the stator assembly 60 . The windings 61 , 64 are responsible for exciting the respective pole teeth of the stator units 63 , 66 . The stator yokes 63 a , 63 b and 66 a , 66 b , and bobbins 62 , 65 with the windings 61 , 64 are integrally fixed together by means of a yoke support member 67 which is formed of resin by injection-molding.
[0023] The rotor assembly 70 is housed in the stator assembly 60 . The rotor assembly 70 is composed of a rotor magnet 71 , a resin segment 72 , and a female screw 73 , and is shaped into a hollow-cylinder. The rotor magnet 71 is shaped in a ring, has a plurality of magnetic poles, and constitutes the outer circumference of the rotor assembly thus opposing the pole teeth of the stator assembly 60 with a predetermined gap therebetween. The resin segment 72 is shaped tube-like, and disposed inside the rotor magnet 71 , and the female screw 73 is attached inside the resin segment 72 by means of resin injection-molding.
[0024] The rear end cap 90 is positioned at a rear end face 60 b of the stator assembly 60 and covers the hollow of the stator assembly 60 . The rear end cap 90 is formed of resin simultaneously and integrally with the yoke support member 67 by resin injection-molding. The rear end cap 90 has a cavity 91 at its inner side facing the rotor assembly 70 . The cavity 91 constitutes a sleeve bearing and supports rotatably a rear end portion 70 b of the rotor assembly 70 . The cavity 91 is not necessarily configured as shown in FIG. 1 but may alternatively be configured so as to receive a ball bearing fitted thereinto for rotatably supporting the rotor assembly 70 .
[0025] The output shaft 80 is shaped round in its cross section, has a male screw 81 formed at a portion toward a rear end 80 b thereof, has a stopper pin 82 disposed at a portion toward a front end 80 a , and has its rearward portion inserted through the rotor assembly 70 . The male screw 81 engages threadedly with the female screw 73 of the rotor assembly 70 , whereby the output shaft 80 travels in the axial direction linearly without turning or with less than one turn when the rotor assembly 70 rotates. In this connection, the stopper pin 82 prohibits or restricts rotation of the output shaft 80 within one turn.
[0026] The front end protrusion 100 is shaped into a ring and positioned at a front end face 60 a of the stator assembly 60 . The front end protrusion 100 is formed of resin simultaneously and integrally with the yoke support member 67 and also with the rear end cap 90 by resin injection-molding. The front end protrusion 100 has an inner diameter larger than the inner diameter of the stator assembly 60 , and has a front ball bearing 101 fitted thereinto. A portion of the resin segment 72 of the rotor assembly 70 is fixedly fitted into the inner ring of the front ball bearing 101 , whereby the front end portion of the rotor assembly 70 is rotatably supported. The front end protrusion 100 has a stopper member 103 attached to its frontward portion. The stopper member 103 is shaped into a disk, has a center hole for inserting the output shaft 80 , and has a circular recess formed at its inner side facing the front ball bearing 101 . The recess of the stopper member 103 defines a diameter larger than an outer diameter of the inner ring of the front ball bearing 101 thereby forming a clearance from the inner ring so as not to block the rotation of the rotor assembly 70 . In the structure described above, the output shaft 80 is caused to stop its rearward movement when the stopper pin 82 of the output shaft 80 touches the stopper member 103 .
[0027] The front end cap 110 is attached by means of a metal fitting 114 to the front end face 60 a of the stator assembly 60 so as to cover the hollow of the stator assembly 60 housing the rotor assembly 70 . The front end cap 110 has a round center hole 111 , and the output shaft 80 is inserted through the center hole 111 so as to have its front end portion (toward the front end 80 a ) sticking out from the front end cap 110 . The front end cap 110 has a groove 112 extending parallel to the length of the output shaft 80 . The aforementioned stopper pin 82 is lodged in and guided by the groove 112 so as to prohibit or restrict rotation of the output shaft 80 and to restrict the travel distance of the output shaft 80 .
[0028] The actuation of the linear actuator of FIG. 1 will be discussed. Current is caused to flow in the windings 61 , 64 so as to excite the respective pole teeth of the stator units 63 , 66 , whereby the rotor assembly 70 is caused to rotate due to magnetism from the rotor magnet 71 . When the rotor assembly 70 rotates, the output shaft 80 is caused to move in the axial direction by means of the female screw 73 of the rotor assembly 70 threadedly engaging with the male screw 81 of the output shaft 80 . In this connection, the stopper pin 82 moves along the groove 112 while prohibiting or restricting the rotation of the output shaft 80 . The stopper pin 82 moves rearward together with the output shaft 80 moving rearward, and the output shaft 80 stops its movement when the stopper pin 82 touches the stopper member 103 .
[0029] As described above, the linear actuator according to the first embodiment of the present invention includes the stopper member 103 , and the output shaft 80 is caused to stop its rearward movement when the stopper pin 82 touches the stopper member 103 . Thus, the female screw 73 does not touch the proximal end portion of the male screw 81 therefore eliminating the aforementioned screw biting problem, and the stopper pin 82 does not touch any portion of the rotor assembly 70 or the inner ring of the front ball bearing 101 therefore not requiring any extra torque for restarting the rotation of the rotor assembly 70 . Also, the stopper member 103 does not have any pointed portion therefore exhibiting little wear and keeping off damage, eventually resulting in a stable and accurate positioning control of the output shaft 80 .
[0030] (Second Embodiment)
[0031] A linear actuator according to a second embodiment of the present invention will be described with reference to FIG. 2. In FIG. 2, like reference numerals refer to like elements in FIG. 1.
[0032] The linear actuator according to the second embodiment differs from the first embodiment principally in bearing type, and in stopper member structure. Specifically, in the first embodiment, the front and rear end portions of the rotor assembly 70 are rotatably supported respectively by the ball bearing 101 and the cavity 91 constituting a sleeve bearing, and the stopper member 103 is attached to the front end protrusion 100 . On the other hand, in the second embodiment, the front and rear end portions of a rotor assembly are rotatably supported respectively by a sleeve bearing and a ball bearing (reversed compared with the first embodiment), and a stopper member is constituted by a portion of the sleeve bearing which rotatably supports the front end portion of the rotor assembly.
[0033] The linear actuator according to the second embodiment shown in FIG. 2 basically comprises a stator assembly 60 , a rotor assembly 70 , and an output shaft 80 , which are of the same structure as the first embodiment shown in FIG. 1.
[0034] A rear end cap 120 is disposed at a rear end face 60 b of the stator assembly 60 so as to cover the hollow of the stator assembly 60 . The rear end cap 120 is formed of resin integrally with a yoke support member 67 by injection-molding, and has a cavity 121 at its inner side facing the rotor assembly 70 . The cavity 121 has a circular recess formed coaxially therewith, and a rear ball bearing 122 to rotatably support a rear end 70 b of the rotor assembly 70 is fitted into the recess. A front end cap 130 is attached at a front end face 60 a of the stator assembly 60 so as to cover the hollow of the stator assembly 60 housing the rotor assembly 70 . The front end cap 130 defines a cavity at its inner side facing the rotor assembly 70 , and has a round center hole 131 . A sleeve bearing 140 is fitted into the cavity of the front end cap 130 and supports rotatably a front end portion 70 a of the rotor assembly 70 , and the output shaft 80 is inserted through the center hole 131 so as to have its front end portion (toward a front end 80 a ) sticking out from the front end cap 130 . The output shaft 80 is movably inserted through the sleeve bearing 140 . The sleeve bearing 140 has a groove 141 formed at its inner circumference so as to extend parallel to the length of the output shaft 80 . A frontward end of the groove 141 is open, and the other end is blind so as to constitute a stopper member 142 . A stopper pin 82 is lodged in and guided by the groove 141 thereby controlling the movement of the output shaft 80 . A front plate 150 may be attached as required.
[0035] The linear actuator structured above actuates basically in the same way as the linear actuator of the first embodiment. The output shaft 80 moves linearly when the rotor assembly 70 rotates. The stopper pin 82 fixedly disposed at the output shaft 80 also moves linearly along the groove 141 while prohibiting or restricting the rotation of the output shaft 80 . When the output shaft 80 moves rearward, the stopper pin 82 moves also rearward, and the output shaft 80 stops its movement upon the stopper pin 82 touching the stopper member 142 .
[0036] As described above, the linear actuator according to the second embodiment of the present invention includes the stopper member 142 , and the rotor assembly 70 is caused to stop its linear movement when the stopper pin 82 touches the stopper member 142 . Thus, the female screw 73 does not touch the proximal end portion of the male screw 81 therefore eliminating the aforementioned screw biting problem, and the stopper pin 82 does not touch any portion of the rotor assembly 70 therefore not requiring any extra torque for duly restarting the rotation of the rotor assembly 70 . Also, the stopper member 142 does not have any pointed portion therefore exhibiting little wear and keeping from damage, eventually resulting in a stable and accurate positioning control of the output shaft 80 .
[0037] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
[0038] This application is based on Japanese Patent Application No. 2003-50097 filed on. Feb. 26, 2003 and including specification, claims, drawings and summary. The disclosure of the above Japanese Patent Application is incorporated herein by reference in its entirety.
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A stopper member is included in a linear actuator comprising a stator assembly, a rotor assembly, an output shaft, and a stopper pin which is fixedly disposed at a frontward portion of the output shaft, and which is adapted to axially control the mode and amount of movement of the output shaft initiated by rotation of the rotor assembly. The stopper member is disposed fixedly with respect to the stator assembly and stops the axial movement of the output shaft without making it happen that the stopper pin which moves together with the output shaft touches the rotor assembly.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to and claims priority from earlier filed U.S. Provisional Patent Application No. 61/176,402 titled Adjustable Locking Spacer, filed May 7, 2009.
[0002] The present invention relates generally to an adjustable leveling pedestal to support raised access flooring, and more particularly, but not by way of limitation, to an adjustable leveling pedestal that allows for infinite height adjustment of the floor by moving stopping members along a shaft.
BACKGROUND OF THE INVENTION
[0003] Adjustable pedestals for flooring are well known in the art, but suffer from significant drawbacks. For example, prior art adjustable spacers have limited vertical positioning, limited ability to adjust the vertical positioning during loading, and are cumbersome to work with and install. Typical adjustable pedestals are provided with a base, a slotted or notched shaft and a top plate. The shaft is received within, and moves in and out of, the base and locks into position with a clip, rod, cotter pin, or similar mechanism. The spacer is only positionable at heights which correspond to the slots or notches on the shaft.
[0004] Also, typical adjustable pedestals are not adjustable while a load is applied. The downward force of the load precludes vertical adjustment of the adjustable pedestal unless something is provided to support or lift the applied load. Prior art pedestals are also difficult to install and cumbersome to work with.
[0005] Therefore, a need exists for an adjustable leveling pedestal that is selectively adjustable when a load is applied. Simple installation and minimal types of part are also desirable. It is to such an adjustable leveling pedestal that the present invention is directed.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention provides a pedestal to support access flooring. The pedestal includes a base, a head, first and second support members, a threaded support shaft, and first and second threaded nuts. The first support member is inserted into the base and the second support member is inserted into the head. The threaded support shaft is removably inserted into the first and second support members. The first and second threaded nuts are rotatably attached to the support shaft. The first threaded nut abuts the second support member and the second threaded nut abuts the first threaded nut. The first threaded nut can be rotated to move the second support member.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1A is a front elevational view of a portion of an adjustable leveling pedestal in accordance with a preferred embodiment of the present invention.
[0008] FIG. 1B is a front elevational view of the adjustable leveling pedestal of FIG. 1A in accordance with a preferred embodiment of the present invention.
[0009] FIG. 2 is a top plan view of a plurality of floor panels having the adjustable leveling pedestals of FIG. 1B disposed at each corner thereof.
[0010] FIG. 3 is a top plan view of a plurality of floor panels having the adjustable leveling pedestal of FIG. 1B disposed at the adjoining corners.
[0011] FIG. 4A is a side elevational view of aligned pair adjustable leveling pedestals of FIG. 1B .
[0012] FIG. 4B is a side elevational view of the misaligned pair of adjustable leveling pedestals of FIG. 4A before alignment.
[0013] FIG. 5 is a front elevational view of another presently preferred embodiment of an adjustable leveling pedestal.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Referring now to the drawings, and more particularly to FIGS. 1A and 1B , shown therein is an adjustable leveling pedestal 10 for raising and leveling access flooring panels (see FIGS. 4A and 4B ) away from a surface 18 . The adjustable leveling pedestal 10 is provided with a top engaging member 22 , a bottom engaging member 24 , a first adjustable stop 26 , a second adjustable stop 30 and a support shaft 34 .
[0015] In a presently preferred embodiment, the top engaging member 22 is fabricated to interface with a head 14 . The top engaging member 22 preferably has a generally square cross sectional area, although it may have many different geometries that would be apparent to one of ordinary skill in the art. It will be understood that the geometry of the top engaging member 22 should cooperate with the head 14 to provide a substantially secure interface, which can preferably be assembled without tools by inserting the top engaging member 22 into the head 14 . The top engaging member 22 is preferably constructed of a plastic or fiberglass material, but can be fabricated out of any suitable material, such as a resin, other plastic polymer, natural material(s) such as a wood or fiber based material, metal (such as steel, titanium, aluminum or blends thereof) and combinations thereof. The top engaging member 22 is provided with an interface 42 which is fabricated to connect the top engaging member 22 with the support shaft 34 . In a presently preferred embodiment, the interface 42 is a bore fabricated such that the support shaft 34 fits snugly within the interface 42 , preferably without using tools.
[0016] The bottom engaging member 24 is preferably similar in construction and function to the top engaging member 22 with a generally square cross sectional area, but can also have any number of differing geometries that would be apparent to one of ordinary skill in the art. It will be understood that the geometry of the bottom engaging member 24 should cooperate with, for example, the geometry of a base 46 to provide a substantially secure interface, preferably without using tools. The bottom engaging member 24 is preferably constructed of a plastic or fiberglass material, but can be fabricated out of any suitable material, such as a resin, other plastic polymer, natural material(s) such as a wood or fiber based material, metal (such as steel, titanium, aluminum or blends thereof) and combinations thereof. The bottom engaging member 24 is provided with an interface 50 which is also made to connect the bottom engaging member 24 with the support shaft 34 . In a presently preferred embodiment, the interface 50 is also a bore fabricated such that the support shaft 34 fits snugly within the interface 50 , preferably without using tools. The lengths of both the top engaging member 22 and the bottom engaging member 24 should be of sufficient size and the length of their respective bores should be of sufficient depth to receive portions of the support shaft 34 .
[0017] The support shaft 34 of the adjustable leveling pedestal 10 is provided with a first end 58 and a second end 62 . The support shaft 34 is preferably made of fiberglass and threaded along its entire length (all threading not shown in FIGS. 1A and 1B ). The support shaft 34 should be of a size that can be snugly fit into interfaces 42 and 50 of the top engaging member 22 and the bottom engaging member 24 , respectively, but can be removed with minimal force, preferably without using tools. The support shaft 34 is constructed so as to cooperate with both the first adjustable stop 26 and the second adjustable stop 30 to provide height adjustability for the adjustable leveling pedestal 10 . The support shift 34 includes threads 66 that are operable to engage the first adjustable stop 26 and the second adjustable stop 30 . Other shaft configurations (such as partially threaded) that allow the support shaft 34 to engage the first adjustable stop 26 and the second adjustable stop 30 may likewise be utilized.
[0018] The first adjustable stop 26 is preferably a plastic flanged nut (flange not shown) for receiving an end of the support shaft 34 . The flange of the first adjustable stop 26 is preferably oriented such that the flange abuts the top engaging member 22 . The first adjustable stop 26 may be fabricated out of any suitable material, for example, a resin or plastic polymer, natural material(s) such as a wood or fiber based material, metal (such as steel, titanium, aluminum or blends thereof), fiber or glass based materials and combinations thereof. As mentioned above, the flange of first adjustable stop 26 is constructed so as to engage with at least a portion of the top engaging member 22 in order to hold the top engaging member 22 in a fixed configuration relative to the bottom engaging member 24 . In operation, the first adjustable stop 26 is secured against a bottom surface 78 of the top engaging member 22 by turning the first adjustable stop 26 until it abuts the bottom surface 78 of the top engaging member 22 .
[0019] The second adjustable stop 30 is preferably a standard nut similar in construction and operation to the first adjustable stop 26 . The second adjustable stop 30 is positioned below the first adjustable stop 26 and operates to substantially preclude downward movement of the first adjustable stop 26 along the support shaft 34 after the second adjustable stop 30 has been tightened against the first adjustable stop 26 .
[0020] In operation, the first adjustable stop 26 and the second adjustable stop 30 are threaded onto the support shaft 34 . The first end 58 of the support shaft 34 is inserted into the interface 42 of the top engaging member 22 and the second end 62 of the support shaft 34 is inserted into the interface 50 of the bottom engaging member 24 , preferably without using tools. To secure the top engaging member 22 , the first adjustable stop 26 is turned until the flange contacts the bottom surface 78 of the top engaging member 22 . To lock the first adjustable stop 26 and therefore top engaging member 22 , the second adjustable stop 30 is turned until it contacts the bottom of the first adjustable stop 26 . The cooperative use of the first adjustable stop 26 and the second adjustable stop 30 allow for infinite adjustability and fine adjustments to the overall length of the adjustable leveling pedestal 10 .
[0021] To selectively increase the height of the top engaging member 22 , the top engaging member 22 is moved upwardly along the support shaft 34 by turning the first adjustable stop 26 to raise the top engaging member 22 . To lock the first adjustable stop 26 and therefore top engaging member 22 , the second adjustable stop 30 is turned until it contacts the bottom of the first adjustable stop 26 . To selectively lower the height of the top engaging member 22 the second adjustable stop 30 is turned in the opposite direction, moving the second adjustable stop 30 downwardly along the support shaft 34 . Next, the first adjustable stop 26 is turned in the opposite direction moving the first adjustable stop 26 downwardly along the support shaft 34 . The top engagement member 22 is then moved downwardly along the support shaft 34 until the bottom of the top engagement member contacts the first adjustable stop 26 . The first adjustable stop 26 and the second adjustable stop 30 can be turned by hand or using a wrench or other suitable tool.
[0022] The adjustable leveling pedestal 10 is constructed so as to be used for spacing floor panels 14 a distance away from a surface 18 . When utilized for spacing floor panels 14 a distance away from the surface 18 , the adjustable leveling pedestal 10 is preferably provided with a channel (not shown) that is bolted to the head 44 . Preferably, the channel can be slid onto the bolts connecting it to the head (or heads) without the use of tools. This can be accomplished by proper spacing of the bolt and a nut so that during installation of the flooring system the channel can be simply slid onto the nut. The channel is preferably long enough to be bolted to as many adjustable leveling pedestals 10 as are needed to support the floor panels 14 and thereby occupy the area desired for the raised access flooring. In another preferred embodiment, the channel includes a soft material such as foam rubber attached to the top side. The soft material provides an interface between the channel and the floor panels 14 that prevents the floor panels 14 from moving and prevents unwanted noise when loads are applied to the floor panels 14 . In another preferred embodiment, the base 46 is secured to the surface 18 with an adhesive, as will be readily apparent to one skilled in the art. As stated previously, the base 46 is configured to mate with the bottom engaging member 24 . In one embodiment, the base 46 is constructed having a vertical support 108 having a recess 112 for receiving the bottom engaging member 24 , and a base flange 114 for connecting the base 46 to the surface 18 . The base flange 114 is preferably of a square cross section that includes four holes. The adhesive, in addition to securing the base flange 114 (and thereby the base 46 ), extrudes through the holes to additionally secure the base 46 . The base 46 is constructed from any suitable rigid and durable material, for example, a resin or plastic polymer, natural material(s) such as a wood or fiber based material, metal (such as steel, titanium, aluminum or blends thereof), fiber or glass based materials and combinations thereof. The base flange 114 of the base 46 may also be secured to the surface 18 via a fastener such as, for example, threaded fasteners, screws, nails, rivets, in addition to the adhesive.
[0023] The head 44 is substantially identical in construction to the base 46 , though only the head 44 is typically bolted, such as to the channel (not shown). In one preferred embodiment, the head 44 is constructed having a vertical support 110 having a recess 120 for receiving the top engaging member 22 , and a head flange 128 for connecting the head 44 to the channel. The head flange 128 of the head 44 is preferably of a square cross section that includes four holes (not shown) and is preferably bolted to the channel. In a preferred embodiment, the channel runs along the interface of adjacent floor panels 14 and supports the weight of the floor panels 14 . The floor panels 14 are preferably made from fiberglass, and if constructed from such material the floor panels 14 remain securely on the channel.
[0024] Referring now to FIG. 3 , shown therein is a plurality of floor panels 14 , each of which is provided with four adjustable leveling pedestals 10 , one adjustable locking spacer 10 positioned on each corner 116 . Although a raised floor can be assembled in this fashion, the added benefit of using the channel and a fewer number of adjustable leveling pedestals cannot be realized.
[0025] Referring now to FIG. 4B , shown therein is a misaligned pair of floor panels 14 (channel is not shown). When installing floor panels 14 , if the surface 124 is not level, the floor panels 14 will not be level.
[0026] When floor panels 14 are uneven, the height of one or more of the floor panels 14 may be either raised or lowered to align the floor panels 14 via the adjustable leveling pedestal 10 . By way of non-limiting example, a floor panel 14 having an adjustable leveling pedestals 118 A and 118 B and abuts another floor panel 14 having an adjustable leveling pedestal 122 A and 122 B. The floor panel 14 having the adjustable leveling pedestal 122 B is positioned at a height lower than the floor panel 14 having the adjustable leveling pedestal 118 A and 118 B due to, for example, variations of the surface 124 . To adjust the height of the floor panel 14 having the adjustable leveling pedestal 122 B, the first adjustable stop 138 of the adjustable leveling pedestal 122 B is moved upwardly along the support shaft 130 , therefore moving the top engaging member 134 upwardly and in-turn, increasing the height of the floor panel 14 . When the desired height of the floor panel 14 is achieved, the second adjustable stop 126 is moved upwardly along the support shaft 130 until it abuts the bottom of the first adjustable stop 138 . This process may be repeated, extending and retracting the adjustable locking spacer 122 B until the correct floor panel 14 height is achieved (see FIG. 4A ).
[0027] Referring now to FIG. 5 , shown therein is another presently preferred embodiment of the adjustable leveling pedestal 200 with channel 202 . A head 204 is preferably bolted to the channel 202 . Similar to FIGS. 1A and 1B , the adjustable leveling pedestal 200 includes a first adjustable stop 208 and a second adjustable stop 216 , secured to a threaded support shaft 212 .
[0028] From the above description, it is clear that the present invention is well adapted to carry out the objects and to attain the advantages mentioned herein as well as those inherent in the invention. While presently preferred embodiments of the invention have been described for purposes of this disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art and which are accomplished within the spirit of the invention disclosed.
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The present invention provides a pedestal for use in raised access flooring, such as for magnetic resonance imaging rooms and computer rooms. The pedestal includes a base, a head, first and second support members, a threaded support shaft, and first and second threaded nuts. The invention is easy to install and can be made of all non-metalic parts. The base and the head can be constructed identically to minimize the type of parts needed for manufacturing and inventory. The first and second support members can also be constructed identically, further minimizing the parts needed.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of copending International Application No. PCT/DE03/02327 filed Jul. 10, 2003 which designates the United States, and claims priority to German application no. 102 33 906.6 filed Jul. 25, 2002.
TECHNICAL FIELD OF THE INVENTION
[0002] This invention relates to an injection module.
DESCRIPTION OF THE RELATED ART
[0003] According to the embodiment of an injection module, a movable insert is provided which is used for example in order to transfer a deflection of an actuator to an injection needle of an injection valve. If piezoelectric actuators are used, precise adjustment of the movable insert with respect to a final control element is required. This is necessary because on the one hand piezoelectric actuators can only realize a short displacement stroke and on the other hand, because of different thermal coefficients of expansion between the injection valve housing and the piezoelectric actuator, a defined idle stroke must be maintained between the piezoelectric actuator and a final control element to be actuated.
[0004] This defined idle stroke must first be overcome during actuation by the actuator element before the status of the injection valve can be changed. This has the disadvantage that higher actuating voltages and/or relatively large piezoelectric actuator elements are required in order to make the necessary actuating path available for controlling the injection valve.
SUMMARY OF THE INVENTION
[0005] It is therefore the object of the present invention to provide an injection module in which the size of the defined idle stroke can be reduced.
[0006] According to the invention an injection module is provided with a housing in which an actuator element and an injection valve are disposed. The actuator element is designed in such a way as to control the injection valve by means of a change in length. A compensating element is connected to the actuator element in order to compensate the negative effects caused by the change in length of the housing due to thermal expansion.
[0007] Said compensating element exhibits an intrinsic thermal expansion which is added to the thermal expansion of the actuator element. In this way the thermal expansion of the compensating element and the actuator element can be precisely set. Matching the common thermal expansion of actuator element and compensating element to the thermal expansion of the housing removes the need to maintain a defined idle stroke between actuator element and the final control element to be actuated. This permits smaller actuator elements to be provided since the necessary actuating stroke of the actuator element can be reduced. Alternatively the actuating voltage of the actuator element for controlling the injection valve can be reduced.
[0008] According to one embodiment of the invention the compensating element is supported at a retaining point in such a way that the thermal expansion of the housing between the retaining point and the injection valve is essentially equivalent to the common thermal expansion of actuator element and compensating element. In this case the actuator element is connected to the housing via the compensating element rather than directly to the housing.
[0009] According to a further embodiment of the invention it can be provided that a thermally conducting element is disposed on the compensating element in order to effect a temperature compensation between the compensating element and the housing. The function of the thermally conducting element is to counteract a temperature difference between the housing and the compensating element or, as the case may be, actuator element. It permits faster temperature compensation between the various elements. This is necessary because the thermal expansions of the housing and of the compensating element and the actuator element have to be matched to one another when they have the same temperature. More particularly in the starting phase of the engine, the components of the injection module have different temperatures because heat is transferred from the outside to the inside. The provision of the thermally conducting element therefore has the advantage of producing a faster temperature compensation between the exterior, i.e. the housing, and the interior of the injection module, i.e. the compensating element and the actuator element.
[0010] Preferably it is provided that the thermally conducting element is in contact with both the housing and the compensating element. This has the advantage that a better transfer of heat is possible via the thermally conducting element as a result of the direct contact.
[0011] According to a further embodiment of the invention it is provided that the thermally conducting element is embodied as a sleeve, preferably a metal sleeve, made of a material exhibiting good thermal conductivity, which material comprises in particular copper, brass, silver or a similar element. The sleeve can be disposed around the compensating element and is therefore easy to install during assembly simply by slipping it over a cylindrical compensating element.
[0012] It can be provided that the sleeve has longitudinal slits, with the ridges formed by the longitudinal slits being curved. The ridges enable the sleeve to be held in place between the housing and the compensating element, it being immaterial whether the ridges are curved toward the inside or toward the outside. If the ridges are curved toward the inside, they abut the compensating element and press the edges of the sleeve against an internal wall of the housing. If the ridges are curved toward the outside, they abut the internal wall of the housing and the edges of the sleeve are in contact with the compensating element.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] A preferred embodiment of the invention will be explained in more detail below with reference to the attached drawing, in which:
[0014] FIG. 1 shows an injection module according to a preferred embodiment of the invention;
[0015] FIG. 2 shows an enlarged representation of the compensating element according to a preferred embodiment of the invention; and
[0016] FIG. 3 shows a possible embodiment of a thermally conducting element.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] FIG. 1 shows a cross-section through an injection module comprising a housing 1 into which an actuator element 2 is introduced. The housing 1 is bolted by means of a clamping nut 3 . The clamping nut 3 tightens a nozzle body 4 and a valve plate 5 into the housing 1 . In this arrangement an upper end surface of the nozzle body 4 is in contact with a lower end surface of the valve plate 5 . An upper end surface of the valve plate 5 is in turn in contact with a lower end surface of the housing 1 .
[0018] The actuator element 2 is located between a base plate 7 and a compensating element 6 . A spring sleeve is disposed around the actuator element 2 in order to pretension the actuator element 2 . The base plate 7 is disposed movably with respect to the housing 1 . The base plate 7 has a control stud 16 which is associated with a pin part 23 of a closing element 8 . The closing element 8 is disposed in a discharging aperture 17 of the valve plate 5 . The discharging aperture 17 is embodied essentially cylindrically and tapers into a conical shape in its upper area. The conical area of the discharging aperture 17 constitutes a sealing seat for the closing element 8 . The closing element 8 is embodied essentially cylindrically and likewise tapers in its upper area via a conical shape into the pin part 23 . The discharging aperture 17 is connected to a feed channel 10 via a feed hole 18 which is incorporated into the guide plate 11 , the feed channel 10 being routed in the housing 1 and representing a fuel connection.
[0019] Disposed between the feed hole 18 and the discharging aperture 17 is a feed choke 19 . The discharging aperture 17 is hydraulically connected to a control chamber 20 which is incorporated in the guide plate 11 and is delimited by a movably mounted actuating piston 21 . The actuating piston 21 is actively connected to a valve needle 12 whose tip is associated with an injection aperture 14 . Embodied around the injection aperture 14 is a sealing seat for the tip of the valve needle 12 . Embodied between the valve needle 14 and the nozzle body 4 is a fuel chamber 13 which is likewise connected to the feed channel 10 . In addition corresponding fuel holes are incorporated in the nozzle body 4 , in the guide plate 11 and in the valve plate 5 .
[0020] The actuator element 2 is preferably embodied as a piezoelectric actuator and is controlled via control lines 30 which are routed to the actuator element 2 via a control line channel 31 . For this purpose the compensating element 6 is provided with a hole, essentially parallel to its longitudinal axis, through which the control lines 30 are guided.
[0021] The injection valve operates as follows: in the non-activated state of the actuator element 2 the control stud 16 does not act on the pin part of the closing element 8 . The feed channel 10 is connected to a fuel reservoir which makes fuel available at high pressure. Consequently fuel under high pressure is present in the fuel chamber 13 , the control chamber 20 and the discharging aperture 17 . Due to the high fuel pressure the closing element 8 is pressed into the associated sealing seat and closes the discharging aperture 17 . At the same time the valve needle 12 is pressed downward by the high fuel pressure that is present in the control chamber 20 onto the sealing seat of the injection aperture 14 via the actuating piston 21 . As a result the injection aperture 14 is closed and no injection takes place.
[0022] If the actuator element 2 is now activated, that is to say energized with electric current, the actuator element 2 expands and in the process presses the base plate 7 downward, thereby forcing the control stud 16 against the pin part 23 of the closing element 8 . As a result of this the closing element 8 is lifted off from the associated sealing seat. Consequently the discharging aperture 17 is opened and fuel is discharged from the control chamber 20 . This causes the fuel pressure in the control chamber 20 to drop, since less fuel is supplied via the feed choke 19 than flows out via the discharging aperture 17 . As the valve needle 12 has a pressure collar 15 in the area of the fuel chamber 13 , the high fuel pressure present in the fuel chamber 13 lifts the valve needle 12 away from the sealing seat of the injection aperture 14 . This causes the injection aperture 14 to open and the fuel to be discharged from the fuel chamber 13 via the injection aperture 14 . Typically, an idle stroke section is provided between the control stud 16 and the closing element 8 when the actuator element 2 is not activated. The purpose of the idle stroke section is to absorb thermal expansions between housing and actuator element without the control stud 16 being activated.
[0023] The compensating element 6 is connected to the housing 1 by its end facing away from the actuator element 2 via a clamping screw 32 . The compensating element 6 is fixed to the actuator element by its other end. The actuator element 2 abuts the base plate and one end of the compensating element 6 .
[0024] The thermal expansion of compensating element 6 and actuator element 2 is equal to the thermal expansions of the compensating element 6 and the actuator element 2 . Since piezo actuators typically comprise ceramic materials, their thermal expansion is generally low. Conversely, the housing 1 is typically made of a metallic material which has a far higher coefficient of thermal expansion. As the temperature of the injection module rises, the length of the interior therefore increases in the housing in which the actuator element 2 is situated and an idle stroke is formed which makes it necessary for a higher control voltage to be used in order to activate the actuator element 2 or for a larger actuator element 2 to be provided in order to produce the longer actuating path. The compensating element 6 is provided in order to avoid this, said compensating element having a higher coefficient of thermal expansion than the actuator element 2 in order to avoid the idle stroke being produced as a result of thermal expansion. Consequently the compensating element 6 preferably has a higher coefficient of thermal expansion than the coefficient of thermal expansion of the housing 1 in order to compensate the lower coefficient of thermal expansion of the actuator element 2 . A compensating element 6 whose coefficient of thermal expansion is lower than the coefficient of thermal expansion of the housing 1 should of course be provided if the coefficient of thermal expansion of the actuator element 2 is greater than the coefficient of thermal expansion of the housing 1 .
[0025] The coefficients of thermal expansion are matched to the lengths of the actuator element 2 and the compensating element 6 in such a way that in the event of uniform heating the housing and the common thermal expansion of compensating element 6 and actuator element 2 are identical. This is produced according to the following formula:
α Actuator ·L Actuator +α Compensating-element ·L Compensating-element =α Housing ·( L Actuator-element +L Compensating-element )
where α Housing corresponds to the coefficient of thermal expansion of the material of the housing 1 , α Compensating-element corresponds to the coefficient of thermal expansion of the material of the compensating element 6 , α Actuator-element corresponds to the coefficient of thermal expansion of the actuator element 2 , L Actuator-element corresponds to the length of the actuator element 2 , and L Compensating-element corresponds to the length of the compensating element 6 .
[0031] The injection module heats up from the outside to the inside rather than uniformly, more particularly in the starting phase of the engine. This gives rise to thermal stresses which are caused by different changes in length of the elements as a result of different coefficients of expansion. These stresses cannot be avoided entirely. In order to reduce this, however, and thereby reduce the mechanical stress on the overall system, a thermally conducting element 33 is provided. The thermally conducting element 33 is embodied in the form of a sleeve which encloses the compensating element 6 .
[0032] FIG. 2 shows the compensating element 6 and the thermally conducting element 33 in an enlarged view. The thermally conducting element 33 embodied as a sleeve 33 has slits as a result of which ridges are formed. These ridges are preferably curved outward and abut an internal wall of the housing 1 under a certain pretension. The sleeve 33 is preferably embodied as a metallic part and exhibits a particularly good thermal conductivity. The sleeve 33 can contain the materials copper, brass, silver and other materials which have particularly good heat conducting properties.
[0033] As a result of the fact that the ridges of the sleeve 33 are bent outward, they form a contact for the purpose of heat transfer with the housing 1 . The edge areas of the sleeve 33 cause the sleeve 33 to abut the compensating element 6 . A continuous conduction of heat is thus provided between the housing 1 and the compensating element 6 .
[0034] It can of course be provided that the ridges 34 of the thermally conducting element 33 are bent inward, with the edge parts 35 of the sleeve 33 abutting the internal wall of the housing 1 and the inward-curved ridges 34 coming into contact with the compensating element. The essential point is that the thermally conducting element does not impede or prevent the movement of the compensating element 6 due to thermal expansion. Toward that end the thermally conducting element 33 must permit a slipping movement between the compensating element 6 and the thermally conducting element 33 or, as the case may be, between the thermally conducting element 33 and the internal wall of the housing 1 .
[0035] A plurality of thermally conducting elements 33 can also be provided in order to improve the conduction of heat between the housing 1 and the compensating element 6 . This increases the contact area between the internal wall of the housing 1 and the sleeve 33 or, as the case may be, between the sleeve and the compensating element 6 , thereby speeding up the temperature compensation. In this way the thermal stresses which can be produced as a result of different temperatures of housing 1 , actuator element 2 and compensating element 6 are reduced.
[0036] It can further be provided that the thermally conducting element 33 is embodied as a tensioned element which is in contact with the compensating element and the internal wall of the housing 1 under a mechanical tension. Such elements can be curved laminae, for example.
[0037] A further embodiment of a sleeve is shown in FIG. 3 . The sleeve 33 is split down its entire length and is preferably manufactured from a flexible material. This enables the sleeve 33 to make a better fit with the internal wall of the housing 1 and/or the compensating element 6 .
[0038] The important point for the thermally conducting element 33 is that it provides an improved conduction of heat between housing 1 and compensating element 6 .
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An injection module comprises a housing ( 1 ), inside of which an actuator element ( 2 ) and an injection valve are arranged. The actuator element ( 2 ) is designed for controlling the injection valve by a setting stroke. A compensating element ( 6 ) is provided that is connected to the actuator element ( 2 ) in order to compensate for the change in length of the housing ( 1 ) caused by thermal expansion.
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TECHNICAL FIELD
[0001] The present invention relates to a surface covering, in particular to a floor, ceiling or wall covering, comprising panels, including laminate flooring panels, and an extraneous locking element.
PRIOR ART
[0002] A variety of different kinds of surface coverings, in particular floor, ceiling or wall coverings are known in the art. In particular for interior applications, rectangular panels sometimes having the appearance of wood boards or ceramic tiles are quite common.
[0003] Such panels are often provided on one side with a decor for example to reproduce the appearance of a real wood panel. This decor can be provided either as a printed paper layer or a veneer, or the decor can be directly printed onto the carrier board. Often, these panels are of rectangular shape and can be coupled to each other using complementary coupling means which commonly are formed as integral parts at the panel sides. Thus, similar panels can be connected at corresponding adjacent sides to form, for example, a floor covering. Among these coupling means in particular various kinds of tongue and groove based coupling means are known which allow for form fitting connections between similar panels by introducing the tongue of one panel into the groove of another panel. To lock the panels together in horizontal and vertical directions, the coupling means are further provided with suitable locking elements, which allow the panels to be firmly locked to each other. Thereby it is possible that such tongue and groove coupling means with additional locking elements can lock respective coupled panels perpendicular to their common connection joint as well as perpendicular and parallel to the panel plane without the need of additional locking means such as glue or nails.
[0004] In the case of rectangular panels, it is common that panels are provided with two different kinds of coupling means, one for the longitudinal sides and one for the transversal sides. This is often necessary because connection means that work well on a relatively short side (e.g. the transversal side of flooring panels) do not necessarily work well on distinctly longer sides (e.g. the longitudinal sides of flooring panels) and vice versa.
[0005] For example, two opposing longitudinal sides of such panels can be provided with tongue and groove coupling means, which allow similar panels to be connected to each other at adjacent longitudinal sides by angling. Angling in this sense means introducing the tongue into the groove and then laying the panel by a rotational (angling) movement into the laying plane. Often with such systems, the transverse opposing sides of these panels can be provided with coupling means which allow similar panels to be connectable to each other at adjacent transverse sides by vertical folding. Folding in this sense means that the transversal locking means are joined into each other (folded down) by the rotational, scissor-like movement caused by angling around the longitudinal side. This combination of coupling means allows that a panel can be connected to a row of similar panels by angling this panel along corresponding longitudinal adjacent panel sides, while within the same working step this panel is connected to neighboring panels by vertical folding to corresponding adjacent transverse panel sides. Such panel systems are generally called “angling” and/or “fold down systems”.
[0006] An example of such a fold down system is described in WO 01/51732. This document describes angling with a tongue-and groove system on a longitudinal side plus additional tongue and groove coupling means on the transverse sides which include hook-shaped coupling members. Upon folding down of panels at corresponding transverse sides, a transverse tongue of one panel is inserted into a corresponding groove of another panel by the angling motion. To increase the stability of this connection, WO'732 discloses to insert an extraneous locking element into a channel, which is formed by the transverse coupling means. To form this channel, a recess is provided in the transverse tongue which in coupled condition, when two panels are connected to each other, opposes a corresponding recess provided in an adjacent transverse groove. After coupling two panels, the extraneous locking element is inserted into this channel to lock the two panels in a direction perpendicular to their transverse sides and perpendicular to the panel plane.
[0007] Similar coupling mechanisms in which extraneous locking elements are used to lock the transverse sides of panels with each other are e.g. WO 2003/016654 and WO 2007/079845. All these solutions have in common that they utilize relatively complex geometries at the transverse sides. Such geometries with many different surfaces are difficult to machine and require several milling tools and milling passes. These solutions use additional tongue and groove systems or hook-like measures on the transverse side to eliminate relative horizontal movement and an extraneous locking element being inserted into grooves on the transverse side to eliminate vertical and rotational movement.
[0008] It is very expensive to maintain milling tools for such complicated profiles with many surfaces over time because the necessary tight tolerances can not be met if the milling tools wear over time. Constant maintenance and replacement of tools as well as the stopping of production facilities for maintenance is cost intensive.
[0009] Above this, in order to mill such profiles on the transverse sides, a portion of the material of a panel is milled away and thus lost if it cannot readily be recycled. In the case of most wood based materials (such as MDF, HDF, chip boards and OSB boards) not only the wooden material is lost, but often also components of a chemical binder (resin or the like) are milled to a potentially hazardous and flammable fine dust which may be difficult and costly to dispose of.
[0010] Another disadvantage of such prior art is that such complicated profiles cannot be employed on relatively thin panels. With such a tongue- and groove system on the transversal sides, a long and thin lever is left at the short ends of panels, which is easily damaged or broken off during transportation and during installation.
[0011] A further disadvantage of the above prior art is that such profiles demand some amount of overlapping of two panels on the transverse side. While this overlapping portion may seem to be only a small percentage of the overall surface of a panel, it is a waste which translates directly into higher costs for customers.
[0012] A locking system which overcomes some of these defects is disclosed in DE10044016. In DE'016, a dovetail shaped groove together with an insertable locking element is disclosed. Additionally DE'016 also discloses that it is useful for two panels to directly touch only in an upper region, leaving a gap below such an upper region.
[0013] A basic problem which arises from connections with dovetail like grooves such as in DE'016, is that they require undercuts. Such undercuts are difficult to mill and again require a set of several different milling tools and techniques with a set of different corresponding cutting surfaces which must be aligned relative to each other and thus the tools need to be maintained regularly in order to keep tolerances. A relatively high amount of defective products may also be a further consequence of such complex profiles. As with the other prior art further above, they are relatively complex and expensive to produce.
[0014] A further disadvantage of DE'016 is that the disclosed dovetail shaped connecting element may be difficult to insert into its groove due to friction. While the amount of friction on a relatively short transverse side of a panel may not pose a problem to manual insertion, the amount of friction on a standard length flooring panel (1300 mm) renders the dovetail shaped connecting element of DE'016 unusable on longitudinal sides of standard flooring panels.
[0015] Another disadvantage from DE'016 arises when a large load (such as heavy furniture) is placed on one panel next to another panel which carries no load at all. Due to the elasticity of the panels and the often elastic underground (a sound insulation layer, for example), a strong rotational force may be applied to the dovetail shaped connecting element. The shape and the dimensions of the dovetailed connecting element of DE'016 are not well suited to efficiently counteract such rotational forces.
[0016] EP 1119670 generally discloses connection profiles with undercuts and hook shaped elements. Such profiles may be achieved by broaching or by laser cutting according to EP'670, two methods known to be tedious, slow and expensive. The only profile mentioned in EP'670 which could be achieved by traditional methods such as milling, is not well suited for reliable connections. It cannot accommodate large separative forces, neither in horizontal, vertical, nor in rotational directions.
SUMMARY OF THE INVENTION
[0017] It is an object of the present invention to improve the state of the art by providing simple, reliable, durable and cheap coupling means which are easily manufactured and especially well suited for thin panel geometries.
[0018] This and other objects which become apparent upon reading the following description, are solved by a surface covering kit according to claim 1 .
[0019] According to the present invention, a surface covering, for example a flooring, ceiling or wall covering, is provided, comprising panels and at least one extraneous locking element. Generally, such panels can be made of any material such as wood or wood based material, veneer, natural or synthetic fibrous material, metal, metallic alloys, plastic, foams, ceramics, rubber or the like or also of any layered materials. The invention is especially well suited for panels made of HDF, MDF, OSB, chip boards and panels which are made of wood, wood based materials and laminate. The panels can be provided with a decor, as for example a real wood imitation, a stone imitation or a ceramic imitation, in form of a separate decor paper or the decor may alternatively be directly printed onto the panels.
[0020] In the case of laminate flooring where the decorative layer is provided as a paper, further layers are normally added above and below the core. Usually at least one more layer known as overlay will be added on top of the decorative layer to obtain better wear resistance.
[0021] Each panel is provided with parallel, opposing longitudinal sides and parallel, opposing transverse sides, whereby these sides are provided with respective longitudinal and transverse coupling means, which preferably are formed as integral components of the panel sides and which serve for connecting similar panels at their corresponding adjacent sides.
[0022] The present invention offers a simple, reliable and very stable connection by providing grooves on each transverse side to be connected, the grooves forming an insertion channel when two panels are laid next to each other along their transverse sides in a common laying plane, and by providing at least one extraneous locking element adapted to be received by said insertion channel along an insertion direction in parallel to the transverse side to lock two adjacent panels to each other relative to a first direction parallel to their common laying plane and perpendicular to the transverse sides as well as relative to a second direction perpendicular to their common laying plane. The extraneous locking element has a longitudinal dimension and a cross-section perpendicular to said longitudinal dimension which substantially forms a cross with at least four cross arms. Each cross arm has two substantially parallel flank surfaces each. The grooves are oriented in such a manner that each of the cross arms is oriented diagonally between said first and said second directions when said extraneous locking element is received by said insertion channel.
[0023] The term “diagonally between said first and said second directions” is to be understood to relate to a configuration in which each arm extends at an angle relative to each of these directions, wherein this angle is between 15° and 75°, preferably between 30° and 60°.
[0024] The cross-shaped cross-section of the extraneous locking element geometrically provides just enough surfaces to resist attacking forces onto the connection from all possible directions, except of course in parallel to the direction of insertion of the extraneous locking element. The latter however is highly desirable because then two such connected panels can later be disassembled and separated again by pulling them apart by exerting opposing forces in parallel to the insertion direction between two panels. The extraneous locking element can then be similarly removed from the channel by again exerting opposing forces in parallel to the insertion direction between the panel and the locking element.
[0025] The cross-shape of the cross-section is chosen because it is the simplest geometry which can reliably oppose forces in all desired directions, both horizontal and vertical. Additionally, the cross-shape of the cross-section of the extraneous locking element is very well suited to oppose rotational forces which occur if a large load is placed on one panel next to another panel without load (for example a furniture load). A cross-shape of the cross-section of the extraneous locking element with four arms and preferably with two substantially parallel flank surfaces on each of the arms has more surfaces efficiently opposing a rotational movement than a similarly dimensioned dovetail-shaped cross-section would have. Since the cross-arms of the cross-shape of the present invention are essentially diagonally opposed to each other, they provide optimum stability, using a minimal geometrical footprint at the same time.
[0026] A cross-shape of the-cross section of the extraneous locking element with two substantially parallel flank surfaces per arm is preferably chosen because it is exceptionally easy to mill channels receiving such a locking element precisely by rotating milling or sawing wheels with equally parallel surfaces. The free end or tip of each cross arm can be another flat surface or a rounded surface or the like. The arms of the cross each point away from the cross center, so that all cross arms lie in planes which are oriented diagonally between the laying plane and the transversal sides.
[0027] The cross-shape of the cross-section of the extraneous locking element also provides resistance against bending, both during insertion of the extraneous locking element and also after installation, when differential loads might be applied to the panels.
[0028] In a preferred embodiment, the cross-section of the insertion channel is also cross-shaped. In this case, each transverse side of the panels is provided with two grooves which are generally in parallel to the transverse side, but essentially lie in two planes which are inclined towards each other. When two panels which are to be connected are laid next to each other, the then four grooves form a channel with a cross-shaped cross-section. Such channels are exceptionally easy to manufacture, while optimal interaction between the insertion channel and the locking element can be ensured.
[0029] Because the locking means according to the present invention are intended to work well with very thin panel geometries, the cross-shape of the cross-section of the extraneous locking element and/or of the insertion channel is preferably chosen to be somewhat broader along the first direction than high along the second direction (i.e., the cross appears somewhat flattened, the angles between each cross arm and its two neighbors being somewhat different, with a difference of, e.g., 10°-60°). This geometrical compromise results in a connection which is still very reliable against especially horizontal parting forces, but does not unnecessarily thin the panel material above and below the insertion channel with the cross-shaped cross-section. This is essential to make the grooves more stable against fracture and thus the panels more resistant to the tearing out of the extraneous locking elements out of their respective grooves.
[0030] Since a careful balance between locking stability and insertion friction of the extraneous locking element must be found, measures to reduce friction upon manual insertion will also be presented for preferred embodiments.
[0031] The terms “longitudinal” and “transverse” as used herein do not include any limitations with regard to the relative lengths of both sides but are merely used in order to differentiate the different sides of the panel for the sake of a facilitated description. Thus, while usually the longitudinal side is the longer side of a panel and the transversal side is the shorter side, the extraneous locking element of the present invention can of course also be used in connection with the longer side of a panel or with panels in which longitudinal and transverse sides have the same length, i.e. with square panels.
[0032] In this sense, the locking element with the cross-shaped cross-section according to the present invention can be used both on the long and on the short sides. However, since the friction during insertion of the locking element can become excessively large for long panels such as standard 1300 mm length flooring panels, the locking element according to the present invention is preferably used on the short sides in combination with an angling profile on the long sides.
[0033] It is advantageous for the locking stability that all angles between the cross arms of the cross-shaped cross-section of the insertion channel (and correspondingly of the extraneous locking element) are larger than 30, and preferably larger than 45 degrees.
[0034] It is advantageous for the ease of insertion of the locking element and for the locking stability, if the aspect ratio of the total length between the tips (free ends) of two diagonally opposed cross arms divided by the width of the cross arms is smaller than 10 and preferably smaller than 8, but larger than 2 and preferably larger than 2.5.
[0035] The cross-shaped cross-section of the insertion channel (and thus also of the extraneous locking element) will generally have a double plane symmetry by being symmetric about a first plane parallel to the transversal side and about a second plane parallel to the panel plane; however, asymmetric cross shapes are conceivable as well.
[0036] It is advantageous for the stability of the insertion channel if a minimal thickness (h min ) of panel material between the insertion channel and an upper or lower panel surface is not smaller than one tenth, and preferably not smaller than one eighth of the overall thickness of a panel.
[0037] It is advantageous for the ease of insertion of the extraneous locking element that the locking element has between one and four friction reducing grooves near the center of the cross. These grooves each mainly extend in parallel to the longitudinal dimension of the extraneous locking element and each groove is located in a region where adjacent cross arms of the extraneous locking element meet. The cross-section of these grooves extend partially inward from the flank surfaces towards the cross center and can have any arbitrary form such as being V- or U shaped, but generally round and partial-circle shaped cross sections are preferred.
[0038] It is advantageous for the ease of insertion of the extraneous locking element that at least one of the cross arms of the extraneous locking element has wavelike protrusions and grooves on its outer surfaces. The wavelike protrusions and grooves extend in parallel to the longitudinal dimension of the extraneous locking element.
[0039] It is advantageous for the ease of insertion of the extraneous locking element that at least one of the four cross arms of the extraneous locking element is split by a surface which extends in parallel to the longitudinal dimension of the extraneous locking element and inward partially from the tip of a cross arm towards the center of the cross.
[0040] It is advantageous for the stability of the locking, if those two cross arms which extend towards the upper surface of a panel are upper arms and those two cross arms which extend towards the lower surface of a panel are lower arms, when the extraneous locking element is inserted into the insertion channel, an elastic pretension is applied to the connection by pre-bending the upper arms of the extraneous locking element upwardly and the lower arms downwardly relative to the corresponding cross arms of the insertion channel. This pre-bending can be achieved either by applying an angle between the two upper and/or between the two lower cross arms of the extraneous locking element which is slightly smaller (preferably by less than 20°, more preferably by less than 10°) than the corresponding angles between the upper and the lower cross arms of the insertion channel; and/or by applying a small amount of upwardly respectively downwardly bending curvature on the cross arms of the extraneous locking element.
[0041] It is advantageous for the ease of insertion of the extraneous locking element that at least one of the cross arms of the extraneous locking element is interrupted along its longitudinal dimension by one or more gaps. These gaps can have any arbitrary length, number and depth, but preferably the gaps are provided in regular intervals on all arms and extend only partially inwards from the tips of the cross arms towards the center of the cross and most preferably extend only half way inwards from the tips of the cross arms towards the center of the cross.
[0042] For some material pairings and geometries, it can be advantageous if the total length of the extraneous locking element is shorter or even significantly shorter than the total length of the transversal side. For laminate flooring panels however, a total length of the extraneous locking element which is nearly equal to the total length of the transversal side is preferred.
[0043] It is advantageous for the ease of insertion of the extraneous locking element that the ends (tips) of the locking element are rounded or beveled or even that the locking element conically grows thinner towards its ends.
[0044] It is advantageous for the ease of insertion of the extraneous locking element and also to accommodate mild expansion and contraction of the panels, to provide a compensation groove mainly extending in parallel to and in between the transversal sides with two substantially parallel flanks. This compensation groove is provided between two adjacent panels on their transversal side, such that a lower part of the groove extends all the way between the center of the cross of the insertion channel and the lower panel surface; and an upper part of the groove extends from the center of the cross of the insertion channel upwards only partially towards the upper panel surface.
[0045] It is advantageous for the ease of insertion of the extraneous locking element, if one or two lateral friction reducing grooves are provided on one or two of the transversal sides of the panels. These lateral grooves mainly extend in a direction in parallel to the transversal sides of the panels and in the panel plane. If the insertion channel has a cross-shaped cross section, each friction reducing groove preferably extends outward from the center of the cross of the insertion channel only partially towards a surface between the tips of the arms of the insertion channel, i.e. it does not extend outward from the center of the cross of the insertion channel all the way towards the surface between the tips of the arms of the insertion channel, so that sufficient resistance of the locking against rotational forces is still maintained.
[0046] It is advantageous for the laying of the panels, if each panel is provided with at least one protruding lip on one transversal side below the insertion channel on the lower panel side, and each panel is also provided with at least one corresponding recess on the opposing other transversal side below the insertion channel and the lower panel side such that a laying aid is formed when the recess is laid onto the protruding lip. This laying aid is intended to align the two halves of the insertion channel so that the locking element can easily be inserted. For simplicity, the laying aid is preferably provided on the whole length of the transversal side, but alternatively it can also be provided partially or only near one or two of the ends of the transversal side. The laying aid may also be provided in the form of a thin plastic strip attached to the panel below one transversal side. No recess is necessary in conjunction with such a plastic strip.
[0047] It can be advantageous for the resistance against rotational forces for some material pairings and geometries, if the extraneous locking element has a cross-section with six cross arms instead of only four cross arms. For material pairings however in which the grooves of the insertion channel tend to break or tear easily, such as in thin MDF, HDF or LDF laminate flooring, four cross arms are preferred.
[0048] It can be advantageous for the person inserting the locking elements that the extraneous locking element has portions of the two upper arms of the cross marked in some manner or colored in a distinctly different color than the two lower arms. This helps to prevent faulty insertions by wrongly rotating the extraneous locking element before insertion.
[0049] Since it can be difficult to insert extraneous locking elements which are very long, it is advantageous if each panel additionally has a profile with a tongue on one longitudinal side and a groove on the opposed longitudinal side. This groove preferably has an upper lip and a lower lip, the lower lip having an upwardly extending locking protrusion and the tongue being adapted to be introduced into the groove, thus enabling an adjacent panel to be angled down on the longitudinal side, so that locking of the longitudinal side is achieved in parallel to their common laying plane by the upper lip and the lower lip and perpendicular to the longitudinal side by the locking protrusion. In other words, an angling profile and system can further be provided on the longitudinal sides.
[0050] It is advantageous for the locking stability if the extraneous locking element has a first tip at one of its ends which is dimensioned to partially fit into the corresponding groove on a longitudinal side of a previously laid panel element. Such a tip has to be dimensioned in such a way that it can be maneuvered through the cross-shaped cross-section of the insertion channel, past the locking protrusion and into the longitudinal groove and under its upper lip, thereby providing locking stability at a triple panel junction.
[0051] It is advantageous for the locking stability, if the extraneous locking element has a second tip on the end of the locking element opposed to the first tip and this second tip forms the same groove as the longitudinal profile with an upper lip and a lower lip and a locking protrusion. This enables that the tongue of a panel on the longitudinal side can also be introduced into the portion of the longitudinal groove which is partially formed by the second tip of the extraneous locking element when element is inserted into the insertion channel.
[0052] A corresponding laying method for a surface covering comprises:
[0053] (a) providing a surface covering kit as described above;
[0054] (b) laying a first row of panels by laying the panels of the first row side by side along their transverse sides in a common laying plane;
[0055] (c) inserting an extraneous locking element into each insertion channel along the insertion direction to lock each pair of adjacent panels to each other relative to the first direction and the second direction;
[0056] (d) providing a second row of panels parallel to the first row, wherein each panel of the second row is preferably connected to the first row by angling;
[0057] (e) inserting an extraneous locking element into each insertion channel along the insertion direction to lock each pair of adjacent panels of the second row to each other relative to the first and second directions; and
[0058] (f) repeating steps (c) to (e) for each further row of panels.
BRIEF DESCRIPTION OF THE DRAWINGS
[0059] Preferred embodiments of the invention are described in the following with reference to the drawings, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same. In the drawings,
[0060] FIG. 1 shows the laying and the relative positions of panels according to the present invention in a perspective view.
[0061] FIG. 2 shows the laying and the relative positions of panels according to the present invention in a view perpendicular to the laying plane.
[0062] FIG. 3 shows the cross section of a transversal connection according to the present invention.
[0063] FIG. 4 exemplarily shows the cross section of a longitudinal connection of a preferred embodiment.
[0064] FIG. 5 exemplarily shows the cross section of a longitudinal connection of a different preferred embodiment.
[0065] FIG. 6 shows a cross section of a transversal connection according to the present invention.
[0066] FIG. 7 shows a cross section of a transversal connection of a preferred embodiment of the present invention.
[0067] FIG. 8 shows a cross section of a transversal connection of a preferred embodiment of the present invention with a laying aid.
[0068] FIG. 9 shows a preferred embodiment of the cross-shaped cross-section of the extraneous locking element according to the present invention
[0069] FIG. 10 shows a less preferred embodiment of the cross-shaped cross-section of the extraneous locking element according to the present invention with two additional arms.
[0070] FIG. 11 shows a preferred embodiment of the cross-shaped cross-section of the extraneous locking element according to the present invention with wave-like grooves and protrusions.
[0071] FIG. 12 shows a preferred embodiment of the cross-shaped cross-section of the extraneous locking element according to the present invention with split arms.
[0072] FIG. 13 shows two embodiments of the extraneous locking element according to the present invention in a lateral view
[0073] FIG. 14 shows design principles of the cross-shaped cross-section of the extraneous locking element according to the present invention.
[0074] FIG. 15 shows a less preferred embodiment of the cross-shaped cross-section of the extraneous locking element according to the present invention.
[0075] FIG. 16 exemplarily shows a principle of milling the grooves of the cross-shaped cross-section of the insertion channel according to the present invention.
[0076] FIG. 17 shows the tip of the extraneous locking element of a preferred embodiment.
[0077] FIG. 18 shows the tip of the extraneous locking element of a preferred embodiment.
[0078] FIG. 19 shows the tip of the extraneous locking element of a preferred embodiment.
[0079] FIG. 20 shows both ends of the extraneous locking element of a preferred embodiment for a locking of three panels.
[0080] FIG. 21 shows both ends of the extraneous locking element of a preferred embodiment for a locking of four panels.
[0081] FIG. 22 shows a perspective view of the extraneous locking element together with a cut though preferred longitudinal locking means.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0082] FIG. 1 is a schematic illustration showing three exemplary panels 100 laid in a common plane 101 . These panels 100 can be made of any suitable material, however the invention is especially well suited for laminate panels made from HDF, MDF or LDF. The panels 100 can also be made of a wood composite, real wood, veneer, chip boards or OSB. The panels 100 have a mean or average thickness in between 3 mm and 30 mm and most preferably in between 4 mm and 14 mm. Since the connecting elements on the transverse sides according to the present invention have such a simple geometry, they are exceptionally well suited for very thin panels, such as 5 mm flooring laminate.
[0083] A decor 103 can either be provided as a separate decor layer, e.g. a decor printed on paper, or can be directly printed onto the panels 100 . The decor 103 can be for example: a real wood imitation, a stone imitation, a ceramic imitation or the like.
[0084] As one can see in FIG. 1 , each panel 100 defines a panel plane 102 and is provided with parallel, opposing longitudinal sides 104 , 104 ′ and parallel, opposing transverse sides 105 , 105 ′. These sides are provided with respective transverse and longitudinal coupling means 400 , 300 which are adapted to connect similar panels 100 at corresponding adjacent sides 104 , 104 ′ and 105 , 105 ′, respectively.
[0085] FIG. 2 is a schematic illustration showing a surface covering 200 comprising panels 201 , 202 , 203 and 204 and an extraneous locking element indicated at reference numeral 210 . It should be noted that in the figure, the extraneous locking element is only drawn for illustrative purposes, while in reality it is covered by the top surface of the panels, and would therefore be invisible in the shown perspective. In FIG. 2 , two panels 201 , 203 of a first row 205 are connected to each other at adjacent transverse sides. The panels 201 and 203 are connected longitudinally with a further panel 202 in a second row 206 and with a further panel 204 in a third row 207 . As one can derive from FIG. 2 , the extraneous locking element is inserted into a channel (the channel is shown in detail in FIGS. 6 , 7 , 8 , 15 and 16 ) formed by the transversal coupling means of panels 201 and 203 , whereby an end portion 211 of the extraneous locking element 210 in a preferred embodiment can protrude on one end to some extent out of said channel and into the groove of the longitudinal coupling means of the panel 202 in the second row 206 . Alternatively or additionally, the opposite end 211 ′ of the extraneous locking element 210 can protrude a little bit out of the other end of the channel. This will be illustrated further in FIGS. 17-21 .
[0086] The locking element 210 can be made of any suitable material with a favorable friction coefficient, such as plastic, PTFE, aluminum alloys, steel or even wood or wood based materials.
[0087] FIG. 3 shows a cross section of the transverse coupling means 300 . A transverse side 105 is provided with two geometrically simple grooves 301 and 302 along the transversal side. An opposing transverse side 105 ′ is equally provided with the same grooves 301 ′ and 302 ′. All together, the four transversal grooves 301 , 302 , 301 ′ and 302 ′ form an insertion channel 303 which has an cross-shaped cross section on the whole length of the transversal sides 105 and 105 ′.
[0088] Once two transversal sides 105 and 105 ′ are laid in parallel and next to each other and in the same common laying plane, an extraneous locking element 210 is inserted into the corresponding channel 303 , whereby the panels are locked perpendicular to transversal panel sides 105 , 105 ′ and perpendicular to the common laying plane 101 . It is emphasized that no undercuts or additional profile surfaces or additional transversal coupling means are necessary to achieve this locking. Furthermore, an inward, respectively downward bending along transversal sides 105 of the panel surface is prevented by the locking element 210 .
[0089] In the embodiment of FIG. 3 , compensation grooves are machined above 305 and below 306 the insertion channel 303 into the panels. These grooves serve two purposes: they can help to accommodate some mild contraction and expansion since the panels only have contact on a small surface 307 , and additionally the grooves 305 and 306 significantly reduce friction when the extraneous locking element 210 is inserted.
[0090] FIG. 3 also shows forces attacking perpendicular to the transversal sides 311 and perpendicular to the common laying plane 312 . A strong load on one panel may result in rotational forces 310 . The surfaces of the extraneous locking element 210 and the corresponding channel 303 are well suited to counteract such rotational forces, no additional surfaces or undercuts are therefore necessary.
[0091] The extraneous locking element 210 shown in FIG. 3 thus provides excellent mechanical locking properties. However, it may be difficult to manually insert this locking element into its corresponding insertion channel 303 during assembly of panels with large dimensions because friction increases with the length of the locking element. For this reason, the locking element of the present invention is preferably employed on the short sides, while an “angling” system with a tongue-and groove locking system is preferably employed on long sides. The length of the extraneous locking element 210 according to the present invention may be any arbitrary length, ranging from anywhere between 1 cm up to the overall dimension (including the locking means) of a transversal side. In preferred embodiments however, the length of the extraneous locking element is nearly equal to the overall dimension (including the locking means) of a transversal side.
[0092] FIG. 4 exemplarily shows preferred coupling means 400 on a longitudinal side 104 . These coupling means comprise a tongue 401 on one longitudinal side 104 and a corresponding longitudinal groove 402 on a opposing longitudinal side 104 ′. The longitudinal groove 402 comprises a lower lip 403 which is arranged close to a bottom side 309 of a panel 100 and an upper lip 404 which is arranged close to the upper side 308 of a panel which carries for example the visible decor 103 . As one can see, and this arrangement is preferred with any kind of longitudinal coupling means used in connection with the present invention, the lower lip 403 is longer than the upper lip 404 and the lower lip 403 is provided with a locking protrusion 405 at its free end which extends upwardly from the lower lip 403 to be inserted into a corresponding recess.
[0093] It can be recognized from FIG. 4 , that these coupling means can be closed by moving the tongue 401 into the groove 402 at an angle, and by subsequent rotation along arrow 406 . After this rotation (angling), the locking element 405 fixes the mechanism such that the corresponding panels are locked perpendicular to adjacent longitudinal sides 104 and perpendicular to the laying plane as well as in parallel to the laying plane.
[0094] FIG. 5 exemplarily shows a variation of these principles and elements for longitudinal coupling means 400 known as such from prior art (CH562377), the difference being here that more generally rounded surfaces are used.
[0095] FIG. 6 shows a preferred cross section of the transverse coupling means 300 with relative dimensions suitable for 6 mm laminate flooring panels. For clarity, the extraneous locking element 210 is left out of its channel 303 in this figure. In this embodiment, the gaps 305 and 306 of FIG. 3 are not present. As can be deducted from this figure, the locking elements 300 on the transversal side of panels according to the present invention are especially well suited for thin panels due to their simple geometry. A minimal thickness of panel material h min must be left between the upper transversal channel groove 301 and the panel surface as well as between the lower transversal channel groove 302 and the panel surface, so that the panel will not break along the transversal grooves 301 or 302 when large loads are applied. The thickness h min depends on the material of the panels, the thickness of the panels and the forces to be expected (e.g. surface loads such as furniture or the like). In this drawing, the height h min is in proportion for typical 6 mm laminate.
[0096] Preferably the minimal thickness h min of the panel material above and below the transversal insertion channel 303 shall be greater than one tenth of the panel thickness and preferably greater than one eighth of the panel thickness.
[0097] In FIG. 6 , the length of a double arm of the cross in the cross-shaped cross section of the insertion channel 303 is indicated by the letter b, while its width is indicated by the letter a. The aspect ratio of b divided by a governs the relative surface of the insertion channel and the extraneous locking element and thereby also the friction upon insertion.
[0098] Preferably the aspect ratios for b divided by a are smaller than 10 and preferably smaller than 8. The aspect ratio of b divided by a also governs the ability of the extraneous locking element to resist rotational forces. This is why b divided by a should preferably not be smaller than 2 and preferably not smaller than 2.5.
[0099] An additional measure to reduce friction upon insertion of the extraneous locking element 210 is to eliminate contact surfaces between the insertion channel 303 and the extraneous locking element 210 in those places that do not sacrifice too much connection stability. This is a task of the upper and lower transversal gaps 305 and 306 in FIG. 3 .
[0100] FIG. 6 also shows relative dimensions which have proven to be advantageous for 6 mm laminate flooring with an MDF or an HDF core: The length b of the double cross arm is 4.6 mm, the width of a cross arm a is 1.4 mm and the height h min is 1.3 mm. Minimal heights of h min smaller than 0.5 mm have proven to be unpractical for wood based materials.
[0101] FIG. 7 shows additional means to reduce friction upon insertion of a preferred embodiment by eliminating some of the contact surface between the upper and the lower transversal grooves 301 and 302 . This is done by providing an additional lateral groove 700 . The depth of the lateral groove 700 is chosen to be smaller than the minimal distance between transversal panel surface 307 and the tips of the arms of the cross in the cross-shaped cross-section of the insertion channel 303 , so that the extraneous locking element still provides enough resistance against rotational forces because the ends of the arms are still locked.
[0102] FIG. 8 shows a preferred embodiment of the transversal coupling means 300 where a lip 800 and a recess 801 have been added in order to provide an alignment and laying aid when laying the panels on a slightly irregular or elastic underground. The protruding lip 800 is located on one transversal side 105 ′ between the insertion channel 303 and the lower panel side 309 , the corresponding recess 801 is located on the opposing transversal side 105 . This laying aid makes it easier to insert the extraneous locking element 210 into the thereby aligned channel 303 .
[0103] FIG. 9 shows a preferred embodiment of the cross-shaped cross-section of the extraneous locking element 210 according to the present invention. Up to four friction reducing grooves 910 , 910 ′, 910 ″ and 910 ′″ are added near the center of the cross in the region where adjacent cross arms 901 , 902 , 903 and 904 meet.
[0104] FIG. 10 shows another embodiment of the cross-shaped cross-section of the extraneous locking element 210 according to the present invention. In this embodiment, two additional arms 1001 and 1002 have been added to the cross-shaped cross-section of the extraneous locking element 210 . While these additional two arms contribute additional resistance to rotational forces, they do not contribute to resistance against horizontal forces. Especially in the case of thin panels, they might thin the panel material between the arms (for example between the arms 901 and 1001 ). This thinning may assist the rupture of the transversal channel grooves under severe loading conditions. Furthermore, the two additional grooves 1001 and 1002 must be milled at additional cost. Therefore, the embodiment of FIG. 10 may be less preferred.
[0105] FIG. 11 shows a further preferred embodiment of the cross-shaped cross-section of the extraneous locking element 210 . In this embodiment, wave shaped protrusions 1101 and grooves 1102 have been added along the outline of the cross-shaped cross-section of the extraneous locking element 210 . These protrusions, which may also be developed as teeth with an outwardly facing locking direction, significantly add locking stability without adding friction.
[0106] FIG. 12 shows a further preferred embodiment of the cross-shaped cross-section of the extraneous locking element 210 . In this embodiment, one or more of the arms of the cross-shaped cross-section of the extraneous locking element 210 are split by a surface which extends in parallel to the longitudinal dimension of the extraneous locking element 210 and inward partially from the tip of a cross arm 901 , 902 , 903 , 904 towards the center of the cross. This splitting serves the purpose of providing elastic compressibility of the arms of the cross of the extraneous locking element during insertion and thus reduces friction.
[0107] FIG. 13 shows two lateral views of preferred embodiments of extraneous locking elements 210 and 210 ′ according to the present invention. In the upper embodiment 210 , the arms of the cross are fully developed over the whole length of the extraneous locking element. In the lower embodiment 210 , portions 1301 of the arms are left out at intervals in order to reduce friction upon insertion.
[0108] Especially with wood based materials, debris in the form of dust is often left by a milling process. Grooves such as 305 , 306 , 700 , 910 , 1301 as well as the splitting shown in FIG. 12 serve the double friction reducing purpose of reducing the contact surface between the transversal insertion channel 303 and the extraneous locking element 210 and additionally also to accommodate some amount of milling debris (such as saw dust) so that said debris does not have to be pushed all along the whole length of the insertion channel 303 and thereby be accumulated at the tip of the locking element 210 during insertion.
[0109] FIG. 14 illustrates some design principles of the cross-shaped cross-section of the extraneous locking element 210 .
[0110] Left side: in order to obtain small and simple geometries, it is advantageous to choose an angle α 1 which extends between two flank surfaces 905 , 905 ′ of the upper arms 904 and 901 of the cross, so that α 1 is slightly larger than 90 degrees. This helps to maintain a minimal thickness h min as described in FIG. 6 because the overall height of the locking element is reduced (h 2 <h 1 ) without sacrificing too much locking stability. Preferred embodiments of the present invention comprise an angle α 1 larger than 90 degrees and more preferably larger than 100 degrees but not larger than 150 degrees. This enables the extraneous locking element 210 to be smaller in its vertical dimension than in its horizontal dimension. If the angle α 1 is chosen to be larger than 150 degrees (or accordingly the complementary angle is β thus chosen to be smaller than 30 degrees), the arms 901 , 902 of the cross-section of the locking element 210 are not well suited to resist paring forces perpendicular to the transversal sides 105 , 105 ′ any more.
[0111] Right side: If the grooves in the transversal insertion channel 301 and 301 ′ are machined under an angle α 1 and a slightly smaller angle α 2 is chosen between the upper arms of the cross in the cross-shaped cross-section of the extraneous locking elements 210 (i.e. between the arms 901 and 904 ), an elastic pretension pulling two transversal sides towards each other can be obtained. However, this pretension often comes at the cost of increased friction. This is why the angle α 1 between the transversal channel grooves should not be larger than the angle α 2 by more than 20 degrees and more preferably by no more than 10 degrees between the upper arms of the extraneous locking element (before installation) in preferred embodiments.
[0112] This figure also shows that the cross-shaped cross section of the extraneous locking element 210 is preferably symmetrical in both a vertical plane 1401 and in a horizontal plane 1402 . This makes the manufacturing of the insertion channel 303 and the extraneous locking element 210 exceptionally easy and also error safe against wrong insertion during installation.
[0113] FIG. 15 shows a less preferred embodiment of the extraneous locking element wherein the locking is not achieved by a tight geometrical fit of the arms 901 , 902 , 903 and 904 into their respective channels 301 , 302 , 302 ′ and 301 ′, but rather totally by elastic pretension. For this type of locking element, steel or preferably even spring steel is chosen as material.
[0114] FIG. 16 shows in principle how the transversal channel grooves 301 and 302 respectively 301 ′ and 302 ′ can easily and rapidly be cut by a rotating milling- or sawing wheel 1600 . Here only one cutting wheel for the channel 302 ′ is shown. Such cutting wheels may be operated at very high cutting speeds and at low costs. The transversal insertion channel grooves 301 and 302 are essentially cut homogeneously all along the transversal sides 105 .
[0115] Since the surfaces 1601 and 1602 of such low cost and high speed cutting wheels are essentially parallel to each other, it follows that the lateral flanks of each of the transversal insertion channel grooves such as 1603 and 1604 of the groove 302 ′ and 1603 ′ and 1604 ′ of the groove 301 ′ are also essentially parallel to each other.
[0116] When tongue-and groove angling systems are chosen for the longitudinal connection means 400 of panels of the present invention, the ends 211 and 211 ′ of the extraneous locking elements 210 may be adapted in a way that they usefully strengthen the connection between three or even four panels at the same time.
[0117] FIG. 17 exemplarily shows the adaption of a tip 211 of the extraneous transversal locking element 210 according to the present invention when it is used in conjunction with a longitudinal tongue- and groove angling system.
[0118] On the right hand side of the vertical dashed line, a cut in parallel to the transverse side of a panel is shown. The cut in this figure runs through the triple point where two panels on their transverse side join a panel on the longitudinal side. In this embodiment of the present invention, the geometry of the groove on the longitudinal side has been chosen so that a thinned extension of the tip 211 of the extraneous locking element 210 can be inserted past the locking protrusion 405 under the upper lip 404 to fit into the groove 402 . This gives additional mechanical locking strength at the triple point junction of three panels which allows for an exceptionally stable connection at the triple junctions. It is emphasized that no alterations are made to the transversal insertion channel 303 or to the cross-shaped cross-section of the extraneous locking element. Only the tip 211 has been modified and thinned to fit into the longitudinal groove 402 .
[0119] On the left hand side of the vertically dashed line, the extraneous locking element 210 is shown in profile in order to demonstrate which regions of the profile are thinned and extended to reach into the groove 402 of the longitudinal side.
[0120] A further advantage of this embodiment is that the tip 211 now has a distinguishable “upper side” where it is thinned and elongated. This is very helpful because now the person installing the cross-shaped locking element 210 cannot easily mistakenly rotate the locking element by 90, by 180 or by 270 degrees. In other words, the person installing the cross-shaped locking element 210 can easily determine how to correctly fit in the extraneous locking element.
[0121] In order to enhance this further, portions of the two upper arms 901 and 904 of the cross of the cross-shaped cross section of the extraneous locking element 210 may additionally be colored in a distinctly different color than the lower arms 902 and 903 .
[0122] FIG. 18 shows the same perspectives and features as in FIG. 17 , however here right angles have been avoided in the region where the tip of the extraneous locking element 210 is thinned out to protrude into the longitudinal groove. The avoidance of sharp or right angles gives additional stability to the tip 211 of the locking element 210 .
[0123] FIG. 19 shows the same perspectives and features as in FIGS. 17 and 18 but with a different tongue and groove profile on the longitudinal side with more curved surfaces. Essential to both longitudinal profiles in FIGS. 17 , 18 and 19 is that there is a gap between the locking protrusion 405 and the upper lip 404 through which an extended tip 211 of the extraneous locking element 210 can be inserted.
[0124] FIG. 20 shows the same perspective and features as in FIGS. 17 , 18 and 19 but here the other end of the transversal locking element 211 ′ is also shown. In this embodiment, the tip 211 of the locking element 210 is developed to fit into the groove 402 at a triple junction, while the other end 211 ′ of the locking element is left blunt. This embodiment of the extraneous locking element locks three panels simultaneously.
[0125] FIG. 21 shows the same perspective and features as in FIG. 20 , but now the end tip 211 ′ of the extraneous locking element has been given the same profile as the longitudinal groove 402 ′. A locking element with these tips 211 and 211 ′ can contribute to the locking of four boards across three rows 207 , 205 and 206 as shown in FIG. 2 . It follows logically from FIG. 21 that extraneous locking elements of this type of embodiment have an overall length which is equal to the overall transversal width of a panel, including its tongue and the groove.
[0126] The groove-shaped slot 402 ′ at the end 211 ′ of the extraneous locking element 210 additionally provides an ideal guide into which a blunt tool such as a screwdriver tip or a spatula or also a custom made insertion tool may be inserted in order aid the manual insertion of the extraneous locking element.
[0127] FIG. 22 shows the same features as in FIG. 17 , but now a perspective view of the locking element 210 and its tip 211 have been added.
LIST OF REFERENCE SIGNS
[0000]
100 Panels
101 Laying plane
102 Panel plane
103 Decor
104 Longitudinal sides
105 Transversal sides
200 Surface covering
201 First panel
202 Second panel
203 Third panel
204 Fourth panel
205 First panel row
206 Second panel row
207 Third panel row
210 Extraneous locking element
211 End portion of extraneous locking element
300 Transversal coupling means
301 Upper transversal insertion channel groove
302 Lower transversal insertion channel groove
303 Transversal insertion channel
305 Upper compensation groove
306 Lower compensation groove
307 Transversal panel contact surface
308 Upper panel surface
309 Lower panel surface
310 Rotational forces
311 Forces perpendicular to the transversal sides
312 Forces perpendicular to the common laying plane
400 Exemplary longitudinal coupling means
401 Longitudinal tongue
402 Longitudinal groove
403 Lower lip
404 Upper lip
405 Locking protrusion
406 Angling direction
700 Lateral friction reducing groove
800 Protruding lip of laying aid
801 Recess of laying aid
901 First arm of the cross of the cross-shaped cross-section of the locking element
902 Second arm of the cross of the cross-shaped cross-section of the locking element
903 Third arm of the cross of the cross-shaped cross-section of the locking element
904 Fourth arm of the cross of the cross-shaped cross section of the locking element
905 First parallel flank surface of a cross arm
906 Second parallel flank surface of a cross arm
910 Friction reducing groove
1001 Additional fifth arm of the locking element
1002 Additional sixth arm of the locking element
1101 Wave-shaped protrusions
1102 Wave-shaped grooves
1301 Gaps
1401 Vertical symmetry plane
1402 Horizontal symmetry plane
1600 Cutting wheel
1601 Upper surface of cutting wheel
1602 lower surface of cutting wheel
1603 Flank of transversal insertion channel groove
1604 Flank of transversal insertion channel groove
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A surface covering kit is disclosed, comprising a plurality of generally rectangular panels ( 100 ). Each panel is provided with grooves ( 301, 302, 301′, 302′ ) forming an insertion channel ( 303 ) when two panels ( 100 ) are laid next to each other along their transverse sides ( 105, 105′ ) in a common laying plane ( 101 ). An extraneous locking element ( 210 ) is received by the insertion channel ( 303 ), the extraneous locking element ( 210 ) having a longitudinal dimension and a cross-section perpendicular to said longitudinal dimension which forms a cross with at least four cross arms. The corresponding cross arms of the insertion channel have two parallel flank surfaces ( 1603, 1604 ) each, and each of the cross arms is oriented diagonally in a plane perpendicular to the panel plane ( 102 ).
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BACKGROUND OF THE INVENTION
[0001] Somatostatin (SRIF), a tetradecapeptide discovered by Brazeau et al., has been shown to have potent inhibitory effects on various secretory processes in tissues such as pituitary, pancreas and gastrointestinal tract. SRIF also acts as a neuromodulator in the central nervous system. These biological effects of SRIF, all inhibitory in nature, are elicited through a series of G protein coupled receptors, of which five different subtypes have been characterized (sstr 1 -sstr 5 ). These five subtypes have similar affinities for the endogenous SRIF ligands but have differing distribution in various tissues. Somatostatin binds to the five distinct receptor (SSTR) subtypes with relatively high and equal affinity for each subtype. Binding to the different types of somatostatin subtypes have been associated with the treatment of various conditions and/or diseases. (“sstr 2 ”) (Raynor, et al., Molecular Pharmacol. 43:838 (1993); Lloyd, et al., Am. J. Physiol. 268:G102 (1995)) while the inhibition of insulin has been attributed to the somatostatin type-5 receptor (“sstr 5 ”) (Coy, et al. 197:366-371 (1993)). Activation of types 2 and 5 have been associated with growth hormone suppression and more particularly GH secreting adenomas (Acromegaly) and TSH secreting adenomas. Activation of type 2 but not type 5 has been associated with treating prolactin secreting adenomas. Other indications associated with activation of the somatostatin receptor subtypes are inhibition of insulin and/or glucagon for treating diabetes mellitus, angiopathy, proliferative retinopathy, dawn phenomenon and nephropathy; inhibition of gastric acid secretion and more particularly peptic ulcers, enterocutaneous and pancreaticocutaneous fistula, irritable bowel syndrome, Dumping syndrome, watery diarrhea syndrome, AIDS related diarrhea, chemotherapy-induced diarrhea, acute or chronic pancreatitis and gastrointestinal hormone secreting tumors; treatment of cancer such as hepatoma; inhibition of angiogenesis, treatment of inflammatory disorders such as arthritis; retinopathy; chronic allograft rejection; angioplasty; preventing graft vessel and gastrointestinal bleeding. It is preferred to have an analog which is selective for the specific somatostatin receptor subtype or subtypes responsible for the desired biological response, thus, reducing interaction with other receptor subtypes which could lead to undesirable side effects.
[0002] The development of potent, smaller SRIF agonists led to the discovery of differing affinities of the various truncated ligands for the different subtypes. It appears that Trp 8 -Lys 9 sequence often is present in ligands that are recognized by the receptor. The Trp 8 -Lys 9 sequence forms part of a β-bend which is usually stabilized via substitution of D- for L-Trp, cyclization of the backbone, a disulfide bridge, or all constraints. One unintended consequence of such structural simplification, carried out before the discovery of multiple receptor subtypes, was the loss of broad spectrum binding affinity. This is typified by the high type 2 but low type 1, 3, 4, and 5 affinities of peptides in the OCTREOTIDE® series. Thus, the many basic biological studies with this type of analog failed to detect effects mediated by all but one of the somatostatin receptor types. Since then, much work has gone into the re-introduction of broader spectrum binding into small, biologically stable peptides on the one hand and the development of peptides and peptidomimetics with discrete specificity for a particular receptor.
[0003] We have discovered that peptide backbone constraint can be introduced by N-alkylation of individual amino acids. This modification largely restricts the affected residue and the amino acid preceding it to an extended conformation. Thus, additionally blocks potential intramolecular hydrogen bonding sites and also proteolytic enzyme cleavage sites thus potentially enhancing the pharmacokinetic properties of a peptide. Only a few N-methyl amino acids are commercially available and their synthesis is tedious. However, in another aspect of the present invention, we have discovered a procedure to N-methylate truncated somatostatin analogs at every amino acid residue using the solid-phase procedure, adopted from the recent publication reported by Miller and Scanlan.
SUMMARY OF THE INVENTION
[0004] In one aspect, the present invention is directed to a peptide of the formula (I),
A 1 -cyclo{D-Cys-A 2 -D-Trp-A 3 -A 4 -Cys}-A 5 -Y 1 , (I)
[0005] wherein:
[0006] A 1 is an optionally substituted aromatic α-amino acid;
[0007] A 2 is an optionally substituted aromatic α-amino acid;
[0008] A 3 is Dab, Dap, Lys or Orn;
[0009] A 4 is β-Hydroxyvaline, Ser, Hser, or Thr;
[0010] A 5 is an optionally substituted D- or L-aromatic α-amino acid; and
[0011] Y 1 is OH, NH 2 or NHR 1 , where R 1 is (C 1-6 )alkyl;
[0012] wherein each said optionally substituted aromatic α-amino acid is optionally substituted with one or more substituents each independently selected from the group consisting of halogen, NO 2 , OH, CN, (C 1-6 )alkyl, (C 2-6 )alkenyl, (C 2-6 )alkynyl, (C 1-6 )alkoxy, Bzl, O-Bzl, and NR 9 R 10 , where R 9 and R 10 each is independently H, O, or (C 1-6 ) alkyl; and
[0013] wherein the amine nitrogen of each of amide peptide bond and the amino group of A 1 of formula (I) is optionally substituted with a methyl group, provided that there is at least one said methyl group;
[0014] or a pharmaceutically acceptable salt thereof.
[0015] In one embodiment the invention features peptides of formula (I) wherein:
[0016] A 1 is Cpa, 1-Nal, 2-Nal, 2-Pal, 3-Pal, 4-Pal, Phe, Tfm, Tyr or Tyr(I);
[0017] A 2 is 2-Pal, 3-Pal, 4-Pal, Phe, Tyr or Tyr(I); and
[0018] A 5 is Dip, 1-Nal, 2-Nal, 2-Pal, 3-Pal, 4-Pal, Phe or D-Trp;
[0019] or a pharmaceutically acceptable salt thereof.
[0020] In another embodiment the invention features a peptide of the immediately foregoing group of peptides wherein A 1 is Cpa.
[0021] In a further embodiment the invention features a peptide of the immediately foregoing group of peptides wherein A 3 is NMeLys.
[0022] In a still further embodiment the invention features a peptide of formula (I) wherein said peptide is:
[0023] NmeCpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-Cys)-2-Nal-NH 2 ;
[0024] Cpa-cyclo(NMeDCys-3-Pal-DTrp-Lys-Thr-Cys)-2-Nal-NHMe;
[0025] Cpa-cyclo(DCys-NMe3-Pal-DTrp-Lys-Thr-Cys)-2-Nal-NH 2 ;
[0026] Cpa-cyclo(DCys-3-Pal-NMeDTrp-Lys-Thr-Cys)-2-Nal-NH 2 ;
[0027] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0028] Cpa-cyclo(DCys-3-Pal-DTrp-Lys-NMeThr-Cys)-2-Nal-NH 2 ;
[0029] Cpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-NMeCys)-2-Nal-NH 2 ;
[0030] Cpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-Cys)-Nme2-Nal-NH 2 ;
[0031] Cpa-cyclo(NMeDCys-3-Pal-DTrp-Lys-Thr-Cys)-Dip-NHMe;
[0032] Cpa-cyclo(DCys-3-Pal-NMeDTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0033] Cpa-cyclo(DCys-Tyr-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0034] Tfm-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0035] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ;
[0036] Nal-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ; or
[0037] 3-Pal-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ;
[0038] or a pharmaceutically acceptable salt thereof.
[0039] In yet a further embodiment the invention features a peptide of formula (I) wherein said peptide is:
[0040] NmeCpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-Cys)-2-Nal-NH 2 ;
[0041] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0042] Cpa-cyclo(DCys-3-Pal-NMeDTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0043] Cpa-cyclo(DCys-Tyr-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0044] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ;
[0045] Nal-cyclo(DCys-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ; or
[0046] 3-Pal-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ;
[0047] or a pharmaceutically acceptable salt thereof.
[0048] In still yet a further embodiment the invention features a peptide of formula (I) wherein said peptide is:
[0049] NmeCpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-Cys)-2-Nal-NH 2 ;
[0050] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0051] Cpa-cyclo(DCys-3-Pal-NMeDTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0052] Cpa-cyclo(DCys-Tyr-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ; or
[0053] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-DTrp-NH 2 ;
[0054] or a pharmaceutically acceptable salt thereof.
[0055] In still yet a further embodiment the invention features a peptide of the immediately foregoing group of peptides wherein said peptide is:
[0056] Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ; or
[0057] Cpa-cyclo(DCys-Tyr-DTrp-NMeLys-Thr-Cys)-2-Nal-NH 2 ;
[0058] or a pharmaceutically acceptable salt thereof.
[0059] In another aspect of the present invention is featured a method of binding one or more somatostatin subtype receptors −1, −2, −3, −4 and −5, which comprises the step of contacting a compound of claim 1 or a pharmaceutically acceptable salt thereof with one or more of said somatostatin subtype receptors.
[0060] In one embodiment of the immediately foregoing aspect the present invention features a method of binding one or more somatostatin subtype receptors −1, −2, −3, −4 and −5 in a human subject or other animal subject, which comprises the step of administering an effective amount of a compound of claim 1 or a pharmaceutically acceptable salt thereof to a subject in need thereof.
[0061] In another embodiment aspect of the present invention is featured a method of eliciting a somatostatin antagonist effect from a cell, wherein said cell comprises one or more somatostatin receptors, said method comprising contacting said cell with an effective amount of a compound of claim 1 or a pharmaceutically acceptable salt thereof.
[0062] In another embodiment, the present invention provides a method for eliciting a somatostatin antagonist effect in a human subject or other animal subject, which comprises the step of administering an effective amount of a compound of claim 1 or a pharmaceutically acceptable salt thereof to a subject in need thereof.
[0063] In a further embodiment of the present invention is featured a method of promoting the release of growth hormone in a human or animal subject, which comprises administering to said subject an effective amount of a compound according to claim 1 or a pharmaceutically acceptable salt thereof.
[0064] In another embodiment of the present invention is featured a method of promoting the release of insulin in a human or animal subject in need thereof, which comprises administering to said subject an effective amount of a compound according to claim 1 or a pharmaceutically acceptable salt thereof.
[0065] In another embodiment of the present invention is featured a method of enhancing wound healing in a human or animal subject in need thereof, which comprises administering to said subject an effective amount of a compound according to claim 1 or a pharmaceutically acceptable salt thereof.
[0066] In yet another embodiment of the present invention is featured a method of promoting angiogenesis in a human or animal subject in need thereof, which comprises administering to said subject an effective amount of a compound according to claim 1 or a pharmaceutically acceptable salt thereof.
[0067] In another embodiment of the present invention is featured a method of treating a disease or condition in a human or other animal subject in need thereof, which comprises the step of administering an effective amount of a compound of claim 1 or a pharmaceutically acceptable salt thereof to said subject, wherein said disease or condition is selected from the group consisting of short stature, cachexia, wasting, type 2 diabetes, poor circulation, and the like.
[0068] In another aspect of the present invention is featured a method of imaging cells having somatostatin receptors which comprises contacting said cells with an effective amount of a compound according to claim 1 , or a pharmaceutically acceptable salt thereof, which comprises Tyr(I).
BRIEF DESCRIPTION OF THE DRAWING
[0069] [0069]FIG. 1 is a graph showing the in vitro inhibition of hsstr-5 mediated intracellular Ca2+ mobilization.
DETAILED DESCRIPTION
[0070] One skilled in the art can, based on the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrations of the invention and are not meant to be construed as limiting the full scope of the invention.
[0071] As is well known to those skilled in the art, the known and potential uses of somatostatin are varied and multitudinous. Somatostatin and analogs thereof are known to be useful in the treatment of the diseases and/or conditions listed hereinbelow. The varied uses of somatostatin may be summarized as follows: Cushings Syndrome (see Clark, R. V. et al, Clin. Res. 38, p. 943A, 1990); gonadotropinoma (see Ambrosi B., et al., Acta Endocr. (Copenh.) 122, 569-576, 1990); hyperparathyroidism (see Miller, D., et al., Canad. Med. Ass. J., Vol. 145, pp. 227-228, 1991); Paget's disease (see, Palmieri, G. M. A., et al., J. of Bone and Mineral Research, 7, (Suppl. 1), p. S240 (Abs. 591), 1992); VIPoma (see Koberstein, B., et al., Z. Gastroenterology, 28, 295-301, 1990 and Christensen, C., Acta Chir. Scand. 155, 541-543, 1989); nesidioblastosis and hyperinsulinism (see Laron, Z., Israel J. Med. Sci., 26, No. 1, 1-2, 1990, Wilson, D. C., Irish J. Med. Sci., 158, No. 1, 31-32, 1989 and Micic, D., et al., Digestion, 16, Suppl. 1.70. Abs. 193, 1990); gastrinoma (see Bauer, F. E., et al., Europ. J. Pharmacol., 183, 55 1990); Zollinger-Ellison Syndrome (see Mozell, E., et al., Surg. Gynec. Obstet., 170, 476-484, 1990); hypersecretory diarrhea related to AIDS and other conditions (due to AIDS, see Cello, J. P., et al., Gastroenterology, 98, No. 5, Part 2, Suppl., A163 1990; due to elevated gastrin-releasing peptide, see Alhindawi, R., et al., Can. J. Surg., 33, 139-142, 1990; secondary to intestinal graft vs. host disease, see Bianco J. A., et al., Transplantation, 49, 1194-1195, 1990; diarrhea associated with chemotherapy, see Petrelli, N., et al., Proc. Amer. Soc. Clin. Oncol., Vol. 10, P 138, Abstr. No. 417 1991); irritable bowel syndrome (see O'Donnell, L. J. D., et al., Aliment. Pharmacol. Therap., Vol. 4., 177-181, 1990); pancreatitis (see Tulassay, Z., et al., Gastroenterology, 98, No. 5, Part 2, Suppl., A238, 1990); Crohn's Disease (see Fedorak, R. N., et al., Can. J. Gastroenterology, 3, No. 2, 53-57, 1989); systemic sclerosis (see Soudab, H., et al., Gastroenterology, 98, No. 5, Part 2, Suppl., A129, 1990); thyroid cancer (see Modigliani, E., et al., Ann., Endocr. (Paris), 50, 483-488, 1989); psoriasis (see Camisa, C., et al., Cleveland Clinic J. Med., 57, No. 1, 71-76, 1990); hypotension (see Hoeldtke, R. D., et al., Arch. Phys. Med. Rehabil., 69, 895-898, 1988 and Kooner, J. S., et al., Brit. J. Clin. Pharmacol., 28, 735P-736P, 1989); panic attacks (see Abelson, J. L., et al., Clin. Psychopharmacol., 10, 128-132, 1990); sclerodoma (see Soudah, H., et al., Clin. Res., Vol. 39, p. 303A, 1991); small bowel obstruction (see Nott, D. M., et al., Brit. J. Surg., Vol. 77, p. A691, 1990); gastroesophageal reflux (see Branch, M. S., et al., Gastroenterology, Vol. 100, No. 5, Part 2 Suppl., p. A425, 1991); duodenogastric reflux (see Hasler, W., et al., Gastroenterology, Vol. 100, No. 0.5, Part 2, Suppl., p. A448, 1991); Graves' Disease (see Chang, T. C., et al., Brit. Med. J., 304, p. 158, 1992); polycystic ovary disease (see Prelevic, G. M., et al., Metabolism Clinical and Experimental, 41, Suppl. 2, pp 76-79, 1992); upper gastrointestinal bleeding (see Jenkins, S. A., et al., Gut., 33, pp. 404-407, 1992 and Arrigoni, A., et al., American Journal of Gastroenterology, 87, p. 1311, (abs. 275), 1992); pancreatic pseudocysts and ascites (see Hartley, J. E., et al., J. Roy. Soc. Med., 85, pp. 107-108, 1992); leukemia (see Santini, et al., 78, (Suppl. 1), p. 429A (Abs. 1708), 1991); meningioma (see Koper, J. W., et al., J. Clin. Endocr. Metab., 74, pp. 543-547, 1992); and cancer cachexia (see Bartlett, D. L., et al., Surg. Forum., 42, pp. 14-16, 1991). The contents of the foregoing references are incorporated herein by reference.
[0072] The peptides of the invention are useful as antagonists to the activity or activities of somatostatin. For example, the peptides of the invention can be used to promote the release of growth hormone or insulin in a subject (e.g., a mammal such as a human patient). Thus, the peptides are useful in the treatment of physiological conditions in which the promotion of the release of growth hormone or insulin is of benefit. The peptides of the invention can also be used in enhancing wound healing or promoting angiogenesis. Further, peptides of the invention having a Tyr(I) residue can be used to image cells containing somatostatin receptors. Such peptides of the invention can be used either in vivo to detect cells having somatostatin receptors (e.g., cancer cells) or in vitro as a radioligand in a somatostatin receptor binding assay. The peptide of the invention can also be used as vectors to target cells with radioactive isotopes.
[0073] Also contemplated within the scope of this invention is a peptide covered by the above generic formula for both use in treating diseases or disorders associated with the need to promote the release of growth hormone or insulin, and use in detecting somatostatin receptors, e.g., radioimaging.
[0074] A compound of formula (I) or a pharmaceutically-acceptable salt thereof can be administered by oral, parenteral (e.g., intramuscular, intraperitoneal, intravenous- or subcutaneous injection, or implant), nasal, vaginal, rectal, sublingual or topical routes of administration and can be formulated with pharmaceutically acceptable carriers to provide dosage forms appropriate for each route of administration.
[0075] Solid dosage forms for oral administration include capsules, tablets, pills, powders and granules. In such solid dosage forms, the active compound is admixed with at least one inert pharmaceutically acceptable carrier such as sucrose, lactose, or starch. Such dosage forms can also comprise, as is normal practice, additional substances other than such inert diluents, e.g., lubricating agents such as magnesium stearate. In the case of capsules, tablets and pills, the dosage forms may also comprise buffering agents. Tablets and pills can additionally be prepared with enteric coatings.
[0076] Liquid dosage forms for oral administration include pharmaceutically acceptable emulsions, solutions, suspensions, syrups, the elixirs containing inert diluents commonly used in the art, such as water. Besides such inert diluents, compositions can also include adjuvants, such as wetting agents, emulsifying and suspending agents, and sweetening, flavoring and perfuming agents.
[0077] Preparations according to this invention for parenteral administration include sterile aqueous or non-aqueous solutions, suspensions, or emulsions. Examples of non-aqueous solvents or vehicles are propylene glycol, polyethylene glycol, vegetable oils, such as olive oil and corn oil, gelatin, and injectable organic esters such as ethyl oleate. Such dosage forms may also contain adjuvants such as preserving, wetting, emulsifying, and dispersing agents. They may be sterilized by, for example, filtration through a bacteria-retaining filter, by incorporating sterilizing agents into the compositions, by irradiating the compositions, or by heating the compositions. They can also be manufactured in the form of sterile solid compositions which can be dissolved in sterile water, or some other sterile injectable medium immediately before use.
[0078] Compositions for rectal or vaginal administration are preferably suppositories which may contain, in addition to the active substance, excipients such as coca butter or a suppository wax.
[0079] Compositions for nasal or sublingual administration are also prepared with standard excipients well known in the art.
[0080] The dosage of active ingredient in the compositions of this invention may be varied; however, it is necessary that the amount of the active ingredient be such that a suitable dosage form is obtained. The selected dosage depends upon the desired therapeutic effect, on the route of administration, and on the duration of the treatment. Generally, dosage levels of between 25 μg/kg/day to 100 mg/kg/day of body weight daily are administered as a single dose or divided into multiple doses to humans and other animals, e.g., mammals, to obtain the desired therapeutic effect.
[0081] A preferred general dosage range is 250 μg/kg/day to 5.0 mg/kg/day of body weight daily which can be administered as a single dose or divided into multiple doses.
[0082] Further, a compound of formula (I) can be administered in a sustained release composition such as those described in the following patents. Among those formulations, 14-day or 28-day slow release formulations will be preferred. U.S. Pat. No. 5,672,659 teaches sustained release compositions comprising a peptide and a polyester. U.S. Pat. No. 5,595,760 teaches sustained release compositions comprising a peptide in a gelable form. U.S. Pat. No. 5,821,221 teaches polymeric sustained release compositions comprising a peptide and chitosan. U.S. Pat. No. 5,916,883 teaches sustained release compositions comprising a peptide and cyclodextrin. International Patent Application No. PCT/US99/01180, (publication no. WO 99/38536, Aug. 5, 1999), teaches absorbable sustained release compositions of a peptide. The contents of the foregoing patents and applications are incorporated herein by reference.
[0083] The use of immediate or of sustained release compositions depends on the type of indications targeted. If the indication consists of an acute or over-acute disorder, a treatment with an immediate form will be preferred over the same with a prolonged release composition. On the contrary, for preventive or long-term treatments, a prolonged release composition will generally be preferred.
[0084] Abbreviations
[0085] The nomenclature for the somatostatin receptor subtypes is in accordance with the recomendations of IUPHAR, in which sstr 4 refers to the receptor originally cloned by Bruno et al., and sstr 5 refers to the receptor cloned by O'Carroll et al.
[0086] Abbreviations of the common amino acids are in accordance with the recommendations of IUPAC-IUB. Further, as used herein the definitions for certain abbreviations are as follows:
[0087] Abu=α-aminobutyric acid;
[0088] Aib=α-aminoisobutyric acid;
[0089] β-Ala=β-alanine;
[0090] Amp=4-amino-phenylalanine;
[0091] Ava=5-aminovaleric acid;
[0092] Cha=cyclohexylalanine;
[0093] Cpa=3-(4-chlorophenyl)alanine;
[0094] Dab=2,4-diaminobutyric acid;
[0095] Dap=2,3-diaminopropionic acid;
[0096] Dip=3,3′-diphenylalanine;
[0097] Gaba=γ-aminobutyric acid;
[0098] HSer=homoserine;
[0099] 1-Nal=3-(1-naphthyl)alanine;
[0100] 2-Nal=3-(2-naphthyl)alanine;
[0101] Nle=norleucine;
[0102] Nva=norvaline;
[0103] 2-Pal=3-(2-pyridyl)alanine;
[0104] 3-Pal=3-(3-pyridyl)alanine;
[0105] 4-Pal=3-(4-pyridyl)alanine;
[0106] Tfm=Trifluoromethyl; and
[0107] TfmA=4-trifluoromethylphenyl-alanine.
[0108] Tyr(I)=An iodinated tyrosine residue (e.g., 3-1-Tyr, 5-I-Tyr, 3,5-I -Tyr) wherein the iodine may be a radioactive isotope, e.g., I 125 , I 127 , or I 131 .
[0109] The following abbreviations of certain reagents also appear herein:
[0110] DBU=1,8-diazabicyclo[5.4.0]undec-7-ene;
[0111] DCM=dichloromethane;
[0112] DIC=diisopropylcarbodiimide;
[0113] DIEA=diisopropyethylamine;
[0114] DMF=dimethylformamide;
[0115] MTBD=1,3,4,6,7,8-Hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine;
[0116] o-NBS=2-nitrobenzenesulfonyl;
[0117] TBTU=O-Benzotriazol-1-yl-N,N,N′,N′-tetramethyluronium tetrafluoroborate;
[0118] and
[0119] TFA=trifluoroacetic acid.
[0120] With the exception of the N-terminal amino acid, all abbreviations (e.g., Cpa for A 1 ) of amino acids in this disclosure stand for the structure of —NH—CH(R)—CO—, wherein R is the side chain of an amino acid (e.g., CH 3 for Ala). For the N-terminal amino acid, the abbreviation stands for the structure of (R 1 R 2 )—N—CH(R)—CO—, wherein R is a side chain of an amino acid and each of R 1 and R 2 is independently H or as otherwise defined herein.
[0121] An aliphatic amino acid is an α-amino acid having one or two side chains which, independently, are hydrocarbons, e.g., a straight or branched chain of 1-6 carbons. Examples of aliphatic amino acids include Ala, Aib, Val, Leu, Tle, Ile, Nle, Nva, or Abu.
[0122] What is meant by “aromatic α-amino acid” is an amino acid residue of the formula
[0123] where Z 1 is a moiety containing an aromatic ring and Z 2 is hydrogen or a moiety containing an aromatic ring. Examples of such aromatic ring-containing moieties include, but are not limited to, a benzene or pyridine ring and the following structures with or without one or more substituent X on the aromatic ring (where X is, independently for each occurrence, halogen, NO 2 , CH 3 , OCH 3 , CF 3 , or OH):
[0124] Other examples of an aromatic α-amino acid of the invention are substituted His, such as MeHis, His (τ-Me), or His (π-Me).
[0125] As used herein, “alkyl” is intended to include those alkyl groups of the designated length in either a straight or branched configuration. Exemplary of such alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl and the like. When the term C 0 -alkyl is included in a definition it is intended to denote a single covalent bond.
[0126] The term “lower alkyl” is intended to include both branched and straight-chain alkyl groups having 1-6 carbon atoms.
[0127] As used herein, “aryl”, is intended to include any stable monocyclic, bicyclic, or tricyclic carbon ring(s) of up to 7 members in each ring, wherein at least one ring is aromatic. Examples of aryl groups include phenyl, naphthyl, anthracenyl, biphenyl, tetrahydronaphthyl, indanyl, phenanthrenyl, and the like.
[0128] The term “heterocyclyl”, as used herein, represents a stable 5- to 7-membered monocyclic or stable 8- to 11-membered bicyclic or stable 11-15 membered tricyclic heterocyclic ring which is either saturated or unsaturated, and which consists of carbon atoms and from one to four heteroatoms selected from the group consisting of N, O, and S, and including any bicyclic group in which any of the above-defined heterocyclic rings is fused to a benzene ring. The heterocyclic ring may be attached at any heteroatom or carbon atom which results in the creation of a stable structure. Examples of such heterocyclic elements include, but are not limited to, azepinyl, benzimidazolyl, benzisoxazolyl, benzofurazanyl, benzopyranyl, benzothiopyranyl, benzofuryl, benzothiazolyl, benzothienyl, benzoxazolyl, chromanyl, cinnolinyl, dihydrobenzofuryl, dihydrobenzothienyl, dihydrobenzothiopyranyl, dihydrobenzothio-pyranyl sulfone, furyl, imidazolidinyl, imidazolinyl, imidazolyl, indolinyl, indolyl, isochromanyl, isoindolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, isothiazolidinyl, morpholinyl, naphthyridinyl, oxadiazolyl, 2-oxoazepinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, piperidyl, piperazinyl, pyridyl, pyridyl N-oxide, quinoxalinyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolinyl, tetrahydro-quinolinyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiazolyl, thiazolinyl, thienofuryl, thienothienyl, thienyl, and the like.
[0129] The term “substituted” is meant to include the recited chemical group (e.g., lower alkyl, aryl, cycloalkyl, etc.) substituted with one or more of the recited substituents (e.g., halo, hydroxy, lower alkyl, etc.). The substituent may be attached to any atom in the chemical group.
[0130] The abbreviation “NMe” stands for “N-methyl-”. As used herein NMe indicates that the amide nitrogen of the associated amino acid is methylated. Thus, “NmeCpa” indicates —N(CH 3 )—CH(R)—CO— where R is 4-chlorophenyl, “Nme2-Nal” indicates —N(CH 3 )—CH(R)—CO— where R is 2-naphthyl, and so forth.
[0131] The term alkoxy is intended to include those alkoxy groups of the designated length in either a straight or branched configuration. Exemplary of such alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tertiary butoxy, pentoxy, isopentoxy, hexoxy, isohexoxy and the like.
[0132] The term halogen or halo is intended to include the halogen atoms fluorine, chlorine, bromine and iodine.
[0133] When the amino acid residue is optically active, it is the L-form that is intended unless the D-form is expressly designated.
[0134] Materials
[0135] 4-Methylbenzhydrylamine hydrochloride resin (0.25 or 0.5 mequiv g −1 ) was obtained from Advanced ChemTech Inc., Louisville, Ky. N α tert-Butyloxycarbonyl (Boc) protected amino acids were purchased from Bachem Inc., Torrance, Calif., Advanced ChemTech Inc., and Synthetech Inc., Albany, Oreg. The reactive side-chains of the amino acids were masked with one of the following groups: Cys, 4-methylbenzyloxycarbonyl; Lys, 2-chlorobenzyloxycarbonyl; Thr, O-benzyl; Tyr, O-2,6-dichlorobenzyl. All reagents and solvents were ACS grade or better and used without further purification.
[0136] Peptide Synthesis
[0137] The peptide synthesis may be summarized by the following reaction
[0138] The compounds of formula (I) can be and were synthesized on 4-methylbenzhydrylamine functionalized, 1% cross-linked polystyrene resin (0.25 or 0.5 mequiv g −1 ), in 0.25 mmol scale on an Advanced ChemTech (model 200) synthesizer, using the following protocol: deblocking, 40% TFA (2 min, 20 min); DCM wash cycle (three washes); neutralization, 10% DIEA (1 min, 5 min); DMF wash cycle; DCM wash cycle (two washes); double coupling; first with 1,3-diisopropyl carbodiimide esters (3 equiv.), 30 min in DCM; DCM wash (three washes); second coupling with preformed TBTU esters (3 equiv.), 90 min in DMF, with a catalytic amount of DIEA; DMF wash (one wash); DCM wash (three washes). Coupling reactions are monitored qualitatively.
[0139] N ∝ -Protection
[0140] After deblocking the amino group at the desired methylation site, the resin was suspended in DCM (20 mL). To this suspension, collidine (3 equiv.) and o-nitrobenzenesulfonyl chloride (3 equiv.) are added and the mixture was shaken using Advanced ChemTech (model 200) synthesizer for 2 h. Then the resin was subjected to DCM wash (2 washes) and DMF wash (3 washes). Protection is monitored qualitatively by the ninhydrin test.
[0141] N α -Methylation
[0142] The o-nitrobenzenesulfonamide protected resin was suspended in DMF (20 mL), to which MTBD (3 equiv.) and methyl 4-nitrobenzenesulfonate or dimethyl sulfate (for Cys 11 ) was added. The mixture was shaken using Advanced ChemTech (model 200) synthesizer for 0.5 h and the resin was subjected to DMF wash (4 washes).
[0143] N α -Me Deprotection
[0144] Once the desired residue was methylated, the resin was again suspended in DMF (20 mL). DBU (3 equiv.) and 2-mercaptoethanol (3 equiv.) were added to the suspension and the mixture was agitated for 0.5 h in Advanced ChemTech (model 200) synthesizer. The resin was then thoroughly washed with DMF (5 washes).
[0145] The foregoing methylation procedure worked well for all residues except for D-Cys 6 , which resulted in dimethylated derivatives, (see, e.g., compounds 2 and 10.) However replacement of D-Cys 6 with Cys 6 gave monomethylated peptides.
[0146] Peptide Cleavage
[0147] The peptides were cleaved from the resin support with simultaneous side-chain deprotection by acidolysis using anhydrous hydrogen fluoride containing the scavenger anisole (˜30% v/v) for 45 min at 0° C. The peptides were cyclized in 90% acetic acid (˜600 mL) with a slight excess of I 2 (15 min). Excess I 2 was then removed by the addition of ascorbic acid.
[0148] Purification
[0149] The crude peptides were purified by preparative RP-HPLC on C-18 bonded silica gel using axial compression columns (Dynamax-300 Å, 5 or 8 μm, 21.4×250 mm). A linear gradient elution system at a flow rate of 20 mL min −1 was employed: A; 0.1% TFA, B; 0.1% TFA in 80% MeCN, 20% B to 50% B at 1% min −1 . The separations were monitored by analytical RP-HPLC at 215 nm. The fractions containing the product were pooled, concentrated in vacuo and subjected to lyophilization. Each peptide was obtained as a fluffy white powder of constant weight by lyophilization from aqueous acetic acid. The purity of the final peptides was assessed at 215 nm by analytical RP-HPLC. Analytical RP-HPLCs were recorded using a Vydac C-18 support (4.6×250 mm, 5 μm, 300 Å pore size, Liquid Separations Group). The linear gradient system was used at a flow rate of 1.5 mL min −1 : HPLC-1, A, 0.1% TFA; B, 0.1% TFA in 80% MeCN; 20% B to 50% B at 1% min −1 ; HPLC-2, C, 5% MeCN in TEAP (0.1 M, pH 3); D, 20% C in MeCN, 10% D to 70% D at 1% min −1 . Column eluent was monitored at 215 nm. The retention time and purity of each peptide was assessed by the Rainin Dynamax HPLC Method Manager. Each peptide was found to have a purity of >98%. The HPLC retention time results are given in Table 1.
TABLE 1 N-Methyl Analogs and Analytical Data Mass Spectrum (M − H + ) HPLC c Peptide No. N—Me Sequence Calcd. a Obsd. b (t R-1 ) d (t R-2 ) e 1 NmeCpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr- 1178.7 1179.2 18.3 19.3 Cys)-2-Nal-NH 2 2 Cpa-cyclo(NmeDCys-3-Pal-DTrp-Lys-Thr- 1192.7 1193.4 19.6 19.3 Cys)-2-Nal-NHMe 3 Cpa-cyclo(DCys-Nme3-Pal-DTrp-Lys-Thr- 1178.7 1178.9 20.3 22.5 Cys)-2-Nal-NH 2 4 Cpa-cyclo(DCys-3-Pal-NMeDTrp-Lys-Thr- 1178.7 1179.2 17.9 17.2 Cys)-2-Nal-NH 2 5 Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr- 1178.7 1178.9 19.2 18.7 Cys)-2-Nal-NH 2 6 Cpa-cyclo(DCys-3-Pal-DTrp-Lys-NMeThr- 1178.7 1179.3 17.4 15.1 Cys)-2-Nal-NH 2 7 Cpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr- 1178.7 1179.0 18.5 16.7 NmeCys)-2-Nal-NH 2 8 Cpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-Cys)- 1178.7 1179.0 20.3 19.0 (Nme)-2-Nal-NH 2 9 Cpa-cyclo(DCys-3-Pal-DTrp-Lys-Thr-Cys)- 1164.8 1164.7 17.2 17.2 Nal-NH 2 10 Cpa-cyclo(NMeDCys-3-Pal-DTrp-Lys-Thr- 1218.9 1218.9 21.9 20.8 Cys)-Dip-NHMe 11 Cpa-cyclo(DCys-3-Pal-NMeDTrp-NMeLys- 1192.7 1192.3 19.9 19.7 Thr-Cys)-2-Nal-NH 2 12 Cpa-cyclo(DCys-Tyr-DTrp-NMeLys-Thr-Cys)- 1193.8 1193.6 24.9 23.1 2-Nal-NH 2 13 Tfm-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr- 1212.2 1212.2 21.4 20.7 Cys)-2-Nal-NH 2 14 Cpa-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr- 1167.8 1168.0 16.6 14.9 Cys)-DTrp-NH 2 15 Nal-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr- 1183.2 1183.5 18.0 16.4 Cys)-DTrp-NH 2 16 3-Pal-cyclo(DCys-3-Pal-DTrp-NMeLys-Thr- 1135.0 1134.8 11.5 9.8 Cys)-DTrp-NH 2
[0150] Amino Acid Analysis
[0151] The peptides were hydrolyzed in vacuo (110° C.; 20 h) in 4 M methanesulfonic acid containing 0.2% 3-(2-aminoethyl)indole. (Pierce). Amino acid analyses were performed on the hydrolyzates following derivatization with o-phthalidaldehyde reagent (Sigma Chemical Co.) using an automatic HPLC system (Rainin Instrument Co.) fitted with a 100×4.6 mm, 3 μm C18 axial compression column with integral guard column (Microsorb AAAnalysis™, Type O; Rainin Instrument Co.) The derivatized primary amino acids were eluted using a binary gradient of buffer A; 0.10 M sodium acetate containing 4.5% v/v methanol and 0.5% v/v tetrahydrofuran at pH 7.2 and buffer B; methanol. The gradient sequence; 0% A at 0 min; 35% A at 16.5 min; 90% A at 30 min and 90% A at 33 min is used with a flow rate of 1.0 mL min −1 at ambient temperature. Eluent is monitored at 340 nm and integrated by the Dynamax HPLC Method Manager (Rainin). Standard retention times were as follows: Asp, 6.6 min; Arg, 19.9 min; Trp, 25.4 min and Lys, 29.5 min. Each peptide of Table I produced the expected analytical results for the primary amino acids. Cysteine is not quantified.
[0152] Mass Spectrometry
[0153] The peptides were analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using a LaserMat 2000 mass spectrometer (Thermal Bioanalysis, San Jose, Calif.) using α-cyano-4-hydroxycinnamic acid as the matrix with Substance P (1348.7 Da) as an internal standard. In each case, the spectra consisted of a major M−H + ion peak for the internal standard, the expected analyte M−H + peak, and a few peaks associated with the matrix (<500 Da). The results are given in Table 1.
[0154] Antagonism of SRIF Inhibition of GH Release
[0155] Anterior pituitaries from adult male rats were collected and dispersed by a previously described trypsin/DNase method. (Murphy, W. A.; Taylor, J.; Moreau, J. P. and Coy, D. H., Peptide Res. 1989, 2, 128-132.) The dispersed cells were diluted with sterile-filtered Dulbecco's modified Eagle medium (MEM, Gibco Laboratories, Grand Island, N.Y.), which was supplemented with 2.5% fetal calf serum (Gibco), 3% horse serum (Gibco), 10% fresh rat serum (stored on ice for no longer than 1 h) from the pituitary donors, 1% MEM nonessential amino acids (Gibco), gentamycin (10 ng mL −1 ; Sigma) and nystatin (10,000 U mL −1 ; Gibco). The cells were randomly plated at a density of approximately 200,000 cells/well (Costar cluster 24; Rochester Scientific Co., Rochester, N.Y.). The plated cells were maintained in the above Dulbecco's medium in a humidified atmosphere of 95% air/5% CO 2 at 37° C. for 4-6 days. In preparation for a hormone challenge, the cells were washed with medium 199 (Gibco, 3×1 mL). Each dose of a compound of this invention (6 doses/plate) was tested in triplicate wells in the presence of 1 nM SRIF in a total volume of 1 mL medium 199 containing 1% BSA (fraction V; Sigma Chemical Co.). All wells contained GHRH(1-29)NH 2 (1 nM). A GHRH(1-29)NH 2 (1 nM) stimulated control group and an SRIF (1 nM) with GHRH(1-29)NH 2 (1 nM) inhibited control group were included on each cell culture plate. After 3 h incubation in an air/carbon dioxide atmosphere (95/5%, 3 h at 37° C.), the medium was removed and stored at −20° C. until assayed for hormone content. Growth hormone in media was measured by a standard double antibody RIA using components generously supplied by Dr. A. F. Parlow at the National Hormone and Pituitary Program (NHHP) Torrance, Calif.
[0156] Antagonist IC 50 's versus SRIF (1 nM) were calculated using Sigmaplot (Jandel Scientific, San Rafael, Calif.). Values are expressed as the mean IC 50 (nM)±SEM and are given in Table 2.
TABLE 2 Binding Affinities (K 1 ) for Cloned Human sst 1-5 Receptors and Antagonist Data Antagonist N α -Methylation K 1 a ± SEM (nM) IC 50 ± SEM Peptide No. site hsst 1 hsst 2 hsst 3 hsst 4 hsst 5 (nM) b SRIF-14 N/A c 2.0 ± 0.35 0.25 ± 0.03 1.2 ± 0.2 2.0 ± 0.3 1.4 ± 0.3 N/A c SRIF-28 N/A c 1.9 ± 0.4 0.31 ± 0.06 1.3 ± 0.3 5.4 ± 2.5 0.4 ± 0.1 N/A c 1 Cpa 5 1000 36 ± 7.6 330 ± 126 1000 40.1 ± 18.8 7.8 ± 2.7 2 d D-Cys 6 1000 89.0 ± 8.0 576 ± 47 1000 106 ± 36 nd e 3 3-Pal 7 1000 189.0 ± 35 450 ± 132 1000 1000 nd e 4 D-Trp 8 1000 51.8 ± 2.6 390 ± 114 1000 93 ± 17.7 nd e 5 Lys 9 1000 17.1 ± 5.5 66.0 ± 5.8 1000 5.98 ± 0.91 0.73 ± 0.33 6 Thr 10 395 ± 202 1000 315 ± 12.5 1000 88.5 ± 45.7 nd e 7 Cys 11 1000 810 68.7 ± 4.7 575 161 ± 52 nd e 8 2-Nal 12 1000 197 ± 55 1000 1000 1000 nd e 9 N/A c 1395 12.1 ± 1.9 38.2 ± 2.4 1000 140 ± 4.6 2.6 ± 0.7 10 d D-Cys 6 1000 117 ± 24.6 584 ± 305 1000 766 ± 110 nd e 11 DTrp 8 1000 9.33 ± 0.62 140 ± 10.4 1000 112 ± 19 2.5 ± 0.20 & Lys 9 12 Lys 9 1000 5.51 ± 1.85 115.1 ± 16.9 1000 70.7 ± 25.8 0.53 ± 0.17 13 Lys 9 1000 11.3 40.2 1246 45.5 nd e 14 Lys 9 1000 5.45 ± 0.3 91.4 ± 11.9 1000 101 ± 14.1 11.6 ± 4.2 15 Lys 9 1000 27.3 ± 1.45 148 ± 13.2 1000 176 ± 65.1 96 ± 13.8 16 Lys 9 1000 24.7 ± 1.61 537 ± 44.8 1000 313 ± 4.1 287 ± 138
[0157] Functional Expression of the Cloned Human Somatostatin Receptors
[0158] The genomic clones containing the human somatostatin receptors (hsstr 1-5 ) (Yamada, Y., et al. al., Proc. Natl. Acad. Sci. USA. 1992, 89, 251-255; Yasuda, K., et al., J. Biol. Chem. 1992, 267, 20422-20428; Yamada, Y., et al., Mol. Pharmacol. 1992, 42, 2136-2142; Rohrer, L., et al., Proc. Natl. Acad. Sci. USA. 1993, 90, 4196-4200.), were kindly provided by Dr. Graeme I. Bell (University of Chicago). The hsstr 1 , hsstr 2 , hsstr 3 , hsstr 4 and hsstr 5 cDNAs were isolated as a 1.5-kb PstI-XmnI fragment, 1.7-kb BamHI-HindIII fragment, 2.0-kb NcoI-HindIII fragment, 1.4-kb NheI-NdeI fragment, and a 1.2-kb HindIII-XbaI fragment, respectively, each containing the entire coding region of the full-length receptors. These fragments were independently subcloned into the corresponding restriction endonuclease sites in the mammalian expression vector pCMV5, downstream from the human cytomegalovirus (CMV) promoter, to produce the expression plasmids pCMV5/hsstr 1 , pCMV5/hsstr 2 , pCMV5/hsstr 3 , pCMV5/hsstr 4 and pCMV5/hsstr 5 . For transfection into CHO-K1 cells, a plasmid, pRSV-neo (American Type Culture Collection, Rockville, Md.), carrying the neomycin mammalian cell selectable marker was added.
[0159] Receptor Expression and Transfection
[0160] Transfections were performed by the calcium phosphate method. CHO-K1 cells are maintained in α-minimum essential medium (α-MEM; Gibco) supplemented with 10% fetal calf serum and transfected with each of the expression plasmids using calcium phosphate precipitation. Clones that had inherited the expression plasmid were selected in α-MEM supplemented with 500 μg mL −1 of geneticin (G418; Gibco). Independent CHO-K1 clones were picked by glass-ring cloning and expanded in culture in the selective media. Membranes were prepared from the isolated clones and hsstr expression was initially assessed for binding with [ 125 I]Tyr 11 -SRIF and [ 125 I]MK-678 (for sstr 2 ).
[0161] Radioligand Binding Assays
[0162] Cell membranes of the 5 receptor types were obtained from homogenates (Polytron setting 6, 15 sec) of the corresponding CHO-K1 cells, in ice-cold Tris-HCl (50 mM) and centrifuged (39000 g, 10 min×2), with an intermediate resuspension in fresh buffer. The final pellets are resuspended in Tris-HCl (10 mM) for assay. Aliquots of the membranes are incubated (30 min at 37° C.) with 0.05 nM [ 125 I]Tyr 11 -SRIF (types 1,3,4,5) or [ 125 I]MK-678 (type 2) in 50 mM HEPES (pH 7.4) containing BSA (10 mg mL −1 ); MgCl 2 (5 mM), Trasylol (200 kIU mL −1 ), bacitracin (0.02 mg mL −1 ), and phenylmethanesulfonyl fluoride (0.02 mg 1 mL −1 ). The final assay volume is 0.3 mL and incubations are terminated by rapid filtration through GF/C filters pre-soaked in 0.3% poly(ethylenimine) using a Brandel rapid filtration module. Each tube and filter is then washed with aliquots of cold buffer (3×5 mL).
[0163] Specific binding is. defined as the total radioligand bound minus that bound in the presence of 1.0 μM SRIF. The following total radioligand binding and non-specific binding (nsb) values are typically obtained with these assay systems: hsstr 1 , 7000 cpm total versus 3500 cpm nsb; hsstr 2 , 9000 cpm total versus 1000 cpm nsb; hsstr 3 , 8000 cpm total versus 1000 cpm nsb; hsstr 4 , 6000 cpm total versus 3500 cpm nsb; and hsstr 5 , 7500 cpm total versus 3500 cpm nsb. The binding affinities are expressed as K i values±SEM (nM) for each of the five receptor subtypes and are given in Table 2.
[0164] Type 5 Mediated Intracellular Ca 2+ Mobilization
[0165] CHO-K1 cells, expressing the human sst5 receptor, were harvested by incubating in a 0.3% EDTA/phosphate buffered saline solution (25° C.), and washed twice by centrifugation. The washed cells were resuspended in Hank's -buffered saline solution (HBSS) for loading of the fluorescent Ca 2+ indicator Fura-2AM. Cell suspensions of approximately 10 6 cells/ml were incubated with 2 μM Fura-2AM for 30 min at about 25° C. Unloaded Fura-2AM was removed by centrifugation twice in HBBS, and the final suspensions were transferred to a spectrofluorometer (Hitachi F-2000) equipped with a magnetic stirring mechanism and a temperature-regulated cuvette holder. After equilibration to 37° C., the somatostatin peptides were added for measurement of intracellular Ca 2+ mobilization. The excitation and emission wavelengths were 340 and 510 nm, respectively.
[0166] Exemplary data appears in FIG. 1 which depicts results from the immediately foregoing assay using Analog 5 as the Test Compound.
[0167] Molecular Modeling
[0168] Molecular modeling was performed on a Silicon Graphics Indigo 2 High Impact 10000 computer, using SYBYL molecular modeling software, version 6.6, (Tripos Associates Inc., St. Louis Mo., USA), with the Kollman all atom force field. (Weiner, S. J., et al., J. Comp. Chem. 1986, 7, 230-252.) The PDB files for the three solution NMR structures of the initial compound Sandostatin/Octreotide; D-Phe 5 -c[Cys 6 -Phe 7 -D-Trp 8 -Lys 9 -Thr 10 -Cys 11 ]-Thr 12 -ol (1 SOC and 2SOC) were obtained from the PDB database. These structures were imported into SYBYL 6.6 and mutated to form the N-methylated compounds based on analog 9. The Kollman partial atomic charges were loaded from the monomer dictionary. The structures were optimized by annealing the mutated residue and then by full energy minimization using the conjugate gradient algorithm to a final root mean square (rms) gradient of ≦0.01 Kcal molÅ −1 . A distance-dependent dielectric function (McCammon, J. A., et al., Biochem. 1979, 18, 927-942) was employed together with the default settings for all the other minimization options. The results are detailed in Table 3.
TABLE 3 Kollman all atom energy change on sequential methylation of each residue of Cpa-cyclo(DCys-3- Pal-DTrp-Lys-Thr-Cys)-2-Nal-NH 2 (analogue 9) in each of the three solution conformations expressed as Kcal mol −1 . Methylation Analogue No Site I II III 1 NMeCpa 5 −2 0.4 −1 2 NMeDCys 6 , NHMe 17 12 31 3 NMe3-Pal 7 7 17 6 4 NMeDTrp 8 5 6 5 5 NMeLys 9 6 6 5 6 NMeThr 10 16 10 12 7 NMeCys 11 12 14 23 8 Nme-2-Nal 12 4 19 7
[0169] Other Embodiments
[0170] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, that the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the claims.
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The present invention is directed to a somatostatin antagonist according to formula (I), wherein A 1 is an optionally substituted aromatic ∝-amino acid; A 2 is an optionally substituted aromatic ∝-amino acid; A 3 is Dab, Dap, Lys or Orn; A 4 is β-Hydroxyvaline, Ser, Hser, or Thr; A 5 is an optionally substituted D- or L-aromatic -amino acid; and Y 1 is OH, NH 2 or NHR 1 , where R 1 is (C 1-6 )alkyl; wherein each said optionally substituted aromatic -amino acid is optionally substituted with one or more substituents each independently selected from the group consisting of halogen, NO 2 , OH, CN, (C 1-6 )alkyl, (c 2-6 )alkenyl, (c 2-6 )alkynyl, (C 1-6 )alkoxy, Bzl, O-Bzl, and NR 9 R 10 , where R 9 ad R 10 each is independently H, O, or (C 1-6 )alkyl; and wherein the amine nitrogen of each of amide peptide bond and the amino group of A 1 of formula (I) is optionally substituted with a methyl group, provided that there is at least one said methyl group; or a pharmaceutically acceptable salt thereof, and to uses thereof.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part application of prior copending application Ser. No. 001,449, filed Jan. 8, 1979 and now abandoned.
BACKGROUND OF THE INVENTION
This invention is directed to novel dye developers which are useful in photographic products and processes and more particularly to novel magenta chrome complexed dye developers.
Metal-complexed dyes are well known in the art. One group of metal-complexed dyes are those referred to in the art as 1:1 complexes, a term embracing complexes of one dye molecule complexed to a metal ion. Metal-complexed dyes having a sillver halide developing capability, i.e., metal-complexed dye developers are also well known in the art. Such dye developers are described, for example, in U.S. Pat. No. 3,551,406 and may be illustrated schematically as follows:
Dye-Me-Ligand-Developer
wherein "Dye" is a chelatable or complexable dye, "Me" is a metal-complexing atom, "Ligand" is a substantially colorless ligand which contributes at least one and preferably two of the coordinating or donor atoms necessary to form the desired complex, and "Developer" is a silver halide developing agent or substituent. It is also known in the art that the developing function in dye developers may be contained on the ligand or on the dye. Many dye developers which are within the class illustrated above have been disclosed in the art. Nevertheless, as the art of photography advances and more stringent demands are imposed upon the materials used because of increased performance standards there continue to be discovered novel compositions of matter which are useful in the art. The present application relates to novel magenta chrome-complexed dye developers and their use in photographic products and processes.
PRIOR ART STATEMENT
U.S. Pat. No. 3,544,545 discloses 1:1 chromecomplexed azo dye developers which are useful in color photography. These dye developers include ligands, or compounds contributing two oxygen atoms bonded to the chromium atom, which may be defined as β-hydroxy-α,β-unsaturated carbonyl compounds, or compounds capable of tautomerizing to such a structure. U.S. Pat. No. 3,551,406 also discloses dye developers for use in color photography. It is disclosed that the ligand moiety may be selected from various groups of organic ligands including various amino acid compounds.
SUMMARY OF THE INVENTION
It is therefore the object of this invention to provide novel dye developer materials which are useful in photographic products and processes.
It is another object of the invention to provide photographic products and processes utilizing the novel dye developer materials.
It is a further object to provide novel magenta chrome-complexed dye developers.
It is still another object to provide such dye developers which are zwitterionic compounds.
Still further it is an object to provide such dye developers which include an onium salt and a colorless ligand which is a radical of an iminodiacetic acid.
BRIEF SUMMARY OF THE INVENTION
These and other objects and advantages are accomplished in accordance with the invention by providing novel compounds which are magenta chrome-complexed dye developers and which include an ortho, ortho'-dihydroxyazo dye, an onium salt and a colorless ligand which is a radical of an iminodiacetic acid. Since the chromium complexes of ortho, ortho'-dihydroxyazo dyes and iminodiacetic acids bear a single negative charge, the dye developer molecule is required to include a positive counterion in order to possess electrical neutrality. The novel compounds are represented by the structural formula ##STR1## wherein ##STR2## is the radical of an ortho, ortho'-dihydroxyazo dye represented by the structural formula ##STR3## wherein A is a divalent aromatic radical, for example, a radical of benzene or naphthalene; B is a divalent aromatic or a nitrogen containing heterocyclic radical, for example, a radical of benzene, naphthalene, pyrazolone or pyrimidine; Y is a silver halide developing substituent; each n is 0, 1 or 2 with the proviso that at least one n is 1; R may be H, alkyl having from 1 to 6 carbon atoms or X m ; X is the radical of an onium salt; each m is 0 or 1 with the proviso that only one m is 1; and R 1 and R 2 may be H or when taken together represent the carbon atoms necessary to complete a five or six member heterocyclic moiety.
It will be apparent to those skilled in the art that where the onium salt and the silver halide developing substituent(s) are integrated with the dye moiety each of them may be attached directly to the dye moiety or the onium salt may be attached to a developing substituent which in turn is attached to the dye moiety or the reverse thereof. All such structures are intended to be encompassed by structural formula (I).
For the present invention, a silver halide developing substituent (Y) is one containing a benzene or naphthalene nucleus containing at least a hydroxy and/or amino substituent ortho or para to another such substituent. Silver halide developing substituents of this type are well known to the art as evidenced, for example, by Neblette's Handbook of Photography and Reprography, 7th Edition, published by Van Nostrand Reinhold Company, Inc. (1977), pp. 115-118. A preferred group of developing substituents are the hydroquinonyls, including substituted derivatives such as alkyl, phenyl and/or alkoxy substituent derivatives of hydroquinone.
In addition to the silver halide developing substituents, the benzene or naphthalene nucleus may contain substituents linking the developing moiety to the azo dye moiety. Such linking substituents include amino phenyl alkyl-thio substituents such as disclosed in U.S. Pat. No. 3,009,958; amino alkyl-amino substituents such as disclosed in U.S. Pat. No. 3,002,997; amino phenyl alkyl substituents such as disclosed in U.S. Pat. No. 3,043,690; amino-alkyl substituents such as disclosed in U.S. Pat. No. 3,062,884; amino phenyl substituents such as disclosed in U.S. Pat. No. 3,142,564; amino phenoxy substituents such as disclosed in U.S. Pat. No. 3,061,434 as well as the various linking substituents disclosed in U.S. Pat. No. 3,255,001.
The positive counterion, X, may be any onium salt, such as, for example, ammonium, sulfonium and phosphonium salts, which does not impair photographic processing, i.e., impair the absorption characteristics of the dye moiety or impair the functionality of the complex as a dye developer. A preferred class of onium salts which may be used is represented by the formula
N.sup.+ R.sub.3 R.sub.4 R.sub.5 R.sub.6
wherein R 3 is alkylene having from 2 to 8 carbon atoms and R 4 , R 5 and R 6 may be H or alkyl, preferably alkyl having from 1 to 6 carbon atoms. Other onium salts which may be used include the ammonium or quaternary salts of heterocyclic bases, e.g., pyridinium or alkyl picolinium. It will be apparent to those skilled in the art that the onium salt is connected to the ligand or the dye moiety through one of the R groups.
As noted the ligand is a radical of an iminodiacetic acid which is represented by the structural formula ##STR4## wherein R 1 and R 2 may be H or when taken together represent the carbon atoms necessary to complete a five or six member heterocyclic moiety. A preferred ligand of the latter type is a radical of an iminodiacetic acid which is represented by the structural formula
BRIEF DESCRIPTION OF THE DRAWING
For a better understanding of the invention as well as other objects and further features thereof, reference is made to the following detailed description of various preferred embodiments thereof taken in conjunction with the accompanying drawings wherein:
FIG. 1 is the reflection absorption spectrum of one of the preferred dye developers of the invention; and
FIG. 2 is a partially schematic, cross-sectional view of one embodiment of a film unit according to the invention especially suited for the formation of a monochromatic image.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Specific magenta dye developers of the present invention are represented by the following structural formulas: ##STR6##
The preferred dye developers of the invention typically exhibit desirable absorption characteristics. FIG. 1 illustrates the reflection absorption spectrum of dye developer (II). The preferred dye developers exhibit transmission characteristics in the blue region of the spectrum which provide desirable bright blues in the final photographic print. For monochromatic images made with film units including the preferred dye developers, the ratio of the minimum density in the blue region to the maximum density in the green region is typically a relatively smaller value thus evidencing increased blue transmission. Dye developer (II) is particularly preferred because of its absorption characteristics and its ability to transfer at a very wide range of alkali concentrations in diffusion transfer film systems.
As noted previously, the magenta chromecomplexed dye developers including an ortho, ortho'-dihydroxyazo dye which is chrome complexed to a particular ligand. Thus, as mentioned previously, the dyes which are useful in the preparation of the novel dye developers of the invention may be represented by the general formula ##STR7## wherein A and B are as previously described. The dyes which correspond to the general formula may be prepared by techniques which are well known in the art and therefore extensive discussion of such techniques is not required. Generally the preparation of such azo dyes involves the diazotization of an aromatic ortho hydroxy amine and coupling of the diazotized amine by known techniques with an aromatic, heterocyclic or active methylene compound which can provide a hydroxy group ortho to the azo linkage. Such couplers are known and include, for example, beta naphthols, pyrazolones and acetoacetanilides among others.
The dye developers of the present invention include one or more silver halide developer substituents which can be integrated with the dye portion. Suitable silver halide developing substituents for incorporation in the dye developers of the invention have been described previously. Details relating to such substituents and ways of integrating them in the dye developers can be found in various patents including U.S. Pat. Nos. 3,086,005; 3,134,762; 3,141,772; 3,236,643; 3,235,645; 3,252,990; 3,299,041. In some instances it may be desirable to employ a protected form of the silver halide developing substituent, i.e., where the hydroxy groups are replaced by acyloxy, benzyloxy, alkoxy or acetoxy substituents. These protecting substituents can be connected to the dihydroxyphenyl developing substituents by known techniques.
Chrome complexing of the dye moieties or dye developer moieties of the chrome-complexed magenta dye developers of the invention can be carried out according to known procedures including those described in U.S. Pat. No. 2,028,981. Generally, a chrome salt is reacted with an ortho, ortho'-dihydroxy azo dye or dye developer to form the complex having a silver halide developing capability. The ligand is then attached to the chrome complex.
The dye developers of the present invention may be utilized in any film unit which is useful in monochromatic or multicolor photography. Particularly preferred film units according to the present invention are those diffusion transfer integral negative-positive film units of the type described in detail in U.S. Pat. Nos. 3,415,644 and 3,647,437. Other preferred film units are those which are designed to be separated after processing such as those described in U.S. Pat. No. 2,983,606. Extensive discussion of the film units of the invention is not required in view of the state of the art. However, for the purposes of illustration the invention will be further described with respect to a monochromatic film unit. Referring now to FIG. 2 there is seen the monochromatic film unit, generally designated 10, which comprises a conventional paper or plastic film support 12, a layer 14 containing a magenta dye developer according to the invention, and a photosensitive layer 16 comprising a suitable silver halide emulsion. Container 18 includes a viscous processing reagent and may be formed of a composite sheet material comprising an inner layer which is substantially chemically inert to the processing reagent, an intermediate layer which is substantially impervious to vapor and an outer backing layer which can be readily affixed to a layer of the film assembly such as, for example, the print receiving element 20. The print receiving element comprises a dyeable material and may comprise a single print receiving layer or a composite structure as shown made up of image-receiving layer 22, spacer layer 24, polymeric acid layer 26 and transparent support 28. In practice, the film unit is employed with any suitable photographic camera apparatus and is exposed to provide a negative latent image. Processing of the film unit typically occurs by bringing the exposed portion of the unit in superposed relation with a portion of the print receiving element 20 while drawing these portions of the unit between a pair of pressure rollers which rupture container 18 and spread the processing composition contained thereon between and in contact with the photosensitive layer and the corresponding area of the print receiving element. The processing composition permeates or migrates into the photosensitive layer 16 and dye developer layer 14. During the permeation of the processing composition into layer 14 dye developer contained in the layer is dissolved in the processing composition and is transported in solution into photosensitive layer 16 to distribute dye developer in the photosensitive layer. Where the dye developer interacts with exposed silver halide in layer 14 it is oxidized as a function of the amount of silver halide reduced to silver while the oxidation product of the dye developer forms an image that is substantially coextensive with the developed silver. The dye developer provides an oxidation product as a result of silver development which is of considerably lower solubility in the processing composition than the dye developer itself. Under these conditions the oxidation product is substantially immobilized or retained in the photosensitive layer 16.
At the time that the dye developer is interacting with exposed silver halide and providing an immobile oxidation product an imagewise distribution of unoxidized dye developer is formed in the negative material in areas where exposure and subsequent development are less than complete. Dye developer present in solution in the imagewise distribution is transportable at least in part by imbibition to print receiving element 20. Thus, the print receiving element is dyed or otherwise colored by the transported dye developer where the dye developer is deposited to provide the desired reverse image in color of the latent image. In this instance the transfer or positive image is magenta. After formation of the positive image the print receiving element is separated from the photosensitive element.
The invention will now be described further in detail with respect to specific preferred embodiments by way of examples, it being understood that these are illustrative only and the invention is not intended to be limited to the materials, conditions, process parameters, etc., recited therein. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
PREPARATION OF INTERMEDIATES
(A) A β-keto ester intermediate was prepared by the following reaction: ##STR8##
Compound (XV) was prepared by initially adding 3-(2,5-dibenzyloxy phenyl) propionic acid (30 g; 0.083 mole) to a solution of oxalyl chloride (11.4 g; 0.09 mole) in benzene (300 ml) at room temperature. The solution was stirred under nitrogen for two hours and then evaporated in vacuo at 40° C. 200 ml of benzene were added and reevaporated under the same conditions described above to ensure complete removal of excess oxalyl chloride. Pumping on the residue at 0.1/mm for about one hour yielded 31.5 g of crude acid chloride which should be used immediately.
Compound (XVI) was prepared by initially charging a flame dried, three neck, two liter round bottom flask equipped with a 500 ml pressure equalized addition funnel, an overhead stirrer and a nitrogen inlet with n-butyllithium (Alfa Inorganics 2.2 M in hexane; 114 ml, 0.25 mole) and dry tetrahydrofuran (100 ml). The solution was cooled to -10° C. and equilibrated over 10 minutes. Diisopropylamine (25.2 g; 34.5 ml; 0.25 mole) was added dropwise over a 20 minute period under nitrogen with stirring. The solution was stirred an additional 20 minutes at -10° C., cooled to -78° C. and allowed to equilibrate over 20 minutes. Ethyl acetate (predried over 4 A sieves; 18 g; 20.1 ml; 0.25 mole) was added dropwise to the solution over a 15 minute period. The solution was stirred an additional 20 minutes at -78° C. A solution of compound (XV) (31.5 g; 0.083 mole) in 150 ml tetrahydrofuran was added to the flask at -78° C. over a 30 minute period. The solution was stirred an additional 10 minutes and then poured slowly and continuously into 400 ml of saline solution. The mixture was extracted three times with 200 ml of ether, twice with 20 ml of 5% sodium bicarbonate solution, once with saline solution and then dried over calcium sulfate. The solvent was removed in vacuo to yield 35 g of a light yellow oil.
(B) A hydrazine intermediate was prepared according to the following reaction: ##STR9##
To a refluxing solution of 117 g of 95% H 2 NNH 2 and 13.5 g of water in 400 ml absolute ethanol was added with stirring under nitrogen a solution of 90.45 g (0.18 mole) of compound (XVII) in 340 ml diethyl ether and 400 ml absolute ethanol over a period of 51/2 hours. The solution was then refluxed for an additional half hour. The reaction mixture was evaporated in vacuo. Water was added to the residue and then extracted twice with ether. The ether extracts were washed twice with water, dried over anhydrous sodium sulfate, the sodium sulfate filtered off and to the ether filtrate was added with stirring a solution of ether saturated with hydrogen chloride gas until no more precipitation occurred. The precipitate was filtered, washed with ether and dried to give 60 g of solid which was then recrystallized from 450 ml of isopropanol to yield 52 g of a white solid.
(C) A pyrazolone intermediate having the structural formula: ##STR10## was prepared by initially forming a mixture of 1 g (0.0023 mole) of compound (XVIII) and 0.377 g (0.0046 mole) of sodium acetate in 30 ml of absolute ethanol and stirring at room temperature for several minutes. Then 1.1 g (0.00254 mole) of compound (XVI) was added and the mixture stirred for 11/2 hours. The solid which formed was filtered, washed with ethanol and then with water and dried to give 1.35 g of a white solid, m.p. 93°-95° C.
(D) A pyrazolone compound having the structural formula: ##STR11## was prepared by initially combining 10.1 g (0.022 mole) of methyl hydrazine and 95 g (0.022 mole) of compound XVI in 250 ml of absolute ethanol at 0° C. The reaction mixture was stirred at ambient temperature overnight. The solid product was collected by filtration, rinsed with diethyl ether and air dried to yield 60 g of a white solid, m.p. 135°-136° C.
(E) A pyrazolone having the structural formula: ##STR12## was prepared by initially forming a mixture of 7 g (0.0161 mole) of compound (XVIII) and 2.64 g (0.0322 mole) of sodium acetate in 210 ml of absolute ethanol and stirring at room temperature for several minutes. Then 2.73 g (0.021 mole) of ethyl acetoacetic ester was added to the mixture and the reaction mixture stirred at room temperature for 1 hour and 20 minutes. The reaction mixture was then diluted with 210 ml of water and stirred until a solid was obtained. The solid was filtered, washed with water and then ether and dried to provide 5 g of a white solid.
(F) A pyrazolone having the structural formula: ##STR13## was prepared by initially forming a solution of 2.1 g (0.012 mole) of 2,6-dimethylphenylhydrazine hydrochloride and 1.48 g (0.018 mole) of sodium acetate in 15 ml of acetic acid and adding to it a solution of 6.5 g (0.015 mole) of compound (XVI) in 5 ml of acetic acid. The resulting solution was kept at 50° C. overnight. The reaction mixture was diluted with about 1.5 liters of water and then extracted three times with 100 ml of ether. The ether extracts were washed successively with sodium bicarbonate solution, water, saturated salt solution and then dried over anhydrous magnesium sulfate. The ether was evaporated and the residue triturated with ethanol to yield 3.5 g of the pyrazolone, m.p. 157°-158° C.
C 33 H 32 N 2 O 3 requires 78.54% C; 6.39% H and 5.55% N. Elemental analysis of the compound found 78.4% C; 6.3% H and 5.5% N.
EXAMPLE II
PREPARATION OF LIGANDS
(A) A ligand having the structural formula: ##STR14## was prepared in the following manner: 26 g (0.2 mole) of 3-diethylamino-n-propylamine and 37.8 g (0.4 mole) of chloroacetic acid were combined with 200 ml of water in a 500 ml three-neck, round bottom flask equipped with temperature control, heating mantle and an overhead stirrer. The solution was warmed to 50° C. with stirring and 126 g (0.4 mole) of solid barium hydroxide hydrate was added as needed to maintain a slightly alkaline medium (pH˜9) over a two hour period at which point the remaining hydroxide was added all at once. The solution was stirred overnight at 50° C. The solution was cooled and filtered. The solid product was washed twice in hot water, once in hot methanol and dried in vacuo to yield 52.5 g of a white solid.
C 11 H 20 N 2 O 4 Ba requires 34.6% C; 5.2% H; 7.3% N and 36.0 Ba. Elemental analysis gave 34.3% C; 5.3% H; 7.3% N and 34.3% Ba.
41 g (0.11 mole) of the N(3-diethylaminopropyl)iminodiacetic acid barium salt were slurried in 300 ml of water at 90° C., stirred, and to the slurry were added 44 ml (0.1 mole) of 5 N sulfuric acid dropwise over a 30 minute period. The end point was determined by centrifuging a small sample and adding one drop of 5 N sulfuric acid to the supernatent liquid. A clear solution indicated the completed reaction. The paste-like slurry was filtered through a Celite pad and water was evaporated from the filtrate in vacuo. The resultant semi-solid residue was treated with warm acetone while scratching. The white solid, N[3-(N',N'diethylaminopropyl)]iminodiacetic acid, was collected by filtration, pressed dry and finally dried in vacuo to yield 27.5 g of the solid, m.p. 101°-102° C.
19.2 g (0.096 mole) of cupric acetate monohydrate and 27.5 g (0.096 mole) of N[3-(N',N'diethylaminopropyl)]iminodiacetic acid were combined in 100 ml of water and stirred at room temperature until all the solids had dissolved. To the blue solution were added 800 ml of acetone. The product settled and the supernatent liquid was decanted. The product was washed in this manner until it became solid. It was then filtered and dried in vacuo to yield 29 g of the blue copper salt; λ max 255 nm (ε 2.550), 740 nm (ε 64.0).
C 13 H 28 N 2 O 8 Cu requires 42.1% C; 6.5% H; 7.6% N and 17.0% Cu. Elemental analysis found 42.2% C; 7.0% H; 7.6% N and 17.2% Cu.
20 g (0.054 mole) of the copper salt were combined with 14.9 g (0.1 mole) of methyl iodide and 2.9 g (0.054 mole) of sodium methoxide in 200 ml of methanol and heated to reflux under nitrogen for 12 hours. To the cooled solution were added 400 ml of water and the mixture filtered from the solid by-product. The clear blue filtrate was then treated with hydrogen sulfide until a dark solid no longer formed (about 15 minutes). The solution was filtered through a Celite pad, treated with charcoal and refiltered. The solvent was removed in vacuo to yield a residue which crystallized on treatment with isopropanol. The white solid, 3(N',N'-biscarboxymethylaminopropyl)N,N-diethyl-N-methylammonium iodide, was collected by filtration to yield 11 g after drying.
(B) A ligand having the structural formula: ##STR15## was prepared as follows: 55.9 g (0.2 mole) of triphenyl methyl chloride were added at one time to a stirred solution of 26 g (0.2 mole) of 3-diethylaminopropyl amine, 20 g (0.2 mole) of triethylamine and methylene chloride under nitrogen at room temperature. The mixture immediately warmed to 40° C. A solid began to form after two hours. The reaction mixture was stirred for 12 hours. The solution was filtered from triethylamine hydrochloride and the filtrate washed twice with 100 ml of water followed by 100 ml of saturated salt solution and then dried over sodium sulfate. The solution was filtered and evaporated to dryness to yield 74.5 g of a light yellow oil, N-(triphenylmethyl)3-N',N'diethylaminopropyl amine.
23 g (0.062 mole) of the amine prepared above and 8.6 g of ethyl bromide were combined in 30 ml of toluene in an autoclave and heated to 90° C. on a steam bath for 9 hours. The solid product was collected from the cooled reaction mixture by filtration, rinsed with toluene and dried in vacuo to yield 29 g of an off-white solid, N-(triphenylmethyl)-3-triethylamino propylamine bromide salt.
20 g (0.04 mole) of the bromide salt were combined with 60 ml (0.04 mole) of 1 N ethanolic hydrogen chloride in 140 ml of ethanol and heated to reflux for one hour. The reaction was followed by thin layer chromatography. 400 ml of ether were added to the cooled solution and a solid was collected by filtration yielding, on drying, 10 g of a light grey solid, triethyl-3-aminopropyl ammonium hydrochloride bromide salt.
10 g (0.03 mole) of the ammonium hydrochloride bromide salt and 6.8 g (0.072 mole) of chloroacetic acid were combined with 100 ml of water in a 250 ml three-neck round bottom flask equipped with a heating mantle and overhead stirrer. The solution was warmed to 50° C. with stirring and 28.35 g (0.09 mole) of solid barium hydroxide hydrate were added in portions over a two hour period. Stirring at 50° C. was continued overnight. The cloudy cooled solution was filtered and the product was carried on to the next step as the aqueous filtrate.
To a solution of the previous product (17.6 g, 0.036 mole) in 400 ml of water were added 14.4 ml (0.036 mole) of a solution of 5 N sulfuric acid dropwise over a 30 minute period. The endpoint was determined by centrifuging a small sample and adding one drop of 5 N sulfuric acid to the supernatent liquid. A clear solution indicated the completed reaction. The paste-like slurry was filtered through a Celite pad and the filtrate evaporated in vacuo. The residue was treated with 2-propanol to yield 10 g of a tan solid (compound XXIV) on drying.
(C) A ligand having the structural formula: ##STR16## was prepared as follows: 18.6 g (0.1 mole) of dibutylaminopropylamine and 18.9 g (0.2 mole) of chloroacetic acid were combined with 200 ml of water and warmed to 50° C. with stirring. Over a period of 2 hours 63.1 g (0.2 mole) of solid barium hydroxide hydrate were added as needed to maintain a pH of 9-10 after which the remaining hydroxide was added and the reaction stirred overnight at 50° C. The solid was collected by filtration, treated twice with hot water and then with hot methanol and dried in vacuo to yield 32 g of a white powder.
A slurry of 10 g (0.023 mole) of the white powder in 100 ml of water was formed, stirred and to it were added 9.2 ml (0.023 mole) of 5 N sulfuric acid dropwise over a half hour period. The end point was determined by adding one drop of sulfuric acid to the supernatent liquid of a centrifuged aliquot. A clear solution indicated the completed reaction. The paste-like slurry was filtered through a Celite pad and water was evaporated from the filtrate in vacuo. The resultant semi-solid was treated with acetone while scratching. The white solid was collected by filtration, pressed dry and dried in vacuo to yield 5.7 g of compound XXV.
NMR (D 2 O,DSS)δ: 3.8 (s,4H), 3.1 (m,8H), 2.1 (m,2H), 1.5 (m,8H), 0.9 (t,6H).
EXAMPLE III
PREPARATION OF COMPOUND (II)
A compound having the structural formula: ##STR17## was prepared by initially forming a mixture of 36.5 g (0.05 mole) of compound (XIX) and 15.5 g (0.05 mole) of a compound having the structural formula: ##STR18## in 500 ml of acetone. There was then added to the mixture with stirring a solution of 8.4 g (0.1 mole) of sodium hydrogen carbonate in 250 ml of water. The mixture was stirred at room temperature for two hours, poured into 125 ml of concentrated hydrogen chloride water and ice, filtered, washed well with water and dried to provide 48.7 g of solid (compound XXVI).
To a solution of 88.55 g of boron tribromide in 800 ml of methylene chloride cooled to -78° C. and under nitrogen was added, dropwise and with stirring, a solution of 46 g (0.0442 mole) of compound XXVI in 400 ml of methylene chloride over a period of two hours. The solution was stirred for an additional half hour at -78° C. Ether was added twice and by warming to room temperature, evaporated to dryness with nitrogen. The residue was triturated with ether, filtered, washed with ether and dried. It was then dissolved in warm methanol and evaporated in vacuo to dryness to yield 30 g.
A mixture of 30 g (0.044 mole) of the previous product and 42 g (0.157 mole) of chromium chloride hexahydrate in 300 ml of deaerated methyl cellosolve was refluxed under nitrogen for two hours. The reaction was cooled, poured into a saturated salt and ice solution. The water was then decanted from the precipitated gummy material. To this was added salt solution and it was triturated until a solid was obtained. The solid was filtered, washed with cold water and dried to yield 31 g of the 1:1 chrome complex.
A solution of 25 g (0.0305 mole) of the 1:1 chrome complex in 250 ml of deaerated methyl cellosolve was formed and to it was added a solution of 14.2 g (0.0366 mole) of compound XXIII, first dissolved in 10 ml of water and then 7.4 g (0.0732 mole) of triethylamine. The reaction mixture was stirred under nitrogen on a steam bath for a half hour, then cooled and poured into a solution of 6.25 g of sodium hydrogen carbonate in water and ice. The precipitate was filtered, washed well with water and dried. The solid was purified by extraction under nitrogen in a Soxhlet extractor for several days whereupon the dye developer (compound II) crystallized in the flask.
λmax(meth. cell) 354 nm (ε=10,800); 537 nm (ε=20,800); 576 nm (ε=22,000).
A film unit was prepared as follows: the negative was made by coating a subcoated 4 mil polyethylene terephthalate film base with the following layers:
1. a layer of compound II dispersed in cellulose acetate hydrogen phthalate at a coverage of about 52.6 mgs/ft 2 (0.0512 m moles) of compound II and 52.6 mgs/ft 2 of cellulose acetate hydrogen phthalate;
2. a green sensitive gelatino silver iodobromo emulsion coated at a coverage of about 120 mgs/ft 2 of silver and about 120 mgs/ft 2 of gelatin;
3. a layer coated at a coverage of about 30 mgs/ft 2 of gelatin and about 7.5 mgs/ft 2 of 4'-methyl phenyl hydroquinone.
The image receiving element comprised a 4 mil polyethylene terephthalate film base with the following layers coated thereon in succession:
1. as a polymeric acid layer, a partial butyl ester of polyethylene/maleic anhydride copolymer at a coverage of about 2,450 mgs/ft 2 ;
2. a timing layer containing about a 75:1 ratio of a 60-30-4-6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid and polyvinyl alcohol at a coverage of about 350 mgs/ft 2 ;
3. a polymeric image receiving layer containing a 3:1 blend of a mixture of 1 part poly-4-vinylpyridine and 2 parts polyvinyl alcohol and a 2.2:2.2:1 graft copolymer of hydroxyethylcellulose, 4-vinylpyridine and vinyl benzyl trimethyl ammonium chloride coated at a coverage of about 300 mgs/ft.
The film unit was processed with a processing composition comprised of:
______________________________________ (GMS/100 gm H.sub.2 O)______________________________________Titanium dioxide 94.08Sodium carboxymethyl cellulose 2.29Potassium hydroxide 9.42Lithium hydroxide 0.26N-benzyl-α-picolinium bromide 2.81N-phenethyl-α-picolinium bromide 1.62Benzotriazole 1.255-methyl-6-bromo- azabenzimidazole 0.066-methyl uracil 0.66Lithium nitrate 0.22Ethylene diamine tetraacetic acid 1.86Colloidal silica 1.23Carbowax 1.21Bis-2-aminoethyl sulfide 0.05N-benzylamino purine 0.89______________________________________
The film unit was exposed to green and blue light and then passed through a pair of rollers at a gap of about 0.0020 inches. The unit was allowed to remain in the dark for 10 minutes and the maximum and minimum reflection densities were then measured. The resulting image had a D max/ D min=1.95/0.80 and the ratio of the minimum density in the blue region to the maximum density in the green region was 0.32.
EXAMPLE IV
PREPARATION OF COMPOUND III
The dye developer was prepared by combining 2 g (0.02 mole) of triethylamine, 30 ml of 2-methoxyethanol, 6.0 g (0.007 mole) of the 1:1 chrome complex described in Example III and 3.8 g (0.01 mole) of ligand B (compound XXIV) and warming to 90° C. for a half hour under an inert atmosphere. The cooled solution was diluted with 100 ml of acetone and the solid was collected by filtration. The solid was rinsed well with water and air dried to yield 6.5 g.
Vis(meth.cell.) λ max; 576 mμ (ε=21,600); 530 nm; (ε=20,400).
EXAMPLE V
PREPARATION OF COMPOUND IV
The dye developer was formed as follows: initially there were combined 0.98 g (0.005 mole) of 4-cyan-1-diazo-2-naphthol, 2.5 g (0.005 mole) of compound XXII and 1 g (0.01 mole) of sodium carbonate in 30 ml of acetone and 10 ml of water at room temperature and the mixture was stirred for two hours. The mixture was quenched in 10% hydrochloric acid and ice. The solid was collected by filtration, washed with water and dried to give 2.3 g of the blocked dye developer, m.p. 157°-159° C. C 44 H 37 N 5 O 4 requires 75.52% C; 5.33% H; and 10.01% N. Elemental analysis gave 75.6% C; 5.4% H and 10.1% N.
A solution of 2.1 g (0.003 mole) of the blocked dye developer in 20 ml of methylene chloride was formed and it was added dropwise to a stirred solution of 10 g of 30% HBr/HOAc in 60 ml of methylene chloride at room temperature. The solution was stirred for one hour. Hexane was added and the solid collected by filtration. The solid was washed with water and recrystallized from 2-methoxyethanol to give 0.75 g of a red solid, m.p. 232°-233° C. (dec.) C 30 H 25 N 5 O 4 requires 69.35% C; 4.85% H; 13.48% N and 12.32% O. Elemental analysis gave 69.1% C; 4.8% H and 13.5% N.
1.5 g (0.0029 mole) of the red solid and 1.6 g (0.006 mole) of chromium trichloride hexahydrate were combined in 30 ml of 2-methoxyethanol and heated at 90° C. for 12 hours. The solution was cooled, diluted with saturated salt solution and the product collected by filtration. The magenta solid was rinsed with water and air dried to yield 1.25 g of the 1:1 chromium complex.
The dye developer was prepared by combining 0.2 g (0.002 mole) of triethylamine, 20 ml of 2-methoxyethanol, 0.76 g (0.001 mole) of the 1:1 chromium complex described immediately above, and 0.6 g (0.002 mole) of ligand C (compound XXV) and warming to 90° C. for a half hour under an inert atmosphere. The cooled solution was diluted with water and the solid was collected by filtration, rinsed well with water and air dried to yield 1 g.
Vis(meth.cell) λ max: 580 nm (ε=26,800); 540 nm (ε=22,000)
The dye developer was tested in the manner described in Example III using the same processing composition and film unit with the exception that compound IV was used in place of compound II. The positive image had a D max/ D min=1.57/0.48 and the ratio of the minimum density in the blue region to the maximum density in the green region was 0.29.
EXAMPLE VI
PREPARATION OF COMPOUND V
A solution of 4.0 g (0.01 mole) of compound XX and 5 g (0.05 mole) of sodium carbonate was formed and stirred and to it was added 1.96 g (0.01 mole) of ##STR19## After two hours, the reaction was quenched by adding the mixture to a stirred slurry of 100 ml of 10% hydrochloric acid and 100 g of ice. The orange solid was collected by filtration and rinsed with water to yield 5.8 g, m.p. 159°-160° C., on drying.
Vis(methyl cell) λ max 490 nm (ε=24,800), 345 nm (ε=7,200).
To a stirred solution of 100 g (0.04 mole) of boron tribromide in 600 ml of dry methylene chloride at -78° C. there was added dropwise a solution of 37 g (0.06 mole) of the orange solid in 500 ml of methylene chloride. The reaction mixture was stirred an additional hour at -78° C. and then 200 ml of diethyl ether were added cautiously. The volatiles were removed by purging the system with nitrogen for one hour with the cooling bath removed. The remaining slurry was quenched with 20 ml of methanol and added to a stirred slurry of 300 g of ice and 500 ml of 10% hydrochloric acid. The gummy solid was dissolved in 600 ml of ethyl acetate. The solution was washed with three 50 ml of volumes of water and then with 75 ml of saturated salt solution, dried over calcium sulfate and concentrated in vacuo to yield 25 g of an orange solid, m.p. 205° -206° C.
Vis(methyl cell) λ max 490 nm (ε=26,400).
10 g (0.023 mole) of the orange solid and 12.4 g (0.046 mole) of chromium trichloride hexahydrate were combined in 30 ml of 2-methoxyethanol and heated at 90° C. for 12 hours. The solution was cooled, diluted with saturated salt solution and the product collected by filtration. The magenta solid was rinsed with water and air dried to yield 12.0 g.
0.3 g (0.03 mole) of triethylamine, 0.3 g (0.0058 mole) of the magenta solid, 0.53 g (0.0017 mole) of compound XXV were combined in a reaction vessel and warmed to 90° C. for a half hour under an inert atmosphere. The solution was cooled, diluted with 50 ml of water and acidified (to pH 5) with dilute hydrochloric acid. The solid was collected by filtration, washed with water and dried in vacuo to yield 0.4 g of magenta dye developer.
Vis(methyl cell) λ max 575 nm (ε=26,500), 538 nm (ε=19,800)
The dye developer was tested in the same manner described in Example II using the same processing composition and film unit with the exception that compound V was used in place of compound II. The positive image had a D max/ D min=1.70/0.85 and the ratio of the minimum density in the blue region to the maximum density in the green region was 0.30.
EXAMPLE VII
PREPARATION OF COMPOUND VI
To a stirred solution of 8 g (0.02 mole) of compound XX and 10 g (0.1 mole) of sodium carbonate in 200 ml of acetone and 100 ml of water were added 5.8 g (0.02 mole) of ##STR20## The solution was stirred for two hours at room temperature. The reaction was quenched at 0° C. by adding it to a stirred slurry of 100 ml of 10% hydrochloric acid and 100 g of ice. The orange solid was collected by filtration and rinsed with water to yield 13 g on drying, m.p. 175°-176° C.
Vis(methyl cell) λ max 498 nm (ε=22,000).
To a stirred solution of 6.25 g (0.025 mole) of boron tribromide in 100 ml of dry methylene chloride at 78° C. there was added dropwise a solution of 3.5 g (0.005 mole) of the previous product in 300 ml of methylene chloride. The reaction mixture was stirred for one hour at -78° C. and then purged with nitrogen for one hour to remove excess reagent. 50 ml of ethyl ether were added cautiously and the slurry added to a stirred slurry of ice and 10% hydrochloric acid. The organic layer was washed with water, dried over calcium sulfate and concentrated on a steam bath to cause precipitation. The solid was collected by filtration and dried in vacuo to yield 2 g, m.p. 215°-216° C. (dec).
Vis(methyl cell) λ max 498 nm (ε=21,600).
A 1:1 chromium complex was formed by combining 0.2 g (0.0039 mole) of the previous product and 0.3 g (0.0011 mole) of chromium trichloride hexahydrate in 5 ml of 2-methoxyethanol and heating to 90° C. for twelve hours. The cooled solution was partitioned between saturated salt solution and ethyl acetate. The organic phase was washed with brine and dried over calcium sulfate. Solvent removal gave 0.25 g of a magenta solid.
The dye developer was formed by combining 0.6 g (0.006 mole) of triethylamine, 20 ml of 2-methoxyethanol, 2 ml of water, 1.0 g (0.0028 mole) of ligand C (compound XXV) and 0.89 g (0.0014 mole) of the previous product and warming to 90° C. for a half hour under an inert atmosphere. The cooled solution was diluted with 50 ml of water and acidified to pH 5 with dilute hydrochloric acid. The solid was collected by filtration, washed with water and dried in vacuo to yield 1.0 g.
Vis(methyl cell) λ max: 574 nm (ε=22,400); 535 nm; (ε=19,400).
C 43 H 5 N 6 O 10 SCr requires 57.6% C; 5.7% H; 9.4% N; 3.6% S and 5.8% Cr. Elemental analysis gave 57.6% C; 6.0% H; 9.2% N; 3.3% S and 5.3% Cr.
EXAMPLE VIII
PREPARATION OF COMPOUND VII
To a mixture of 5 g (0.01165 mole) of compound XXI and 3.62 g (0.01165 mole) of ##STR21## there was added with stirring a solution of 1.96 g (0.0233 mole) of sodium hydrogen carbonate in 50 ml of water. The reaction mixture was stirred at room temperature for 2 hours and then poured into dilute hydrogen chloride solution. The precipitate was filtered, washed well with water and dried. The solid was recrystallized from 100 ml of acetic acid to give 6.8 g of an orange-red solid.
To a stirred solution of 2 ml of boron tribromide in 50 ml of methylene chloride cooled to -40° C. and under nitrogen there was added dropwise over a period of a half hour a solution of 1.5 g (0.00203 mole) of the orange-red solid in methylene chloride. The solution was stirred at -40° C. for an additional half hour. Ether was added twice and evaporated to dryness by passing in nitrogen. After triturating with ether, the solid was washed well with ether and dried. This material was boiled with methanol for several minutes and the precipitated solid was collected to yield 0.8 g.
To a hot solution of 4 g (0.00716 mole) of the previous product in 40 ml of methyl cellosolve there was added a solution of 7.64 g (0.02864 mole) of chromium chloride ydrate in 45 ml of methyl cellosolve. The reaction mixture was refluxed for 2 hours and then poured into hydrochloric acid and ice. The precipitate was filtered, washed with cold dilute hydrochloric acid and then with cold water and dried to yield 4.2 g of the 1:1 chromium complex. To a solution of 4.2 g (0.006 mole) of the 1:1 chromium complex in 60 ml of deaerated ethanol there was added a solution of 1.81 g (0.006 mole) of compound XXV and 1.21 g of triethylamine in 60 ml of deaerated ethanol. The reaction mixture was refluxed under nitrogen for a half hour, cooled at room temperature and filtered. The crystals were washed with ethanol and dried to yield 3.7 g of the dye developer.
Vis(methyl cell) λ max 355 nm (ε=11,600); 536 nm; (ε=22,000); 574 nm (ε=27,000).
Although the invention has been described in detail with respect to various embodiments thereof, these are intended to be illustrative only and not limiting of the invention but rather those skilled in the art will recognize that modifications and variations may be made therein which are within the spirit of the invention and the scope of the appended claims.
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There are described novel magenta chrome complexed dye developers which are particularly useful in photographic products and processes. These novel magenta dye developers are zwitterionic compounds which include an onium salt such as a quaternary ammonium salt and a colorless ligand which is a radical of an iminodiacetic acid.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to pressure relief means, and in particular to such means providing fluid crossover and fluid dumping functions.
2. Description of the Prior Art
In one form of hydraulic system, a working element, such as a snowplow, is held at a desired angular position by a pair of single acting cylinders connected to the snowplow blade through the piston rods thereof. The plow blade may be pivoted about a vertical central axis with the disposition of the blade being fixed by blocking the hydraulic connections with the blade in the desired disposition.
Adjustment of the plow blade disposition is effected by causing hydraulic fluid delivery to one or the other of the cylinders through a conventional direction control valve which may comprise a spool-type valve. The blocking condition in such a spool-type valve is effected by spring biasing the spool to a centered neutral position.
A problem arises in such hydraulic control systems in that, at times, an overload may be applied to a portion of the plow blade so as to produce a high pressure condition in one or the other of the cylinders. Unless some dissipation of this high pressure condition is provided, failure of the components of the system may result from the impact surges.
It has been conventional to provide some pressure relief means to provide a crossover relief between the cylinders under such abnormal high pressure conditions. It has also been conventional to provide some high pressure relief when both cylinders reach a high pressure condition as caused by a high load being applied concurrently thereto through the blade. Conventionally, such blades not only pivot about a vertical axis at the center thereof, but also about a horizontal axis at the bottom of the blade as a result of the concurrent forces applied thereto.
Heretofore, the control of such overload conditions has required the use of three different crossover relief valves resulting in a relatively expensive and complicated structure which, because of a large number of moving parts, further presents a serious maintenance problem.
SUMMARY OF THE INVENTION
The present invention comprehends an improved pressure relief means for use in such apparatus wherein a single relief valve provides the three relief functions required relative to such blade overload conditions.
As the pressure relief means of the present invention utilizes a single movable valve member and a single biasing means, the construction of the pressure relief means of the present invention is extremely simple and economical while yet providing an improved overload control.
More specifically, the improved pressure relief means of the present invention is adapted for use in an apparatus having a working element defining first and second spaced support portions, a first cylinder having a piston provided with a rod connected to the first support portion, a second cylinder having a piston provided with a rod connected to the second support portion, and adjustably controlled hydraulic supply means connected to the cylinders to provide hydraulic fluid to the cylinders for adjustably positioning the piston rods to position and retain the working element as desired. The relief means includes a body defining a piston chamber, a first port opening to the chamber and connected to the first cylinder, and a second port opening to the piston chamber and connected to the second cylinder, a piston in the chamber having a valve portion removably seating on the body at the first port for selectively closing the first port and defining in the chamber an annular space communicating with the second port at all times, the piston defining at an inner end of the space a pressure surface, and means biasing the piston to cause the valve portion to close the first port, the piston and ports being arranged in a closed condition of the pressure relief means to have fluid pressure from the first cylinder act on the valve portion closing the first port and fluid pressure from the second cylinder act on the pressure surface and to cause the piston to move against the action of the biasing means and provide communication between the first and second ports through the annular space as an incident of a preselected high cumulative fluid pressure being delivered to the first and second ports.
In the illustrated embodiment, the pressure relief means body further defines a third port opening to the piston chamber and connected to a return, or relief, tank. The piston and ports are arranged further to cause the piston to move further against the action of the biasing spring and provide communication between the first, second and third ports through the piston chamber to dump fluid therethrough to the return tank as an incident of a second preselected cumulative fluid pressure higher than the first preselected pressure being delivered to the first and second ports.
In the illustrated embodiment, the cross-sectional area of the first port is substantially equal to the cross-sectional area of the annular surface of the piston. In the illustrated embodiment, the first and second ports open perpendicularly to each other.
In the illustrated embodiment, the piston chamber defines a relief space behind the piston and closed from the annular space by the piston when the relief means is in the closed condition. The relief space communicates with the annular space when the piston is moved by the existence of the second preselected pressure so as to provide communication between the annular space and the third port for dumping hydraulic fluid through the first and second ports to the relief tank.
In the illustrated embodiment, the biasing means comprises spring means disposed within the relief space.
Guide means may be disposed in the relief space for guiding the piston in its movement as effected by the different cylinder pressure conditions.
BRIEF DESCRIPTION OF THE DRAWING
Other features and advantages of the invention will be apparent from the following description taken in connection with the accompanying drawing wherein:
FIG. 1 is a side elevation of an apparatus embodying the invention;
FIG. 2 is a top plan view thereof;
FIG. 3 is a fragmentary vertical section of the pressure relief means with the valve in the closed condition;
FIG. 4 is a fragmentary vertical section thereof with the valve in a crossover position as caused by a high pressure condition in the first port;
FIG. 5 is a fragmentary vertical section thereof with the valve in the crossover position as a result of high pressure in the second valve port; and
FIG. 6 is a fragmentary vertical section thereof with the valve in the dump-to-tank position as a result of high pressure existing in both the first and second ports.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In the exemplary embodiment of the invention as disclosed in the drawing, an apparatus generally designated 10 is shown to comprise a wheeled vehicle adapted to move a working element, such as a snowplow 11, over a surface 12. The snowplow defines a blade which is mounted to the vehicle by a lower support 13 having a pivotal connection 14 to a lower portion 15 of the blade. The upper portion 16 of the blade is connected by means of pivots 17 and 18 to a pair of piston rods 19 and 20 extending from pistons 21 and 22, respectively, of hydraulic cylinders 23 and 24, respectively.
As shown in FIG. 2, the piston rods 19 and 20 are variably extensible relative to the cylinders 23 and 24 so as to turn blade 11 about a vertical axis 25 (FIG. 1). In operation of the snowplow, the blade may also pivot about the horizontal axis 26 of pivot 14.
The hydraulic pressure system generally designated 27 for operating the cylinder devices 23 and 24 is schematically illustrated in FIGS. 1 and 2 as including a relief tank 28. Hydraulic fluid is delivered under pressure to a supply line 29 by means of a high pressure pump 30 connected to the tank 28. A manually operable valve 31 is provided for delivering the high pressure hydraulic fluid from supply line 29 to either of delivery lines 32 connected to cylinder 23 or delivery line 33 connected to cylinder 24 as desired.
As seen in FIG. 2, when high pressure fluid is delivered to cylinder 23 from pump 30, piston rod 19 is extended to the right so as to pivot the blade about the vertical axis 25 to the desired angular disposition. Concurrently, piston rod 20 may be retracted by exhausting the cylinder 24 to the return tank 28.
In the illustrated embodiment, the control valve 31 comprises a conventional four-way valve. As shown, cylinder 23 may be mounted to the frame 34 of the apparatus by a pivot 35 and cylinder 24 may be mounted to the frame by a pivot 36 to permit the desired control of the blade disposition discussed above.
As indicated briefly above, the present invention comprehends the provision of a unitary overload relief valve generally designated 37 for controlling overload conditions on the blade as may occur during normal operation thereof. As shown in FIG. 2, relief valve 37 is connected to delivery line 32 by a crossline 38 and is connected to delivery line 33 by a crossline 39. The relief valve is connected to the relief tank 28 by a relief line 40.
The construction of relief valve 37 is illustrated in FIGS. 3-6. As shown therein, the relief valve includes a body 41 defining a piston chamber 42 in which is movably received a piston 43. The piston is slidably received in a cylindrical portion 44 of the body defining a midportion of the piston chamber when the valve is in the closed condition of FIG. 3.
As further shown, the piston carries a valve portion 45 extending from the piston to a valve seat 46 defined by a first port 47 connected to crossline 38.
The valve chamber further defines an annular space 48 surrounding the valve portion 45 and communicating through a second valve port 49 with the crossline 39. Annular space 48 communicates with annular space 44, which is confronted by an annular surface 50 of the piston and thereby exposed to fluid pressure conditions within the annular spaces 48 and 44.
The piston chamber further defines a rearward relief space 51 into which piston 43 may move as the result of an opening of the valve 45,46. A piston rod 52 is connected to the piston to extend through space 51 and into a guide bore 53 so as to effectively guide the piston coaxially in its movement toward and from valve seat 46. A compression spring 54 is provided about the piston rod 52 in relief space 51 and is effectively compressed between body 41 and the rearward surface 55 of the piston so as to bias the piston and valve portion 45 to the left, or seated condition of the valve, as shown in FIG. 3.
The arrangement of the valve under different high pressure conditions of apparatus 10 is illustrated in FIGS. 4-6. Thus, referring more specifically to FIGS. 2 and 4, when the hydraulic fluid in cylinder 23 increases in pressure as by a substantial force acting against the righthand portion of blade 11 connected to piston 21 by piston rod 19, this high pressure is transmitted through crossline 38 to port 47 and, thus, acts against the inner end 52 of the valve portion 45 of piston 43. spring 54 is preselected so as to prevent opening of port 47 until such time as the pressure reaches a preselected first high value, whereupon the force generated by the pressure acting against valve and 52 overcomes the biasing force of spring 54 and shifts the piston and valve to the right, as seen in FIG. 4, to provide communication from port 47 through annular space 48 to second port 49 which is connected by crossline 39 to the cylinder 24. Thus, the cylinders are cross-connected under such high pressure conditions so as to relieve the high pressure from cylinder 23 to cylinder 24, thereby avoiding damage to the hydraulic system 27.
As the piston 43 moves to the right in FIG. 4, the piston rod 52 displaces hydraulic fluid from the bore 53 through a relief passage 57 to a third port 56 of body 41 communicating with relief space 51. Relief port 56 communicates with tank 28 through the return line 40 so as to return the hydraulic fluid to the tank for recirculation by pump 30, as discussed above.
In the event that a high pressure condition exists in cylinder 24 as by a high force being applied to the left portion of blade 11 so as to urge piston 22 rearwardly, as seen in FIG. 2, the high pressure condition is transmitted through crossline 39 to port 49 of the valve body 41 communicating with space 48 inwardly of the valve seat 46. This high pressure condition acts against the annular surface 50 of piston 43 exposed to the annular space 48,44. In the illustrated embodiment, the area of the annular surface 44 is substantially equal to the cross-sectional area of port 47, or valve seat 46. Thus, a hydraulic pressure in space 48,44 delivered thereto by crossline 39 causes a movement of the valve 45 and piston 43 to the right, as shown in FIG. 5, similarly to the movement effected to the right, as shown in FIG. 4, by a high pressure condition existing in port 47. Resultingly, the high pressure fluid is transferred to the port 47 and, thus, through crossline 38 to the cylinder 23 to relieve the high pressure condition acting on the cylinder 24 and thereby avoid damage to the hydraulic system 27.
Thus, when a preselected pressure is induced in either of ports 47 or 49, the valve 45 and piston 43 are moved to the right, as seen in FIGS. 4 and 5, to relieve that high pressure condition to the opposite cylinder.
At certain times, a high pressure condition may exist in both cylinders 23 and 24 as when a high load is applied uniformly across the blade which would tend to pivot the blade about the horizontal axis 26 and, thus, move each of piston rods 19 and 20 rearwardly, or to the left, as seen in FIG. 2, thereby applying a high pressure to both ports 47 and 49 through the respective crosslines 38 and 39. This second preselected high pressure condition being substantially greater than the first preselected high pressure conditions effecting operation of the valve means as shown in FIGS. 4 and 5, causes a further, or greater, movement of the valve 45 and piston 43 to the right, as seen in FIG. 6, so as to move piston 43 into the relief space 51, thereby providing communication between the annular space 48,44 and the relief port 56 so as to dump the hydraulic fluid to tank 28 through the return line 40 connected to relief port 56. The relief of the high pressure condition again prevents damage to the hydraulic system 27 under this second, higher pressure condition.
Upon relief of any of the above discussed pressure conditions, spring 54 returns the valve 45 to the closed position of FIG. 3, thereby again permitting normal use of the apparatus 10 as in a snowplowing operation.
It may be seen that the relief valve 37 is extremely simple and economical of construction utilizing only a single movable valve member and biasing means while yet providing the improved cross relief and dumping relief functioning discussed above.
The foregoing disclosure of specific embodiments is illustrative of the broad inventive concepts comprehended by the invention.
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An overload relief valve for use in preventing damage to the hydraulic system for adjustably positioning a working element, such as a blade. A single relief valve permits relief of high fluid pressure developed in either of the control cylinders by providing a crossover function therebetween under such conditions, as well as to relieve the fluid to tank in the event of a high pressure condition existing in both cylinders concurrently. The crossover relief may be effected by a similar first preselected high pressure condition in either of the cylinders.
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CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation of application Ser. No. 09/208,112, filed Dec. 9, 1998, now U.S. Pat. No. 6,090,217.
BACKGROUND OF THE INVENTION
This invention relates generally to the treatment of the surfaces of devices, especially semiconductor wafers and other electronic or electro-optical devices, at various stages of production. It relates more particularly to novel cleaning, chemical treatment and drying processes in which, instead of a condensed phase medium (liquid), a foam is used as a medium for the various operations such as cleaning, etching, neutralization and drying.
Semiconductor cleaning, chemical treatment and drying technology is well developed. Examples of known processes are those described in U.S. Pat. No. 4,781,764, dated Nov. 1, 1988, U.S. Pat. No. 4,911,761, dated Mar. 27, 1990, U.S. Pat. No. 5,271,774, dated Dec. 21, 1993 U.S. Pat. No. 5,656,097, dated Aug. 12, 1997 and U.S. Pat. No. 5,571,337, dated Nov. 5, 1996. However, cleaning, chemical treatment and drying of semiconductors is very expensive. Moreover, performance requirements will soon exceed the present and expected capabilities of current cleaning techniques.
Current processes for the cleaning and treatment of semiconductor wafers and other electronic devices have several serious drawbacks from the standpoint of cost, safety and effectiveness.
High purity deionized water is typically used as a solvent. However, achieving the necessary high purity levels is very expensive. Indeed, all phases of the cleaning operation, including purchasing, transportation, storage, internal distribution, consumption, and disposal, are expensive.
Most of the substances used in the cleaning and chemical treatment processes, such as fluorides, solvents, acids, heavy metals, oxidizers, etc., are toxic, flammable, or otherwise hazardous or obnoxious.
Chemical treatment and cleaning operations are also major sources of chemical contamination of the final product. Such contamination results from errant surface reactants, and physical contamination by undesired, very small solid particles. These very low levels of contaminants are delivered to the product, in part from the chemical treating and cleaning materials themselves, even though they are ultrapure. They are also delivered to the product from fittings, piping, tanks, valves, and other components of storage and delivery systems.
Contaminants on semiconductor wafer surfaces exist as films, discrete particles or groups of particles and adsorbed gases. Surface films and particles can be classified as molecular compounds, ionic materials and atomic species. Molecular compounds are mostly particles or films of condensed organic vapors from lubricants, greases, photo resists, solvent residues, organic components from deionized water or plastic storage containers, and metal oxides or hydroxides. Ionic materials comprise cations and anions, mostly from inorganic compounds that may be physically adsorbed or chemically bonded, such as ions of sodium, fluorine and chlorine. Atomic or elemental species comprise metals, such as gold and copper, which may be chemically bonded to the semiconductor surface, or they may consist of silicon particles or metal debris from equipment.
Semiconductor devices, especially dense integrated circuits, are vulnerable to all of these contamination sources. The sensitivity is due to the small feature sizes and the thinness of the deposited layers on the wafer surface. These dimensions are in the submicron range. The small physical dimensions of the devices make them very vulnerable to particulate contamination in the air, from workers, generated by the equipment, and present in processing chemicals. As the feature size and films become smaller, the allowable particle size must be controlled to smaller dimensions. In general, the particle size should be 10 times smaller than the minimum feature size. Currently, the minimum feature size for commonly available semiconductor chips is 0.25μ, therefore suggesting particle control to 0.025μ.
Conventional cleaning technologies, utilizing condensed phase solutions, when properly applied, remove a majority of the contaminants generated during the chemical processing of the semiconductor wafers. Liquid systems currently in use can delivery satisfactory results, and acceptable product can be produced. However, the current trend is to require the chemical and equipment suppliers to provide increasingly clean performance. Equipment and chemical suppliers are facing tremendous performance challenges as the feature size decreases. At the same time, semiconductor manufacturers do not want their costs to increase.
Another problem addressed by this invention is the drying of surfaces in the production of semiconductor wafers and similar devices.
Semiconductor wafers are not manufactured in a continuous process. Since there are many semiconductor wafer configurations, batches of wafers are processed through certain steps, and then stored. Later the batches are subjected to additional processing steps, and again stored. The processing and storage sequence may be repeated several times before processing is completed.
In general, at the end of each process sequence, the semiconductor wafers are dried, often even when the next step will proceed almost immediately. Wafers can be transported from one process sequence to the next only after they have been dried, and they can only be stored safely when they are dry. Therefore, the drying process is carried out frequently in the processing of a given wafer, and is very important.
Recently, isopropyl alcohol has become a preferred drying solvent. A variety of processes have been developed and commercialized using isopropyl alcohol either hot or cold, and as a vapor, a liquid or a combination of vapor and liquid. Semiconductor wafer producers have been moving toward reduced isopropyl alcohol usage because of its cost, fire hazards, disposal problems, and VOC (volatile organic compound) emissions.
U.S. Pat. No. 4,911,761, dated Mar. 27, 1990, describes semiconductor wafer processing in which various fluids passed over wafers in fixed positions. The drying sub-system utilizes superheated isopropyl alcohol vapor generated in a distillation apparatus.
U.S. Pat. No. 5,271,774, dated Dec. 21, 1993 describes a technique for removing water from a semiconductor wafer using low levels of solvents such as isopropyl alcohol, applied as a vapor, to reduce the surface tension of a film of liquid on the substrate, and thereby reduce the quantity of material remaining on the surface of the substrate. A centrifuge is used to facilitate the removal of the liquid film.
U.S. Pat. No. 5,571,337 describes another technique for drying semiconductor wafers, utilizing a trace amount of a polar organic compound in a carrier gas composed of oxygen, nitrogen, argon, or mixtures. This patent describes the drying of wafers without the use of isopropyl alcohol, using only warm nitrogen gas. Thus, the industry has proceeded from the use of large quantities of isopropyl alcohol, to minimal quantities of isopropyl alcohol, and then to processes which use no isopropyl alcohol at all.
The principal objects of this invention are to increase the effectiveness of chemical treatment, cleaning and drying operations, and to reduce the cost of such operations. Further objects of the invention are to improve the safety of the chemical treatment, cleaning and drying operations and to reduce the discharge of hazardous or obnoxious substances from the treating and cleaning operations.
SUMMARY OF THE INVENTION
Briefly, the invention takes advantage of a desirable characteristic of foam, namely that, from a volumetric standpoint, a given quantity of foam consists mostly of gas. Therefore the quantity of small particles delivered to a substrate by the liquid component of the foam is much smaller than the quantity of particles delivered to a substrate by an equivalent volume of a liquid.
The expansion ratio of foam, i.e. the volume of the foam divided by the volume of its liquid component, defines the cost and performance benefit available from the use of foam. For example, if the expansion ratio is 10, the volume of liquid is reduced to {fraction (1/10)} of the volume of liquid to which the substrate is exposed in a condensed phase chemical treatment or cleaning step. This not only achieves a theoretical materials cost reduction of 90% but also reduces the quantity of contaminating particles delivered to the substrate by a factor of 10. A small increase in the expansion ratio results in a relatively large overall benefit. Additional cost savings can be obtained as a result of the reduction in the volume of the cleaning medium. The resulting smaller inventory of cleaning medium, and the size reductions that can be achieved in components such as tanks, valves, pipes, pumps, etc., lead to lower floor space requirements, which, for semiconductor fabrication facilities, is very significant.
In accordance with one aspect of the invention, the treatment, i.e. cleaning or chemical treatment, of a semiconductor substrate is carried out by the steps of generating a foam consisting of gas bubbles and a liquid component, and causing the foam to pass over the substrate while in moving contact therewith.
In accordance with another aspect of the invention, a semiconductor substrate is dried by a process comprising the steps of generating a foam consisting of carbon dioxide bubbles and deionized water, and causing the foam to pass over the substrate in moving contact therewith.
The cleaning or chemical treatment steps, and the drying step can be carried out in the same treatment vessel. The cleaning, chemical treatment and drying steps can be carried out in sequence without removing the substrate from the treatment vessel.
Other features of the invention are applicable not only to the cleaning, chemical treatment and drying of semiconductor substrates, but also to the cleaning, chemical treatment and drying of other substrates where the removal of extremely small particles or other contaminants, or avoidance of their deposition onto the substrate, is important.
Preferably, the semiconductor substrate is supported in a foam treatment vessel, the foam is generated outside the foam treatment vessel and introduced into the foam treatment vessel, and foam in contact with the semiconductor substrate is caused to pass over the substrate as a result of its displacement by foam introduced into the foam treatment vessel. A sufficient quantity of foam may be introduced to fill the treatment vessel and thereafter, by continued introduction of foam into the treatment vessel, foam may be caused to discharge from the treatment vessel.
For cleaning the substrate, the liquid component of the foam may consist of a surface tension-reducing agent and deionized water, and the movement of the foam removes particles from the substrate. For chemical treatment of the substrate, the liquid component of the foam may include one or more reactants, such as ammonium hydroxide, hydrofluoric acid, nitric acid, etc., so that a chemical reaction takes place between the substrate and the reactant as the foam passes over the substrate. The reactants themselves may serve as surface tension-reducing agents. However, ordinarily, since the reactants will be present in insufficient concentrations to produce adequate quantities of foam, conventional surfactants or other additional surface tension-reducing agents will be included along with the reactants.
In a preferred embodiment, the foam introducing step is carried out by first introducing a foam consisting essentially of a surface tension-reducing agent and deionized water, thereafter introducing a foam comprising deionized water, a surface tension-reducing agent and at least one reactant for chemical treatment of the substrate whereby a chemical reaction takes place between the substrate and the reactant, and thereafter introducing a foam consisting essentially of a surface tension-reducing agent and deionized water, whereby said at least one reactant is rinsed from the substrate.
A foam-based cleaning system in accordance with the invention can effectively substitute for a liquid phase system using sonic energy.
The process may be carried out by alternately introducing foam consisting essentially of a surface tension-reducing agent and deionized water, and foam comprising a surface tension-reducing agent, deionized water and at least one reactant for chemical treatment of the substrate. By carrying out the process in this manner, a series of chemical treatment steps can be carried out on a semiconductor substrate, all using foam as a vehicle for the reactants.
In accordance with another aspect of the invention, for drying the substrate, the foam treatment vessel is preferably located within a pressurizable containment vessel. The substrate is submerged in a solution of carbon dioxide in deionized water under pressure, and thereafter foam is generated by reducing the pressure within the containment vessel. The pressure reduction causes carbon dioxide bubbles to form a foam layer on the surface of the solution. Thereafter the foam layer is caused to pass over the substrate in moving contact therewith by discharging the solution from the foam treatment vessel.
Other objects and advantages of the invention will be apparent from the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a treatment apparatus for cleaning or chemically treating a semiconductor substrate, in accordance with the invention;
FIG. 2 is a schematic diagram showing the treatment apparatus in operation;
FIG. 3 is a schematic diagram of a chemical feed and foam generating system for use with the treatment apparatus of FIGS. 1 and 2;
FIG. 4 is a schematic diagram illustrating the wetting of a semiconductor substrate by a mass of foam;
FIGS. 5 ( a )- 5 ( f ) are schematic diagrams illustrating successive stages in the wetting of a substrate by a foam bubble;
FIG. 6 is a schematic diagram of an apparatus for supplying a solution of carbon dioxide in deionized water for drying a substrate;
FIG. 7 is a schematic diagram of an apparatus for drying a semiconductor substrate, in accordance with the invention;
FIGS. 8, 9 and 10 are schematic diagrams illustrating successive stages in the drying process using the drying apparatus of FIG. 7;
FIGS. 11-15 are schematic diagrams illustrating details of the drying process; and
FIGS. 16 and 17 are schematic diagrams, corresponding to FIGS. 8-10, illustrating final stages of the drying process.
DETAILED DESCRIPTION
The physical and chemical conditions prevailing in the cleaning of semiconductor wafers lend themselves to easy and simple foaming performance optimization. The solvent system is extremely pure water, and therefore no minerals or hardness are present to interfere with foaming. The temperature can be readily adjusted to optimize foaming behavior. (Foaming is always better in warmer water because the surface tension decreases as the temperature increases.) The required persistence of the foam medium is generally less than one or two minutes. Accordingly, it is possible to use very fast-draining foams. In fact the use of fast-draining foams is desirable so that the foam self-destructs, avoiding the need for additional measures to remove it.
Foams are metastable and are formed by adding energy to a gas/liquid combination. As soon as the agitation, or mixing, force is removed the foam will start draining, thereby providing a liquid phase essentially identical to that provided in a condensed phase, all liquid, system. Therefore, for any liquid system shown to be an effective cleaning medium, a corresponding foam system will perform identically, because the surface layer composition, next to the semiconductor wafer, will be the same in both cases.
The significance of the use of foam in semiconductor surface cleaning technologies is that a foam-based cleaning system is capable of removing more particles than it generates. In contrast, with a condensed phase liquid system, the particle count potentially increases in successive processing steps, yielding potentially unsatisfactory final results.
The apparatus depicted in FIG. 1 is used for cleaning and chemically treating a substrate. It comprises an inner vessel 18 having a top opening 20 , located within an outer vessel 22 , which is also open at the top. A substrate 24 is supported within vessel 18 on a supporting frame 26 . The substrate is typically a semiconductor substrate such as a silicon wafer, either in the raw state or at one of the many stages in the fabrication process. Although only one wafer is shown, it should be understood that, in a wafer cleaning or chemical treatment operation, the support frame may carry a large number of wafers.
A foam inlet line 28 is connected to the interior of vessel 18 at or near the bottom of the vessel. A discharge line 30 is connected to the bottom of the outer vessel 22 through a valve 32 , and to the bottom of the inner vessel 18 through valves 32 and 34 in series.
The foam inlet line 28 carries foam into the inner vessel from a static mixer 36 shown in FIG. 3 . The static mixer can be any of a variety of known devices used to produce foam by mixing a gas with a liquid containing a surface tension-reducing agent. Suitable static mixers are described in U.S. Pat. No. 4,400,220, dated Aug. 23, 1983 and U.S. Pat. No. 5,133,991, dated Jul. 28, 1992. A suitable surface tension-reducing agent is a nonionic surfactant available from Wako Chemical of Richmond, Va. under number NCW-601A. A wide variety of substances can be used as surface-tension reducing agents for the purpose of forming foams in deionized water. These include conventional surfactants, i.e. soaps and detergents of course, but also include a wide range of other substances such as isopropyl alcohol, nitrous oxide, isobutane, and carbon dioxide. The concentration of the surface tension-reducing agent should be sufficiently low to provide a fast drain time since, as will be apparent, it is important to avoid filling the outer vessel with foam. In the case of conventional surfactants, the appropriate concentration is typically in the range of 100 ppm. to 2000 ppm. For isopropyl alcohol, the concentration will typically be in the range of 1.0%. Various other solutes, including reactants such as ammonium hydroxide, nitric acid, hydrofluoric acid, etc. are normally used in concentrations too low to produce effective foams, and need to be supplemented by other surface tension reducing agents such as conventional surfactants.
As shown in FIG. 3, a gas supply line 38 delivers a gas to the static mixer 36 and also to liquid supply tanks 40 , 42 , 44 , 46 and 48 . The gas pressure is thus used to drive liquids from the tanks into the static mixer. The gas can be any of many suitable gases, including nitrogen, argon, air, carbon dioxide and other gases. In general, nitrogen is preferred.
Tank 40 contains a solution consisting of a surface tension-reducing agent in deionized water. Tanks 42 - 48 hold a variety of reactants used for chemical treatment of the substrates. Examples of such reactants are cleaning mixtures such as solutions of ammonium hydroxide and hydrogen peroxide in deionized water, and etchants such as solutions of hydrofluoric acid in water. Valves 50 , 52 , 54 and 56 control the flow of reactants from the reactant supply tanks so that the reactants can be supplied selectively to the static mixer along with the solution of surface tension-reducing agent.
As shown in FIG. 2, foam is introduced through the foam inlet line 28 until the inner vessel 18 is filled, and then continued introduction of foam causes excess foam to overflow the inner vessel and drop into the outer vessel. The foam is relatively short-lived, and the layer 60 in the lower portion of the outer vessel 22 quickly drains, forming a layer 62 of liquid, which is carried off though valve 32 to discharge line 30 .
The introduction of foam into vessel 18 causes the foam within the vessel to rise continuously so that it passes over the substrate 24 in moving contact with the substrate.
As shown in FIG. 4, the foam bubbles 64 adjacent the surface 66 of the substrate are draining. As shown in FIG. 5 ( a ), when a bubble 68 approaches the surface 66 , and the bubble has not yet wetted the surface, the surface is dry. However, as shown in FIG. 5 ( b ), as soon as the bubble contacts the surface, it almost immediately wets the surface over an area approximately equivalent to the cross-section of the original bubble through its center. FIGS. 5 ( c )- 5 ( f ) show that, as the bubble drains, the wetted area gradually increases until the bubble is fully drained as in FIG. 5 ( f ). The mass of bubbles, as shown in FIG. 4, forms a continuous film on the surface 64 of the substrate.
As the mass of bubbles moves across the surface of the substrate, particles are scrubbed from the surface. Thus, if the foam consists only of deionized water and surface tension-reducing agent, it serves to clean the substrate. On the other hand, if the foam also includes a reactant, it not only removes any remaining particles from the surface, but also delivers a film of reactant to the surface. In both cases, the quantity of particles delivered to the surface of the substrate by the foam itself is far lower than the quantity that would be delivered by a liquid in a cleaning or chemical treatment operation.
The fast drain time of the foam is important not only in order to prevent the outer vessel from filling with foam, but also in order to allow the reactant to be applied to the substrate in a liquid phase.
While in the treatment vessel 18 , the substrate can be exposed to a series of cleaning and chemical treating steps. For example, the substrate may be cleaned by first introducing a foam consisting essentially of a surface tension-reducing agent and deionized water. Thereafter, by opening the appropriate valve in the chemical feed and foam generating system of FIG. 3, a foam comprising a surface tension-reducing agent, deionized water and a reactant is introduced in order to effect a chemical reaction, e.g. chemical cleaning, on the surface of the substrate. Thereafter, the flow of the reactant is cut off, and the reactant is rinsed from the surface of the substrate by foam once again consisting essentially of the surface tension-reducing agent and deionized water. The rinsing step may be followed by another chemical treatment step, e.g. etching, carried out by opening an appropriate valve in FIG. 3 to introduce an etchant into the static mixer along with the surface tension-reducing agent solution so that the foam film in contact with the substrate applies the etchant to the substrate. Chemical treatment and rinsing steps may be carried alternately in an extended sequence of steps in which the reactants are different in the successive reactant introduction steps.
The use of foam not only reduces the quantity of particles delivered to the surface of the substrate in the cleaning and chemical treatment process, but also reduces the quantity of reactants needed to carry out chemical treatment.
The drying process utilizes a carbon dioxide solution in deionized water. Carbon dioxide has a number of desirable properties, which make it ideal for use in a foam drying process. It is inexpensive, readily available, water soluble, and non-flammable. It is also non-toxic, causes no VOC emissions, and a water solution of carbon dioxide can be disposed of in a conventional sanitary sewer without special treatment or other precautions. Although a solution of carbon dioxide in water forms carbonic acid (H 2 CO 3 ), the level of carbonic acid formed is very low, and it has little, if any, effect on the pH of the solution. In water, carbon dioxide serves as a surface tension reducing agent, thereby allowing foaming.
The carbon dioxide solution is generated by the apparatus shown in FIG. 6 . Carbon dioxide is maintained under pressure in a tank 70 , which is refilled from time to time through a valve 72 in inlet line 74 . In tank 70 , carbon dioxide is present in the liquid phase at 76 and in the gaseous phase at 78 . The gaseous carbon dioxide is fed, through valve 80 and check valve 82 , to a tank 84 , where it is dissolved in deionized water to form a solution 86 . The solution has a layer 88 of gaseous carbon dioxide above it, which is under pressure. The pressure of this layer of gaseous carbon dioxide is used to discharge the solution, through line 90 and valve 92 , to a drying apparatus. Deionized water is replenished through line 94 and valve 96 , and the solution is kept in motion by agitator 98 to maintain homogeneity.
The carbon dioxide solution is delivered through line 90 to the apparatus shown in FIGS. 7-10. The apparatus of FIGS. 7-10 can be the same apparatus as depicted in FIG. 1, but is provided with a top closure 100 , allowing the outer vessel to be pressurized, a pressure control valve 102 for controlled venting of pressure within the outer vessel, and a valve 104 , which can be closed after the carbon dioxide solution is fed into the inner vessel 18 .
In the drying operation, the inner vessel 18 is filled with carbon dioxide solution through valve 104 while the pressure control valve 102 is either closed, or only partly opened, in order to prevent carbon dioxide bubbles from being released from the solution as it fills the inner vessel 18 . As shown in FIG. 8, the carbon dioxide solution fills the inner vessel to a level 106 , above the uppermost part of the substrate 24 .
After filling the inner vessel 18 , valve 102 is opened in a controlled manner to relieve the pressure within the outer vessel. The relieving of the pressure causes carbon dioxide bubbles to be released from the solution. These bubbles form a layer 108 of foam on the surface of the solution as shown in FIG. 9 .
Promptly after the layer of foam is formed, valves 34 and 32 are opened to discharge the carbon dioxide solution from the inner vessel through line 30 . The discharge takes place by gravity, but may be assisted by residual gas pressure within the enclosure. The foam layer 108 descends, as shown in FIG. 10, passing downwardly over the substrate.
As shown in FIGS. 11-15, the foam layer scrubs particles from the surfaces of substrate 24 as it descends. In FIG. 11, the substrate is completely submerged in the carbon dioxide solution. Particles 110 are shown adhering to the surfaces of the substrate. As shown in FIGS. 12 and 13, the particles 110 are scrubbed by the interface of the foam layer and the carbon dioxide solution, and carried downward by the foam layer along the surfaces of the substrate so that they are removed from the substrate as shown in FIG. 14 and carried toward the bottom of the vessel.
As the solution continues to be discharged from the vessel, the foam layer 108 clears the substrate, leaving the substrate in an atmosphere of carbon dioxide with some water vapor, as shown in FIG. 16 . Ultimately, the foam layer 108 collapses leaving a residue 112 as shown in FIG. 17 .
An example of a typical drying operation in accordance with the invention is as follows: The process starts with a frame carrying fifty 200 mm wafers, with 6 mm spacing, submerged in an overflow tank, i.e. vessel 18 in FIG. 8, within the drying unit containment vessel, i.e. vessel 22 . The overflow tank contains, pure deionized water with either air or nitrogen as the overhead gas at atmospheric pressure or slightly above. The tank size is 25 cm (depth)×25 cm (width)×50 cm (length). Therefore, the volume is 31.25 liters without considering the volume of the carrying frame or the wafers. The wafers are about 100 cm 3 each, or 5000 cm 3 (5 liters) total, and the carrying frame is 1000 cm 3 (1 liter). Therefore, the liquid volume is 25.25 liters.
The containment vessel includes the necessary valves, check valve, pressure relief valves, baffles, channels, inlets, outlets, and access panels (doors, lids, etc.) to allow the process to operate safely at a total pressure of approximately 300 psig. To simplify calculations, assume that the total volume of the containment vessel is 30.00 liters. The external containment vessel is closed and prepared for pressurization.
The surface tension of CO 2 in water at 300 psig total pressure is between 57 dynes/cm at 11° C. and 59 dynes/cm at 45° C. This suggests that temperature is not an important variable, but that is misleading, since the solubility of CO 2 in water at 300 psig is very dependent upon the temperature. At 300 psig and 10° C. the solubility of CO 2 in water will produce a 4.5 weight percent solution. Since the CO 2 not only reduces the surface tension, but also generates the foam, the amount of CO 2 in the water is important, since the foam must be maintained during the liquid discharge interval.
In a separate adjacent vessel, suitably designed and equipped, and plumbed to the drying unit described above, pure deionized water is saturated with carbon dioxide at a pressure slightly higher than the 300 psig design pressure, and at a temperature about 10° C., yielding a concentration of carbon dioxide in water at 4.5 weight percent. The reason for the slight pressure increase is that the liquid will be pressure fed into the drying vessel, thereby eliminating the need for pumping systems which, in general, are sources of contamination due to their moving parts.
The pure deionized submersion water is replaced by equally pure deionized water containing carbon dioxide at 10° C. The atmospheric gas or nitrogen in the containment vessel is discharged and replaced with CO 2 while, at the same time, the total pressure of the system is increased to 300 psig. This step can be executed either of two ways. The dissolved CO 2 in the water can exchange with the air or nitrogen atmosphere, forming a new pressurized atmosphere of CO 2 . Alternatively, the overhead atmospheric gas is displaced by direct injection of CO 2 , purging the air or nitrogen while increasing the pressure within the containment vessel. The latter approach is desirable, because it is faster and produces less waste.
It is not necessary to eliminate every molecule of the original overhead gas. In general three displacement volumes are sufficient. The gas volume in the containment vessel is 30000 cm 3 , which converts to 120,000 cm 3 CO 2 measured at STP (ignoring minor temperature differences). Since 44 grams of CO 2 occupy 22400 cm 3 at STP, the weight of CO 2 used is:
44×120000/22400=236 grams.
The pressure must be elevated to 20 atm, 300 psig, therefore requiring twenty times more CO 2 :
236×20/1=4720 grams.
This procedure removes the overhead gas and pressurizes the containment vessel. The time interval required to carry out this operation is only about one minute, and therefore the amount of CO 2 adsorbed by the submersion water is not significant.
The next step is to displace the original submersion water. The carbon dioxide-saturated water in the storage tank is pressure fed into the containment vessel by a near quantitative displacement. It is not critical if some of the original submersion water is retained. This step requires 25.25 liters of water, 25250 grams, containing 4.5 wt % CO 2 , or,
22250×0.045=1136 grams of CO 2 .
The wafers are now submerged in a solution of carbon dioxide-saturated, deionized water. The surface tension of the solution is 57-59 dynes/cm. The overhead gas is carbon dioxide at 300 psig.
Quiescent, supersaturated solutions of carbon dioxide in water depend upon external forces to initiate the desorption process. Here, however, the carbon dioxide solution has no opportunity to become quiescent if, promptly after the carbon dioxide solution is introduced, depressurization of the outer vessel occurs. Depressurization initiates foaming, and the introduction of new carbon dioxide solution while the liquid level drops causes foaming to continue. Other measures, such as agitation, imparting turbulence to the incoming carbon dioxide solution, or the introduction of small amounts of nitrogen or other gas, can be used to ensure initiation of foaming, where necessary.
For the next step, assume that the carbon dioxide foam provides an expansion ratio of ten (E/R=10); a 100% drain time of 20 seconds; and an average foam thickness on the surface of 25.4 mm. The fluid-atmosphere interface descent rate should be about 50-75 mm/minute. If the 250 mm depth of the overflow vessel is covered in 4 minutes, the average rate is 64 mm/minute.
The surface of the overflow tank is 200 in 2 , so the volume of the foam required is 200 in 3 (3277 cm 3 ). The foam volume has to be maintained for the four minutes required for the venting of the containment vessel and the descent of the gas-liquid interface.
The venting can proceed linearly, and programmed depressurization can be accomplished by the declining liquid level and controlled overhead gas venting.
Since the foam volume needs to be maintained, the amount of carbon dioxide delivered to the drying unit has to be constant, but adjusted for the declining pressure. At 20 atmospheres, the carbon dioxide requirement is twenty times higher than at 1 atmosphere. The only source of carbon dioxide during this process interval is the saturated water solution stored in the adjacent tank.
The liquid level in the tank declines, but as this takes place, carbon dioxide and water are added so that the foaming of the carbon dioxide can maintain the foam blanket. Therefore, the carbon dioxide-water flow rate is defined by the amount of carbon dioxide required, while the liquid discharge rate from the vessel must accommodate the original liquid plus the added influent, while still maintaining a proper gas-liquid interface descent rate.
The system starts at 300 psig (315 psia) and declines to 0 psig (15 psia) in four minutes.
The following Table I, illustrates the conditions under which a constant volume of foam can be maintained as the liquid is discharged.
Column D lists the foam volume, which must be replaced during each 20-second interval. The foam volume is constant and is equal to the horizontal cross sectional area of the foam layer multiplied by its height. Column E collects the cumulative foam volume.
In Column F, the carbon dioxide volume portion of the foam, at pressure, is given. The expansion ratio of the foam is ten. Therefore, 90% of the foam volume is carbon dioxide, the expansion gas, while the balance is water. Column G accumulates Column F.
Column H converts the Column F data to carbon dioxide volume (cc.) at STP, without temperature adjustment. The pressure conversion is measured in absolute pressure, not gauge pressure, so the factor is: (15+P)/15. Column I is the cumulative carbon dioxide volume at STP in cubic centimeters.
Column J converts Column H into carbon dioxide by weight, using 22400 cc/mole as the standard molar volume and 44, the molecular weight of carbon dioxide. Column K is the cumulative carbon dioxide weight.
Columns L, M, N, and O show similar data for the water portion of the incoming feed stream. Since the carbon dioxide is 4.5 weight %, the water portion must be 95.5 weight %. Column L displays the 20-second interval data in grams, while Column M shows the cumulative data, converted to kilograms, without the carbon dioxide portion included.
TABLE I
DRYING VESSEL DISCHARGE DATA
PART 1
F
G
H
I
D
E
INTERVAL
CUMULATIVE
INTERVAL
CUMULATIVE
A
B
C
INTERVAL
CUMULATIVE
CO2 GAS
CO2 GAS
CO2 GAS
CO2 GAS
TIME
TIME
PRESSURE
FOAM
FOAM
at P
at P
STP
STP
(sec)
(min)
(psig)
(cc)
(cc)
(cc)
(cc)
(cc)
(cc)
1
0
0.00
300
3277
3277
2949
2949
61935
61935
2
20
0.33
275
3277
6554
2949
5899
57020
118955
3
40
0.67
250
3277
9831
2949
8848
52104
171059
4
60
1.00
225
3277
13108
2949
11797
47189
218248
5
80
1.33
200
3277
16385
2949
14747
42273
260522
6
100
1.67
175
3277
19662
2949
17696
37358
297879
7
120
2.00
150
3277
22939
2949
20645
32442
330322
8
140
2.33
125
3277
26216
2949
23594
27527
357848
9
160
2.67
100
3277
29493
2949
26544
22611
380460
10
180
3.00
75
3277
32770
2949
29493
17696
398156
11
200
3.33
50
3277
36047
2949
32442
12780
410936
12
220
3.67
25
3277
39324
2949
35392
7865
418801
13
240
4.00
0
3277
42601
2949
38341
2949
421750
PART 2
J
K
N
O
INTERVAL
CUMULATIVE
L
M
INTERVAL
INTERVAL
A
B
C
CO2 GAS
CO2 GAS
INTERVAL
CUMULATIVE
WATER
WATER
TIME
TIME
PRESSURE
WEIGHT
WEIGHT
WATER
WATER
FLOW
FLOW
(sec)
(min)
(psig)
(gm)
(gm)
(gm)
(kgm)
(gm/sec)
(gpm)
1
0
0.00
300
122
122
2704
2.70
141.3
2.24
2
20
0.33
275
112
234
2489
5.19
130.0
2.06
3
40
0.67
250
102
336
2274
7.47
118.8
1.88
4
60
1.00
225
93
429
2060
9.53
107.6
1.71
5
80
1.33
200
83
512
1845
11.37
96.4
1.53
6
100
1.67
175
73
585
1631
13.00
85.2
1.35
7
120
2.00
150
64
649
1416
14.42
74.0
1.17
8
140
2.33
125
54
703
1202
15.62
62.8
1.00
9
160
2.67
100
44
747
987
16.61
51.6
0.82
10
180
3.00
75
35
782
772
17.38
40.4
0.64
11
200
3.33
50
25
807
558
17.94
29.1
0.46
12
220
3.67
25
15
823
343
18.28
17.9
0.28
13
240
4.00
0
6
828
129
18.41
6.7
0.11
As will be apparent from columns N and O, the water flowrate decreases linearly over time.
Ultimately, the drying vessel depressurization is complete and the vessel is empty, closed, and at atmospheric pressure. The atmosphere in the vessel is essentially all carbon dioxide as the vapor pressure of water at 10° C. is about 10 mm Hg., thereby defining that the partial pressure of carbon dioxide is 750 mm Hg. when the total pressure is one atmosphere or 760 mm Hg.
The entire vessel with its wafers and the supporting carriage will have some small amount of water remaining, particularly at the contact points where the wafers touch the carrying frame. That water, and any other within the vessel, can be removed by using carbon dioxide as a purging gas at room temperature for a few minutes, with the final carbon dioxide replaced with nitrogen, if desired. The dry carrier-supported wafers can then be removed from the drying equipment and stored or transported in an appropriate enclosure.
The following example illustrates a flow-through process analogous to the current, continuous phase, flow-through process in which deionized water is the medium and active ingredients are added as the chemical treatment process progresses. The treatment process begins with water, followed by etching, oxidizing, neutralization, each such step being followed by an intervening rinsing step, and finally drying at the end of the sequence.
In accordance with the invention, the same general sequence is executed using a foam medium. The expansion gas can be argon, air, or nitrogen, but nitrogen is preferred.
Instead of deionized water, the initial medium is deionized water with Wako Chemical NCW-601A surfactant, added as a foaming agent. The level of surfactant needs to be low, e.g. 300 ppm, enough to provide a fast drain time.
The wafers are placed in a flow-though system corresponding to the apparatus of FIG. 1, and foam is passed over them. In the first step, treatment with ammonium hydroxide and hydrogen peroxide, the “to-be-foamed” liquid (deionized water and surface tension-reducing agent) has the required amount of ammonium hydroxide and peroxide added. Foaming occurs, and the wafers are treated with this oxidizing solution. It is important that the foam has a fast drain time, as it must produce a liquid phase of the desired composition. For example, if the desired solution requires 1000 ppm of hydrogen peroxide and 500 ppm of ammonium hydroxide, plus surface tension-reducing agent, in deionized water, then that solution is composed, foamed, and injected into the treatment vessel. The appropriately timed drainage provides the liquid phase composition to the surface of the wafer, but reduces the total volume of material required in proportion to the reciprocal of the expansion ratio.
After five minutes of treatment time, the hydrogen peroxide and the ammonium hydroxide injections are stopped, but the surface tension-reducing agent and deionized water continue. The foaming phase is now a rinsing phase utilizing only deionized water and surface tension-reducing agent. This rinsing foam continues to pass through the treatment vessel until the previous reactants are flushed away.
The next sequence is an etching cycle, and the appropriate ingredients are added to the liquid before foaming, foaming occurs, treatment follows, the actives injection is stopped, and the rinsing cycle follows.
The third step follows in the same manner, as does the fourth, and fifth, if required, each ending with a rinsing phase.
Eventually, the chemical treatment is completed, and drying becomes the final step. The injection of surface tension-reducing agent into the water is stopped, the expansion gas injection is stopped, the foaming stops, and the system is converted to a liquid system, while the residual surface tension-reducing agent is flushed from the treatment vessel. This leaves the treatment vessel filled with deionized water, and the drying process can proceed. Carbon dioxide-saturated water, as described above, is injected into the now pressurized vessel, and the drying sequence continues.
It is important to recognize that all of the process variables, including fluid temperature and fluid composition, can be accommodated with a foam based system, simply by heating or cooling the incoming deionized water and injecting the proper levels of ingredients.
Various modifications can be made to the apparatus and processes described. For example, the cleaning and chemical treatments can take place either in the same vessels or in separate vessels, and the drying can take place in the same vessel in which cleaning and chemical treatment take place. Normally, the cleaning and chemical processing steps take place sequentially without any intermediate drying steps, and drying is carried out only as a final step when the wafers are to be removed from the treatment vessel. However, cleaning and chemical treatment steps may be carried out alternately with drying in the same vessel, especially when one or more of the chemical treatment steps is gas treatment.
Furthermore, as indicated previously, in the drying process, carbon dioxide can be introduced to purge the air, nitrogen or other atmosphere by introduction of carbon dioxide solution rather than by direct carbon dioxide injection. Still other modifications can be made without departing from the scope of the invention as defined by the following claims.
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Surface cleaning, chemical treatment and drying of semiconductor substrates is carried out using foam as a medium instead of a condensed phase liquid medium. In cleaning and chemical treatment, by introducing a foam into an overflow vessel the foam is caused to pass over the substrate in moving contact therewith. Drying of the substrate is carried out, using a water solution of carbon dioxide in a pressurizable vessel. By releasing the pressure in the vessel, a layer of foam is established on the surface of the solution. The solution is discharged from the vessel, causing the foam layer to pass over the substrate in moving contact therewith. The carbon dioxide reduces the surface tension of the water, thereby enabling the foam layer to be produced and also assisting in the elimination of water from the surface of the substrate. In both cases, the use of foam reduces materials requirements and also reduces the quantity of particles deposited onto the substrate in the treatment process.
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RELATED PATENT APPLICATIONS
This patent application is related to U.S. patent application Ser. No. 13/168,047 entitled “Curable composition comprising a di-isoimide, method of curing, and the cured composition so formed;”, U.S. patent application Ser. No. 13/168,062 entitled “Laminate comprising curable epoxy film layer comprising a di-isoimide and process for preparing same;” U.S. patent application Ser. No. 13/168,069 entitled “Printed wiring board encapsulated by adhesive laminate comprising a di-isoimide, and process for preparing same;” and, U.S. patent application Ser. No. 13/168,081 entitled “Process for Preparing Substituted and Unsubstituted Diamino triazine aromatic di-isoimides.”
FIELD OF THE INVENTION
The present invention deals with a novel aromatic di-isoimide chemical compound that has utility as a catalyst and as a curing agent in epoxy compositions. It also can be used as a flame retardant in thermoplastic and thermoset polymers.
BACKGROUND OF THE INVENTION
Epoxy compositions are widely used in many applications including, among others, the electronics industry. In some applications they are blended with rubber to provide enhanced flexibility, toughness, and adhesive strength. One such application is as a flexible cover layer for flexible printed wiring boards.
While epoxies offer many desirable properties, they are known to be undesirably flammable, often requiring the addition of a flame retardant to a curable epoxy formulation in order to meet fire resistance standards. In addition, it is desirable to have a curable epoxy composition with as long a shelf life as possible. One approach to achieving long shelf-life is to prepare a so-called latent curing catalyst or cross-linking agent (curing agent). A latent catalyst or curing agent could be inactive at room temperature but thermally activated at a temperature well above room temperature. For practical reasons, it is desirable for uncured compositions to remain stable at temperatures up to 40 or 50° C. Thus a latent catalyst or curing agent activated at a temperature above 50° C. but below a temperature that will degrade the epoxy or electronic circuit elements is highly desirable in the art. A catalyst or curing agent that further obviates the need for a flame retardant additive would be so much the better for the properties of the resultant composition.
SUMMARY OF THE INVENTION
The composition of the present invention provides a curing catalyst and cross-linking agent suitable for use in a curable epoxy composition, a curable epoxy composition prepared therewith, a cured composition prepared therefrom, a film or sheet coated with the curable composition, and an encapsulated printed wiring board comprising the cured composition.
In one aspect, the present invention provides a di-isoimide composition represented by Structure I
wherein R 1 is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″ where R′ and R″ are independently H, alkyl or aromatic, substituted or unsubstituted.
In another aspect, the invention provides a first process for preparing a di-isoimide composition represented by the Structure I, the process comprising mixing, at a temperature in the range of −10 to 160° C., in a first solvent pyromellitic dianhydride (PMDA) with a substituted or unsubstituted di-amino triazine represented by the Structure II
wherein R 1 is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″ where R′ and R″ are independently H, alkyl or aromatic, substituted or unsubstituted.
In a further aspect, the present invention provides a curable composition comprising a solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I
wherein R 1 is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″ where R′ and R″ are independently H, alkyl or aromatic, substituted or unsubstituted.
In a further aspect, the present invention provides a second process comprising heating the curable composition hereof to a temperature in the range of 100 to 250° C. for a period of time in the range of 30 seconds to 5 hours, thereby forming the corresponding cured composition.
In another aspect, the present invention is directed to a laminated article comprising a substrate and a coating deposited thereupon wherein said substrate is a polymeric sheet or film and said coating comprises a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I.
In a further aspect, the present invention is directed to a printed wiring board comprising in order a first layer of a first dielectric substrate, a second layer of one or more discrete electrically conductive pathways disposed upon said first dielectric substrate, a third layer of an adhesively bonding layer in adhesive contact with said discrete electrically conductive pathways, and a fourth layer of a second, flexible, dielectric substrate, said adhesively bonding layer comprising a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I.
In another aspect, the present invention provides a process for preparing an encapsulated printed wiring board, the process comprising adhesively contacting the coated surface of a laminated article having a surface with a coating disposed thereupon to at least a portion of the discrete conductive pathways disposed upon a dielectric substrate thereby forming a multilayer article; and, applying pressure to the printed wiring board so formed at a temperature in the range of 100 to 250° C. for a period of time in the range of 30 seconds to 5 hours, thereby forming an encapsulated printed wiring board; wherein said printed wiring board comprises in order a first layer of a first dielectric substrate, a second layer of one or more discrete electrically conductive pathways disposed upon said first dielectric substrate, a third layer of an adhesively bonding layer in adhesive contact with said discrete electrically conducting pathways, and a fourth layer of a second, flexible, dielectric substrate, said adhesively bonding layer comprising a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic representation of the process hereof for creating the printed wiring board hereof, as described in Example 12.
DETAILED DESCRIPTION OF THE INVENTION
The term “epoxy” refers to a polymeric, generally an oligomeric, chemical comprising epoxide groups. A cross-linking agent suitable for use in the processes disclosed herein is a multifunctional molecule reactive with epoxide groups. The cross-linked reaction product thereof is the reaction product formed when the cross-linking agent reacts with the epoxide or other group in the epoxy molecule. The term “epoxy” is conventionally used to refer to the uncured resin that contains epoxide groups. With such usage, once cured, the epoxy resin is no longer actually an epoxy. However, reference to epoxy herein in the context of the cured material shall be understood to refer to the cured material. The term “cured epoxy” shall be understood to mean the reaction product of an epoxy as defined herein and a curing agent as defined herein.
The term “cured” refers to an epoxy composition that has undergone substantial cross-linking, the word “substantial” indicating an amount of cross-linking of 75% to 100% of the available cure sites in the epoxy. Preferably more than 90% of the available cure sites are cross-linked in a “fully cured” epoxy composition. The term “uncured” refers to an epoxy composition when it has undergone little cross-linking. The terms “cured” and “uncured” shall be understood to be functional terms. An uncured epoxy composition is characterized by solubility in organic solvents and the ability to undergo plastic flow under ambient conditions. A cured epoxy composition suitable for the practice of the invention is characterized by insolubility in organic solvents and the absence of plastic flow under ambient conditions. It is well-known in the art that some of the available cure sites in an uncured epoxy composition could be cross-linked and some of the available cure sites in a cured epoxy composition could remain uncross-linked. In neither case, however, are the distinguishing properties of the respective compositions significantly affected.
The art also distinguishes a partially cured epoxy composition known as a “B-stage” material. The B-stage material may contain up to 10% by weight of solvent, and exhibits properties intermediate between the substantially cured and the uncured state.
For the purposes of the present invention the term “curable composition” shall refer to a composition that comprises all the elements necessary for producing a “cured” composition, but that has not yet undergone the “curing process” and is therefore not yet cured. The curable composition is readily deformable and processable, the cured composition is not. The terms “curable” and “cured” are similar in meaning, respectively, to the terms “crosslinkable” and “crosslinked.”
While the invention is not limited thereto, it is believed that the cure reaction of an epoxy with the di-isoimide hereof is mostly a reaction of an amine group of the di-isoimide to open the oxirane ring (or epoxy group, as it is often referred to) resulting in a nitrogen carbon bond, and an alkyl hydroxyl group. So in the above instance, the di-isoimide serves as a cross-linking agent. When, for example, a phenolic novolac is also present, the oxirane ring opening reaction is effected primarily by the reaction of the phenol hydroxyl group of the novolac with the oxirane ring, thereby creating an oxygen-carbon bond and an alkyl hydroxyl group. When a more active cross-linking agent, such as the phenol is not present, the di-isoimide serves as both cross-linking agent and a catalyst.
The terms “film” and “sheet” refer to planar shaped articles having a large length and width relative to thickness. Films and sheets differ only in thickness. Sheets are typically defined in the art as characterized by a thickness of 250 micrometers or greater, while films are defined in the art as characterized by a thickness less than 250 micrometers. As used herein, the term “film” encompasses coatings disposed upon a surface.
The term “discrete conductive pathway” as used herein refers to an electrically conductive pathway disposed upon a dielectric substrate in the form of a film or sheet which leads from one point to another on the plane thereof, or through the plane from one side to the other.
There are several terms that are repeated throughout this invention that are described in detail only upon the first mention thereof. However, in order to avoid prolixity the descriptions of the term are not repeated when the term reappears further on in the text. It shall be understood for the purposes of the present invention that when a term is repeated in the text hereof, the description and meaning of that term is unchanged from and the same as that provided for the term upon its first mention. For example the term “di-isoimide composition represented by Structure I” shall be understood each time it appears to encompass all the possible embodiments recited with respect to Structure I upon its first appearance in the text. For another example, the term “second solvent” shall be understood to refer to the same set of solvents described for the “second solvent” at the first appearance of the term in the text.
For the purposes of this invention, the term “room temperature” is employed to refer to ambient laboratory conditions. As a term of art, “room temperature” is normally taken to mean about 23° C., encompassing temperatures ranging from about 20° C. to about 30° C.
The term “printed wiring board” (PWB) shall refer to a dielectric substrate layer having disposed thereupon a plurality of discrete conductive pathways. The substrate is a sheet or film. In one embodiment of the invention the dielectric substrate is a polyimide film. In a further embodiment, the polyimide film has a thickness of 5-75 micrometers. In one embodiment the discrete conductive pathways are copper.
PWBs suitable for the practice of the present invention can be prepared by well-known and wide-spread practices in the art. Briefly, a suitable PWB can be prepared by a process comprising laminating a copper foil to a dielectric film or sheet using a combination of an adhesive layer, often an epoxy, and the application of heat and pressure. To obtain high resolution circuit lines (≦125 micrometers in width) photoresists are applied to the copper surface. A photoresist is a light-sensitive organic material that when subject to imagewise exposure an engraved pattern results when the photoresist is developed and the surface etched. In a suitable PWB, the image is in the form of a plurality of discreet conductive pathways upon the surface of the dielectric film or sheet.
A photoresist can either be applied as a liquid and dried, or laminated in the form, for example, of polymeric film deposited on a polyester release film. When liquid coating is employed, care must be employed to ensure a uniform thickness. When exposed to light, typically ultraviolet radiation, a photoresist undergoes photopolymerization, thereby altering the solubility thereof in a “developer” chemical. Negative photoresists typically consist of a mixture of acrylate monomers, a polymeric binder, and a photoinitiator. Upon imagewise UV exposure through a patterning photomask, the exposed portion of the photoresist polymerizes and becomes insoluble to the developer. Unexposed areas remain soluble and are washed away, leaving the areas of copper representing the conductive pathways protected by the polymerized photoresist during a subsequent etching step that removes the unprotected conductive pathways. After etching, the polymerized photoresist is removed by any convenient technique including dissolution in an appropriate solvent, or surface ablation. Positive photoresists function in the opposite way with UV-exposed areas becoming soluble in the developing solvent. Both positive and negative photoresists are in widespread commercial use. One well-known positive photoresist is the so-called DNQ/novolac photoresist composition.
Any PWB prepared according to the methods of the art is suitable for use in the present invention.
In one aspect, the present invention provides a di-isoimide composition represented by Structure I
wherein R 1 is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″ where R′ and R″ are independently H, alkyl or aromatic, substituted or unsubstituted. In one embodiment, R 1 is NH 2 .
In another aspect, the present invention provides a first process that can be used to prepare the composition represented by the Structure I, the first process comprising mixing in a first solvent, at a temperature in the range of −10 to +160° C., PMDA with a di-amino triazine represented by the Structure II
wherein R 1 is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″ where R′ and R″ are independently H, alkyl or aromatic, substituted or unsubstituted.
In one embodiment, R 1 is NH 2 .
Suitable first solvents include but are not limited to polar/aprotic solvents characterized by a dipole moment in the range of 1.5 to 3.5 D. While the reaction between the aminoazine and PMDA takes place in solution, full miscibility of the reactants in the solvent is not necessary. Even limited solubility will permit the reaction to proceed, with additional reactants dissolving as they are consumed in the reaction. Suitable solvents include but are not limited to acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, ethyl propionate, ethyl-3-ethoxy propionate, cyclohexanone, and mixtures thereof. Mixtures thereof with small amounts (for example, less than 30% by weight) of non-polar solvents such as benzene are also suitable. In one embodiment, the solvent is cyclohexanone.
When the dipole moment is below 1.5 D, solubility of melamine, already low, becomes so low that the reaction can take weeks to go to completion. When the dipole moment of the solvent exceeds 3.5 D the rate of the reaction converting the di-isoimide to di-imide can proceed at an inconveniently rapid rate, causing excessive loss of the desired di-isoimide.
According to the first process of the invention, PMDA and a suitable diamino triazine, substituted or unsubstituted, as described supra, are combined in the presence of a suitable first solvent, and allowed to react. The reaction temperature can be in the range of −10 to +160° C. The yield of di-imide increases with increasing temperature, at the expense of the di-isoimide. While this invention is directed to the preparation of and the advantageous use of the di-isoimide, the presence of some di-imide mixed in with the di-isoimide does not necessarily have any particularly negative impact. In some instances, it could be advantageous to use a higher reaction temperature which results in lower selectivity but higher reaction rate.
In general, higher reaction temperature corresponds to faster reaction. Selectivity depends on temperature and the specific choices of dianhydride, triazine, and solvent. For example PMDA and melamine in cyclohexanone produce pure isoimide at 25° C., almost pure isoimide at 50° C., and produce about 80% isoimide at reflux (˜155° C.). PMDA and melamine react faster in N,N-dimethyl formamide (DMF) than in cyclohexanone at the same temperature but the reaction continues on to form imide from a di-isoimide intermediate if the reaction is not stopped in time.
In one embodiment, the reaction temperature is in the range of room temperature to 100° C. In a further embodiment, the reaction temperature is in the range of room temperature to 50° C.
The first process hereof does not require a water scavenger (such as trifluoroacetic acid) in order to provide the desired di-isoimide as represented by Structure I. It is highly preferred in the first process hereof to omit any water scavenger, in order to avoid having subsequently to remove the water scavenger after reaction is complete.
It is observed in the practice of the invention that the di-isoimide hereof is more soluble than the analogous imide in relatively mild, low boiling point solvents such as cyclohexanone and MEK. Much stronger high boiling point solvents, such as dimethyl acetamide (DMAC) or n-methyl pyrrolidone (NMP), are required to dissolve the imide. This feature of the di-isoimide hereof is of considerable importance in the formulation of epoxies with practical commercial applicability. It is difficult to remove high boiling point solvents without also initiating the epoxy cure. For adhesive applications, particularly highly critical applications such as the fabrication of encapsulated PWBs as described herein, it is essential to have the solvent removed completely since the adhesive is sealed between the two surfaces it is binding together, and there is no place to which solvent can escape without causing bubbles and voids in the finished product. Bubbles and voids adversely affect the uniformity of the dielectric constant.
Maintaining a high degree of mixing during reaction is important for achieving full conversion of the reactants into the di-isoimide product. For example, melamine is of very limited solubility in the suitable solvents. PMDA is also only poorly soluble. In order to achieve high conversion within a commercially viable time frame, it is necessary to maintain good intermixing of the reactants with each other and with the solvent. While the invention is not thereby limited, it is believed that the solution equilibrium for the reactants causes small amounts of reactants to dissolve, and that the thus dissolved reactants react to form a precipitate of the di-isoimide, thereby causing additional reactants to dissolve. This process is believed to continue until the reactants are exhausted, and conversion is quantitative as indicated by the disappearance of the reactant peaks in the infra-red (IR) spectrograph of the solvent dispersion.
Suitable mixing can be achieved using mechanical stirring such as magnetic stirring. A satisfactory state of mixing is one wherein the dispersion of reactants (and product) in the solvent has a uniform appearance with no regions of stagnant solids. It is preferred to stir to maintain a uniform appearance throughout the duration of the reaction.
It is found in the practice of the invention, as herein exemplified infra in Examples 7 and 8, performing the first process hereof in the presence of a rubber compound containing carboxylic acid groups in solution causes the reaction to achieve a higher rate of conversion than the same reaction when run without the rubber.
In a further aspect, the present invention provides a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I. In one embodiment, the second solvent is the same as the first solvent.
Solvents suitable for use as the second solvent include but are not limited to acetone, MEK, cyclohexanone, pentanone, dioxolane, tetrahydrofuran, glycol ethers, propylene glycol methyl ether acetate (PMA), N-methyl pyrrolidone, N,N-dimethylacetamide, DMF, dimethyl sulfoxide, N,N-diethylacetamide, N,N-diethylformamide, N,N-dimethylmethoxyacetamide. Preferred solvents are MEK, cyclohexanone, PMA, and DMF. Mixtures of solvents are also suitable.
Referring to Structure I, in one embodiment, R 1 is NH 2 .
Suitable epoxies for the curable composition hereof are epoxies comprising an average of at least two epoxide groups per polymer chain. Suitable epoxies include but are not limited to polyfunctional epoxy glycidyl ethers of polyphenol compounds, polyfunctional epoxy glycidyl ethers of novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, and glycidylated halogenated phenol epoxy resins. Preferred epoxies include epoxy novolacs, biphenol epoxy, bisphenol-A epoxy and naphthalene epoxy. Preferred epoxies are oligomers having 1-5 repeat units. Most preferably the epoxy is bisphenol-A or novolac epoxy, especially a bisphenol A diglycidyl ether.
Epoxies can be derivatized in any manner described in the art. In particular they can be halogenated, especially by bromine to achieve flame retardancy, or by fluorine.
In one embodiment of the curable composition hereof R 1 is NH 2 ; the solvent is MEK, cyclohexanone, propylene glycol methyl ether acetate, DMF, or a mixture thereof; and, the epoxy is of the bisphenol-A type.
The di-isoimide represented by Structure I can serve both as a curing catalyst and/or as a curing agent in the curable composition hereof. The isoimide moiety reduces the flammability of the cured epoxy (vs. phenolic novolac, which does not have a comparable flame retardant effect) and thus reduces the need for flame retardants. In one embodiment, the curable composition further comprises a curing agent. Any curing agent known in the art can be used in the compositions and processes disclosed herein. Suitable curing agents include organic acid anhydrides and phenols. Monoanhydride curing agents are preferred for ease of handling.
In an alternative embodiment, the curable composition hereof does not include a separate curing agent. It is found in the practice of this embodiment of the invention that the nucleophilic character of the amine group is much reduced by the presence of the triazine ring and the isoimide linkage. It is further found that once one of the amine groups on the ring undergoes reaction, the second amine group becomes still less reactive. Therefore in formulating the curable composition in this embodiment, it is found that satisfactory results are achieved by treating each mole of the di-isoimide of Structure I as representing two equivalents from the standpoint of cross-linking the epoxy. A formulation on that basis that contains a 20% excess in equivalents of epoxy has been found to be satisfactory.
The curable composition hereof can include any and all of the numerous additives commonly incorporated into epoxy formulations in the art. This can include flame retardants, rubber or other tougheners, inorganic particles, plasticizers, surfactants and rheology modifiers.
In one embodiment, the curable composition hereof comprises a low molecular weight liquid epoxy that serves as a dispersion medium for the di-isoimide composition represented by Structure I. Low molecular weight epoxies, such as EPON™ Resin 828, are characterized by equivalent weight of 185-192 g/eq. However, such low molecular weight epoxies are less preferred than the pastier, more viscous, higher molecular weight high performance epoxies that are well-known in the art. Higher molecular weight epoxies, such as EPON™ Resin 1001F, are characterized by equivalent weight of 525-550 g/eq. While the reaction mixture formed from the higher molecular weight epoxies can be heated in order to lower viscosity, it is undesirable to apply heat for that purpose, especially in the presence of a catalyst, because of the risk of causing premature curing. In a highly preferred embodiment a high molecular weight epoxy is dissolved in a second solvent hereof—or, less preferably dispersed therein—into which a solution or dispersion of the di-isoimide composition of Structure I is then dispersed to form the curable composition hereof.
Suitable curing agents are phenol and aromatic anhydrides. The epoxy and the curing agent are mixed in quantities based on their equivalent weights. In the case of phenolic curing agents, 0.3-0.9 equivalent of phenol is preferred for each equivalent of epoxy has been found to be suitable. With anhydride curing agents, 0.4-0.6 equivalent of anhydride is preferred for one equivalent of epoxy.
Suitable phenol curing agents include biphenol, bisphenol A, bisphenol F, tetrabromobisphenol A, dihydroxydiphenyl sulfone, novolacs and other phenolic oligomers obtained by the reaction of above mentioned phenols with formaldehyde. Suitable anhydride curing agents are nadic methyl anhydride, methyl tetrahydrophthalic anhydride and aromatic anhydrides.
Aromatic anhydrides curing agents include but are not limited to aromatic tetracarboxylic acid dianhydrides such as pyromellitic dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, thiophene tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, pyrazine tetracarboxylic acid dianhydride, and 3,4,7,8-anthraquinone tetracarboxylic acid dianhydride. Other suitable anhydride curing agents are oligomers or polymers obtained by the copolymerization of maleic anhydride with ethylene, isobutylene, vinyl methyl ether and styrene. Maleic anhydride grafted polybutadiene can also be used as a curing agent.
Suitable tougheners are low molecular weight elastomers or thermolastic polymers and contain functional groups for reaction with epoxy resin. Examples are polybutadienes, polyacrylics, phenoxy resin, polyphenylene ethers, polyphenylene sulfide and polyphenylene sulfone, carboxyl terminated butadiene nitril elastomers (CTBN), epoxy adducts of CTBN, amine terminated butadiene nitril elastomers (ATBN), carboxyl functionalized elastomers, polyol elastomers and amine terminated polyol elastomers. Epoxy adducts of CTBN, CTBN and carboxyl functionalized elastomer are preferred.
In one embodiment, the di-isoimide can be pre-dispersed in the solvent in which it was prepared. In an alternative embodiment, the di-isoimide may be added as particles to the epoxy solution and dispersed therein using mechanical agitation.
In a further aspect, the present invention provides a second process, a process for preparing a cured composition from the curable composition hereof by heating the curable composition to a temperature in the range of 100 to 250° C. for a period of time in the range of 30 seconds to 5 hours. For adhesive applications the solvent needs to be removed completely before curing, as described in the Examples, infra.
The viscosity of the uncured composition can be adjusted by either adding solvent to decrease the viscosity, or by evaporating solvent to increase viscosity. The uncured composition can be poured into a mold, followed by curing, to form a shaped article of any desired shape. One such process known in the art is reaction injection molding. In particular, the composition can be used in forming films or sheets, or coatings. The viscosity of the solution is adjusted as appropriate to the requirements of the particular process. Films, sheets, or coatings are prepared by any process known in the art. Suitable processes include but are not limited to solution casting, spray-coating, spin-coating, or painting. A preferred process is solution casting using a Meyer rod for draw down of the casting solution deposited onto a substrate. The substrate can be treated to improve the wetting and release characteristics of the coating. Solution cast films are generally 10 to 75 micrometers in thickness. The solution casting of a solution/dispersion hereof onto a substrate film or sheet to form a laminated article is further described in the specific embodiments hereof, infra.
In another aspect, the present invention is directed to a laminated article comprising a substrate and a coating adheringly deposited thereupon wherein said substrate is a polymeric sheet or film and said coating comprises a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I. In one embodiment, the substrate is a polyimide film. In a further embodiment said second dielectric substrate is a fully aromatic polyimide film or sheet. In a further embodiment the polyimide film has a thickness of 10-50 micrometers. In one embodiment, R 1 is NH 2 . In one embodiment, the coating has a thickness of 10 to 75 micrometers.
In one embodiment, the substrate is coated on both sides thereof. In a further embodiment, the coatings on both sides are chemically identical.
In a further aspect, the present invention is directed to a printed wiring board comprising in order a first layer of a first dielectric substrate, a second layer of one or more discrete electrically conductive pathways disposed upon said first dielectric substrate, a third layer of a bonding layer in adhesive contact with said discrete electrically conducting pathways, and adheringly disposed upon a fourth layer comprising a second dielectric substrate, said bonding layer comprising a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I.
In one embodiment of the printed wiring board hereof, the first layer is a polyimide film having a thickness of 10-50 micrometers.
In one embodiment of the printed wiring board hereof, the electrically conductive pathways are copper.
In a further embodiment of the printed wiring board hereof, the copper electrically conductive pathways are characterized by a thickness of 10-50 micrometers and lines and spacing from 10-150 micrometers.
In one embodiment of the printed wiring board hereof, in said adhesively bonding layer said second solvent is MEK, cyclohexanone, PMA, DMF, or a mixture thereof.
In one embodiment of the printed wiring board hereof, in said adhesively bonding layer in said di-isoimide composition represented by Structure I, R 1 is NH 2 .
In one embodiment of the printed wiring board hereof, the second dielectric substrate is a polyimide film or sheet. In a further embodiment said second dielectric substrate is a fully aromatic polyimide film or sheet. In a still further embodiment, said second dielectric substrate is a film or sheet comprising a polyimide that is the condensation product of PMDA and 4,4′-ODA. In a still further embodiment, said second dielectric substrate is a fully aromatic polyimide film having a thickness of 10-50 micrometers.
The printed wiring board hereof is conveniently formed by contacting the coating side of the laminated article hereof to the conductive pathways disposed upon the first dielectric substrate. The printed wiring board hereof has several embodiments that differ from one another in the degree of consolidation. In one embodiment the printed wiring board hereof is formed simply by disposing upon a horizontal surface a first dielectric substrate having one or more discrete conductive pathways disposed upon at least one surface thereof, where said conductive pathways are facing upward; followed by placing a coated side of the laminated article hereof in contact with the conductive pathways, thereby preparing a so-called “green” or uncured printed wiring board.
In a further embodiment, the green printed wiring board is subject to pressure thereby causing some consolidation. In a further embodiment the green printed wiring board is subject to both pressure and temperature. The temperature exposure may be sufficient to induce only a small amount of cross-linking or curing. This represents a so-called “B-stage” curing—an intermediate level of consolidation that causes the printed wiring board to have some structural integrity while retaining formability and proccessability. The B-stage can be followed by complete curing. Alternatively, complete curing can be effected in a single heating and pressurization step from the green state.
In one embodiment of the printed wiring board hereof, the first dielectric substrate bears conductive pathways on both sides, permitting the formation of the multi-layer construction described supra on both sides of the first dielectric substrate.
In another embodiment of the printed wiring board hereof, the second dielectric substrate is coated on both sides with a composition comprising a solution/dispersion of epoxy, a second solvent, and the di-isoimide composition represented by Structure I.
In still a further embodiment, the first dielectric substrate bears conductive pathways on both sides, and the second dielectric substrate bears a coating on both sides, that coating comprising a solution/dispersion of epoxy, a second solvent, and the di-isoimide composition represented by Structure I. This embodiment permits printed wiring boards hereof to be constructed with an indefinite number of repetitions of the basic structure of the multilayer article.
In a further embodiment, at least a portion of the conductive pathways disposed upon one side of the first dielectric substrate are in electrically conductive contact with at least a portion of the conductive pathways disposed upon the other side of the first dielectric substrate through so-called “vias” that serve to connect the two sides of the dielectric substrate.
In another aspect, the present invention provides a third process, a process for preparing an encapsulated printed wiring board, the process comprising adhesively contacting the coated surface of a laminated article having a surface with a coating disposed thereupon to at least a portion of the discrete conductive pathways disposed upon a dielectric substrate thereby forming a multilayer article; wherein said coating comprises a curable composition comprising a second solvent having mixed therewithin an epoxy and a di-isoimide composition represented by Structure I; and, applying pressure to the printed wiring board so formed at a temperature in the range of 100 to 250° C. for a period of time in the range of 30 seconds to 5 hours, thereby forming an encapsulated printed wiring board.
In one embodiment, the third process hereof further comprises extracting said second solvent before applying pressure to the printed wiring board. Solvent extraction can be effected conveniently by heating in an air circulating oven set at 110° C. for a period of time ranging from 2-20 minutes.
In one embodiment of the third process hereof, R 1 is NH 2 .
In one embodiment of the third process hereof, the first and second dielectric substrates are both polyimide films.
In a further embodiment of the third process hereof, the polyimide films are fully aromatic polyimides.
In a still further embodiment of the third process hereof, the polyimide films are the condensation product of PMDA and ODA.
The invention is further described in the following specific embodiments though not limited thereby.
EXAMPLES
Determining Reaction Completion Point
In the following examples, infrared spectroscopy (IR) was employed to determine the end-point of the reaction. Small aliquots of the reacting medium were withdrawn by dropper-full, dried in a vacuum oven with N 2 purge at about 60° C. for about 60 minutes. Following conventional methodology for preparing solids for IR spectroscopic analysis, the resulting powder was then compounded with KBr followed by the application of pressure to the resulting compound, thereby forming a test pellet. IR absorption peaks at 1836 cm −1 and 1769 cm −1 were monitored to follow the increase in the concentration of the di-isoimide product. Similarly, IR absorption peaks at 1856 cm −1 and 1805 cm −1 characteristic of PMDA and 1788 cm −1 characteristic of melamine were monitored to follow the consumption of reactants. When the PMDA and melamine peaks became undetectable, the reaction was considered to be complete.
Peaks at 1788 cm −1 and 1732 cm −1 characteristic of imide were also monitored to follow the synthesis of any imide by-product of the present process.
The time to reaction completion was observed to vary considerably with the reaction temperature and the particular choice of solvent.
Reaction Medium
Both melamine and PMDA are only slightly solubile in the solvents employed herein so it was necessary to maintain good mixing during reaction to ensure a high degree of conversion. Without constant vigorous mixing, the solids settled and the reaction slowed down or stopped. The amount of energy that was needed for mixing was determined by observation. When the dispersion was of uniform appearance and no stagnant solid phase was observed, mixing was deemed to be of sufficient energy. The di-isoimide product formed into platelet particles with dimensions in the hundreds of nanometers range. These platelet particles also remained suspended with mixing. By the time reaction was completed, no detectable amounts of PMDA or melamine were present in the reaction mixture—all the suspended particles were di-isoimide, or, in some instances, di-isoimide with some imide mixed in.
Printed Wiring Board
A Pyralux® AC182000R copper clad laminate sheet (Dupont Company) was etched according to a common commercial etching process to form a series of parallel copper conductive strips 35 micrometers high, 100 micrometers wide, and spaced 100 micrometers apart. This was used in Examples 9-12, and is referred to therein as “a PWB test sheet.” Information on methods for preparing printed wiring boards can found in Chris A. Mack, Fundamental Principles of Optical Lithography: The Science of Microfabrication, John Wiley & Sons, (London: 2007). Hardback ISBN: 0470018933; Paperback ISBN: 0470727306.
Reagents
Except where otherwise noted, all reagents were obtained from Sigma Aldrich Chemical Company.
Example 1
6.31 grams of melamine, 5.45 grams of PMDA and 25 grams of MEK were mixed using a magnetic stirrer in a round bottom flask. The mixture was refluxed under nitrogen for two days until conversion was complete. MEK was added as needed during refluxing to keep the volume of the reaction mixture approximately constant. The thus prepared product mixture was cooled to room temperature while maintaining stirring. As confirmed by IR spectroscopy, the product mixture contained only MEK and di-isoimide. No imide was detectable. The dispersion so prepared was suitable for immediate use in formulating a curable epoxy composition.
Example 2
6.31 grams of melamine, 5.45 grams of PMDA and 35 grams of ethyl 3-ethoxypropionate were mixed in a round bottom flask. The mixture was refluxed under nitrogen for two days until conversion was complete. The mixture was cooled to room temperature. A small sample from the mixture was washed with MEK. As confirmed by IR spectroscopy, the product mixture contained MEK, di-isoimide, and a small amount of imide indicated by a small IR peak at 1734 cm −1 . The dispersion so prepared was suitable for immediate use in formulating a curable epoxy composition.
Example 3
69.69 grams of melamine (0.534 moles), 60.26 grams of PMDA (0.267 moles) and 360 grams cyclohexanone are added into a reaction vessel, and stirred at room temperature for 6 days until conversion was complete. A sample from the reaction mixture was dried in vacuum oven. IR spectra of the final solid product showed the disappearance of the PMDA peaks at 1856 & 1805 cm −1 and melamine peak at 1558 cm −1 and the appearance of the isoimide peaks at 1836 & 1769 cm −1 .
Example 4
6.31 grams of melamine, 5.45 grams of PMDA and 25 grams of MIBK (methyl isobutyl ketone) were mixed in a round bottom flask. The mixture was refluxed under nitrogen for 90 minutes. The mixture was cooled to room temperature. A sample was dried. IR spectra of the dried sample showed the formation of isoimide (peaks at 1836 & 1769 cm −1 ). Reaction was complete to the di-isoimide and no imide was detected.
Example 5
5.81 grams of melamine, 5.00 grams of PMDA, 10 grams of DMF and 10 grams of ethyl acetate were mixed overnight in a flask at room temperature. Reaction was complete to the di-isoimide and no imide was detected. A small sample was dried. IR spectra of the dried sample showed the formation of isoimide (peaks at 1836 & 1769 cm −1 ).
Example 6
5.81 grams of melamine, 5.00 grams of PMDA, 10 grams of MIBK, and 10 grams of toluene were mixed overnight in a flask at room temperature. A small sample was dried. IR spectra of the dried sample showed the formation of isoimide (peaks at 1836 & 1769 cm −1 ). Reaction was complete to the di-isoimide and no imide was detected.
Example 7
3 grams of Vamac® G (from DuPont) and 12 grams of MEK were mixed in a round bottom flask to form a solution. 3.30 grams of a phenol/formaldehyde resin (GP 5300 from Georgia Pacific), and 15 grams of DMF were added to the round bottom flask, and mixed to form a solution. 3.48 grams of melamine and 3.01 grams of PMDA were added to the solution. The solution was heated under nitrogen for 30 minutes at 100° C., 30 minutes at 120° C., and 60 minutes at 140° C. The mixture was cooled to room temperature. A small sample from the mixture was washed thoroughly in MEK (to remove GP5300 and Vamac-G). IR spectra show the formation of isoimide (peaks at 1836 & 1769 cm −1 ) The anhydride and melamine peaks disappeared while the isoimide peaks appeared, and a small amount of imide was also present as indicated by a very small peak at 1734 cm −1 .
Example 8
2.90 grams of carboxyl-terminated butadiene-acrylonitrile rubber (CTBN rubber, 1300×13 from CVC Thermoset Specialties), 3.78 grams of melamine, 3.27 grams of PMDA and 15 grams of dry MEK were mixed in a round bottom flask. The solution was refluxed under nitrogen for 5 hours. The mixture was cooled to room temperature. A small sample from the mixture was washed thoroughly in MEK (remove CTBN). IR spectra of this sample showed the formation of isoimide (peaks at 1836 & 1769 cm −1 ). The anhydride and melamine peaks disappeared. A small amount of imide was present.
Comparative Example A
In a reaction vessel, 25.22 grams of melamine (0.2 moles), 21.81 grams of PMDA (0.1 moles) and 125 ml DMF were refluxed for 5 hours. The mixture was cooled and quenched with methanol. The solid product was filtered and dried. The IR spectra of the filtered solid product showed the disappearance of the PMDA peaks at 1856 & 1805 cm −1 and of the melamine peak at 1558 cm −1 and the appearance of the imide peaks at 1788 & 1732 cm −1 .
Comparative Example B
In a reaction vessel, 50.45 grams of melamine (0.4 moles), 43.62 grams of PMDA (0.2 moles) and 400 ml of NMP (N-methylpyrrolidinone) were refluxed for 30 minutes. The mixture was cooled and quenched with methanol. The solid product was filtered and dried. The IR spectra of the filtered solid product showed imide formation (peaks at 1788 & 1732 cm −1 ).
Example 9
3.50 grams of the di-isoimide dispersed in 9.5 grams of cyclohexanone, prepared in Example 3 supra, and 11.5 grams of a copolymer of butadiene and acrylonitrile modified to contain free carboxylic groups (Nipol 1072J from Zeon Chemicals) dissolved in 63 grams of MEK, were mixed in a flask. 11.20 grams of melamine phosphate/melamine polyphosphate/melamine pyrophosphate flame retardant (Phosmel 200 Fine from Nissan Chemical Industries) was then added and mixed in, to form a first solution/dispersion. 9.10 grams of an epoxy-rubber adduct (HyPox RK84L from CVC Thermoset Specialties) was dissolved in 9.10 grams of MEK to form a second solution. The second solution was added to the first solution/dispersion thereby forming an epoxy solution/dispersion. The epoxy solution/dispersion so prepared was coated onto 12 micrometer thick Kapton® 50FPC polyimide film using a 7 mil gauge (177.8 micrometer) doctor blade followed by removal of the solvent by placing the thus-cast film and substrate in a vacuum oven at 60° C. for one hour, to form an approximately 25 micrometer thick coating.
The thus prepared coated Kapton® was then used as a cover-layer on the PWB test sheet. Referring to FIG. 1 , the Kapton® 50FPC film, 1 , coated with the curable composition, 2 , thus prepared was contacted, 5 , to the copper conductive strips, 3 , of the PWB test sheet, 4 , the curable composition, 2 , being in direct contact with the copper conductive strips, 3 . The printed wiring board thereby formed, 6 , was then consolidated, 7 , under vacuum in an OEM Laboratory Vacuum Press by holding the printed wiring board at 175° C. and 2.25 MPa for 80 minutes, thereby forming a flexible printed wiring board, 8 , having fully encapsulated copper conductive pathways.
Example 10
3.50 grams of the di-isoimide dispersed in 9.5 grams of cyclohexanone, as prepared in Example 3. and 9.80 grams of “Nipol 1072J” rubber dissolved in 55 grams of MEK were mixed in a flask. The mixture was stirred for 30 minutes. 1.40 grams of CTBN (Carboxyl-Terminated Butadiene-Acrylonitrile Rubber, CTBN 1300×13 from CVC Thermoset Specialties) and 11.20 grams of “Phosmel 200 Fine” flame retardant (from Nissan Chemical Industries) were added to the mixture. 9.10 grams of HyPox RK84L were dissolved in 13.7 grams of MEK and the solution so formed was added to the mixture. The thus prepared solution/dispersion was coated onto a 12 micrometer thick Kapton® 50ENS polyimide film using a 7 mil gauge (177.8 micrometers) doctor blade, after which the thus coated Kapton® film was placed into an air circulating oven at 110° C. for 10 minutes to remove the solvent. The dry adhesive film thickness was 27 micrometers.
The thus prepared coated Kapton® film was used to prepare a fully encapsulated flexible printed wiring board employing the materials and procedures described in Example 9.
Example 11
61.60 grams of “Nipol 1072J” rubber were dissolved in 350 grams of MEK in a flask to form a first solution. 9.10 grams of the di-isoimide dispersed in 25 grams of cyclohexanone prepared in Example 3 was mixed into the first solution to form a second solution/dispersion, followed by mixing in 42.25 grams of “Phosmel 200 Fine” flame retardant (from Nissan Chemical Industries) to form a third solution/dispersion. 34.45 grams of HyPox RK84L was dissolved in 34.45 grams of MEK and the resulting fourth solution was mixed into the third solution/dispersion to form a fifth solution/dispersion. 2.6 grams of bisphenol A diglycidyl ether epoxy resin (EPON™ 828 from Hexion Specialty Chemicals) were mixed into the fifth solution/dispersion to form an epoxy solution/dispersion. The thus prepared epoxy solution/dispersion was coated onto a Kapton® 50FPC polyimide film using a 7 mil gauge (177.8 micrometer) doctor blade. The thus coated Kapton® film was placed in an air circulating oven at 110° C. for 10 minutes to remove the solvent. The dry coating thickness was approximately 25 micrometers in thickness.
The thus prepared coated Kapton® film was used to prepare a fully encapsulated flexible printed wiring board employing the materials and procedures described in Example 9.
Example 12
55.8 grams of a cyclohexanone dispersion of melamine-PMDA di-isoimide (26.9 weight % isoimide content) prepared according to the method of Example 3 and 51.0 grams of rubber (copolymer of butadiene and acrylonitrile modified to contain free carboxylic groups—Nipol 1072J from Zeon Chemicals) were dissolved in 289 grams of MEK to form a solution. 36 grams of an epoxy-rubber adduct (HyPox RK84L from CVC Thermoset Specialties) and 48.0 grams of melamine phosphate/melamine polyphosphate/melamine pyrophosphate flame retardant (Phosmel 200 Fine from Nissan Chemical Industries) were mixed into the solution using a mechanical stirrer. When all the ingredients were dispersed into the solution, the mixture so formed was homogenized for 2.5 minutes (Silverson model L5M homogenizer) to a dispersion having a visually uniform appearance. The thus homogenized mixture was then mechanically stirred continuously until coating, described infra, was commenced.
The dispersion so prepared was coated onto Kapton® 50FPC polyimide film using a 7 mil gauge (177.8 micrometer) doctor blade. The solvent was removed by placing the thus coated Kapton® film in an air circulating oven for10 minutes at 110° C. The dried coating thickness was approximately 25 micrometers.
The thus dried coated film was laminated to a PWB test sheet. The printed wiring board, 6 , as shown in FIG. 1 was further prepared with a release film and a rubber pad on each side. The combination thus prepared was inserted into a quick lamination press and pressed at a temperature of 185° C. and a pressure of 9.8 MPa for 2 minutes, followed by a cure in an air-circulating oven at 160° C. for 90 minutes.
The adhesion of the coated film to the PWB test sheet was determined to be 2.16 N/mm (Newton/millimeter) according to ISO 6133 IPC-TM-650 2.4.9 using a German wheel attached to an Instron machine.
Example 13
The materials and procedures of Example 12 were employed, except that the quantities were different, as indicated in Table 1, and the procedure was modified as described infra.
Ex. 12 Ex. 13 (g) (g) Melamine-PMDA isoimide (26.9 55.8 33.85 weight-% isoimide) dispersion in Cyclohexanone Nipol 1072J 51.0 41.6 MEK 289 235.7 HyPox RK84L 36 34.5 Phosmel 200 Fine 48.0 42.25
The melamine-PMDA isoimide cyclohexanone dispersion, Nipol 1072J, and MEK were combined to form a first solution, to which the Phosmel 200 Fine was added to form a first solution/dispersion. The HyPox RK84L was first dissolved in 34.5 grams of MEK to which 2.6 grams of Epon 828 (from Hexion) were added, thus forming a second solution. The second solution was then added to the first solution/dispersion. The remaining procedures and method of Example 12 were then followed. The adhesion of the coated film on the PWB test sheet was determined to be 2.15 N/mm.
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The present invention deals with a novel aromatic di-isoimide chemical compound that has utility as a catalyst and as a curing agent in epoxy compositions. The di-isoimide serves effectively as a thermally activated latent catalyst in epoxy curing, thereby increasing shelf life, and avoids premature cross-linking. Novel laminated articles and printed wiring boards, including encapsulated printed wiring boards are also disclosed. The composition hereof also can be used as a flame retardant in thermoplastic and thermoset polymers.
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FIELD OF THE INVENTION
[0001] The present invention relates to a driving mechanism for labeling machine that uses belts as transmission members in a transmission assembly to perform high speed transmission and offers easy maintenance.
BACKGROUND OF THE INVENTION
[0002] The driving mechanism of a conventional labeling machine, referring to FIG. 1 , has a transmission assembly 1 a consisting of a plurality of pulleys 12 a coupled with linking bars 11 a and belts 13 a, and axles 14 a with an adjustable width to mate a center guide post holding label films of varying dimensions.
[0003] The conventional labeling machine also has a linking belt 15 a to link a driving wheel 10 a and a linking pulley 16 a. A pulley shaft 17 a is provided to connect to the pulley 12 a on the linking bars 11 a. The pulleys 12 a at two ends of the linking bars 11 a are transmitted by the belts 13 a. The pulleys 12 a on the neighboring linking bars 11 a are coupled on the pulley shaft 17 a. Thus the linking bars 11 a and the belts 13 a are linked in a selected order. During repair and maintenance, the belts 13 a cannot be removed and displaced individually. All the belts 13 a at the front end and rear end have to be disassembled, then assembled and installed again in the selected order. It takes a great deal of time. Moreover, the belts 13 a between the linking bars 11 a of the transmission assembly 1 a have to be wound in a staggered manner to prevent mutual friction. Hence a greater space is needed. As the tension of the belts 13 a varies, transmission speed also is uneven and transmission quality is affected. Furthermore, the adjustment mechanism comprising the linking bars 11 a can only be anchored on the junction of the linking pulley 16 a and the axle 14 a, and the rest elements are suspended. Hence shaking frequently occurs on the linking bars 11 a that further impacts transmission effect of the belts 13 a. This results in a shortened life span of the elements. There are still rooms for improvement.
[0004] In short, the driving mechanism of the conventional labeling machine still has many drawbacks in practice, notably:
[0005] 1. A greater number of belts are needed. Replacement of the belts is tedious and wastes a lot of manpower and time.
[0006] 2. The transmission elements occupy a great deal of space and result in difficult space configuration.
[0007] 3. The belts are numerous and their tension is difficult to control, and result in uneven speed.
[0008] 4. The transmission elements have many moving hinges. Shaking takes place and steadiness suffers.
SUMMARY OF THE INVENTION
[0009] The primary object of the present invention is to overcome the problems of the driving mechanism of the conventional labeling machine such as difficulty of maintenance and replacement of belts. The present invention provides a single transmission member to couple and transmit two axle wheels of a transmission assembly located on a base of a labeling machine. A linking member may be a belt to concurrently transmit a plurality of transmission assemblies. Each transmission assembly requires only one transmission member and one linking member. Assembly and repair and maintenance are easier.
[0010] To achieve the foregoing object, the present invention provides a driving mechanism for labeling machine that has a linking assembly driven by a driving wheel connected to a power source to drive a transmission wheel of a transmission assembly, and a transmission member engaged with the transmission wheel so that two axle wheels are rotated concurrently in opposite direction. A pushing wheel is provided adjacent to the axle wheels to form close engagement between the linking member and the axle wheels. In addition, the two axle wheels and pushing wheel are respectively installed on two sliders of a base. The sliders can keep the axle wheels steady without wobbling during rotation. With two sets of axles firmly mounted on the axle wheels, the distance between the two axles can be adjusted through an axle adjustment assembly. Therefore, the distance between two feeding wheels also can be adjusted.
[0011] The invention provides three main features: first, through the two slidable sliders, the distance between the two sliders can be adjusted without changing the location of the transmission member, thus it can be incorporated with center posts of varying dimensions. Second, coupling of multiple transmission assemblies can be done by linking the linking wheels thereof through a linking member so that the transmission assemblies can be driven concurrently. Third, each element is independently installed. If replacing one element is required, it can be accomplished by merely unfastening the transmission member. The moving elements need only lubrication by dispensing lube oil regularly. Life span of the elements and machine can be enhanced. In short, the invention provides many benefits, notably:
[0012] 1. Linking structure is simpler and can be incorporated with the center posts of varying dimensions.
[0013] 2. The transmission wheels, driven wheels, axle wheels and pushing wheels of the transmission assembly are coupled and transmitted through the transmission members. Operation is steadier and quieter with less shaking or vibration.
[0014] 3. Multiple sets of transmission assemblies can be coupled in series according to requirements. And the transmission members and linking members are independent and can be replaced easily.
[0015] The foregoing, as well as additional objects, features and advantages of the invention will be more readily apparent from the following detailed description, which proceeds with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a perspective view of the driving mechanism of a conventional labeling machine.
[0017] FIG. 2 is a perspective view of the labeling machine of the invention.
[0018] FIG. 3 is a rear view of the labeling machine of the invention.
[0019] FIG. 4 is a perspective view of the driving mechanism of the labeling machine of the invention.
[0020] FIG. 5 is a rear perspective view of the driving mechanism of the labeling machine of the invention.
[0021] FIG. 6 is a front view of the driving mechanism of the labeling machine of the invention.
[0022] FIG. 7 is a rear view of the driving mechanism of the labeling machine of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] Please refer to FIGS. 2 through 5 , the driving mechanism for labeling machine according to the invention is connected to a power source such as an electric motor and includes a driving wheel 3 formed with teeth, a base 4 , a linking assembly 5 , a transmission assembly 6 , an axle assembly 7 and an adjustment assembly 8 .
[0024] Also referring to FIGS. 3 and 6 , the base 4 is fastened to a chassis 2 of a labeling machine 1 through an angular post 21 and has at least one sliding track 41 holding two sets of sliders 42 corresponding to each other. An anchor dock 421 is mounted onto the sliders 42 .
[0025] Referring to FIGS. 4 and 5 , the linking assembly 5 runs through the base 4 and is anchored thereon. It includes an actuation shaft 51 , an actuation wheel 52 , a linking wheel 53 , a linking member 54 and an idler pulley 55 . The actuation shaft 51 runs through the base 4 . The actuation wheel 52 and the linking wheel 53 have teeth formed on the perimeters thereof, and are located on a back side of the base 4 and coupled on one end of the actuation shaft 51 . The linking member 54 may be a belt and is annular with teeth formed on an inner side. The idler pulley 55 is located on the base 4 and has the perimeter engaging with the linking member 54 to push the linking member 54 to adjust the tension thereof.
[0026] The driving wheel 3 is connected to the power source such as the electric motor and the linking assembly 5 by engaging with the actuation wheel 52 thereof through the teeth formed thereon.
[0027] Referring to FIGS. 4 , 5 and 6 , the transmission assembly 6 is mounted onto the base 4 and connected to the linking assembly 5 . It includes a transmission wheel 61 , a transmission member 62 , a driven wheel 63 , two sets of axle wheels 64 and two sets of pushing wheels 65 . The transmission wheel 61 has teeth formed on the perimeter and is coupled on another end of the actuation shaft 51 run through the front side of the base 4 , and rotates concurrently with the actuation wheel 52 and the linking wheel 53 . The transmission member 62 may be an annular belt with teeth formed on two sides to couple and engage with the teeth of the transmission wheel 61 . The driven wheel 63 is mounted onto the base 4 and engages with the transmission member 62 . The two sets of axle wheels 64 and pushing wheels 65 have teeth formed on the perimeters, and are located respectively on the anchor dock 421 of the two sliders 42 . The axle wheels 64 and pushing wheels 65 are spaced from each other to form a desired gap between them to allow the transmission member 62 to pass through. The pushing wheels 65 provide pressing to make the transmission member 62 in close contact with the axle wheel 64 . The teeth on one side of the transmission member 62 engage with the teeth of the axle wheels 64 and the teeth on another side thereof engage with the teeth of the pushing wheels 65 . The transmission wheel 61 can drive the two sets of axle wheels 64 to move concurrently through the transmission member 62 .
[0028] The axle assembly 7 includes two sets of axles 71 , a set of axle adjustment member 72 and two sets of feeding wheels 73 . The two axles 71 are respectively coupled with the two axle wheels 64 on the axes thereof. The axle adjustment member 72 is located on a middle portion of the axle 71 . By moving the axles 71 , the distance between them can be adjusted. Each feeding wheel 73 is mounted on a distal end of each axle 71 .
[0029] The adjustment assembly 8 includes an adjustment dock 81 and an idler pulley 82 . The adjustment assembly 8 is located on the base 4 and engages with the transmission member 62 of the transmission assembly 6 . The idler pulley 82 also engages with the transmission member 62 . The position of the idler pulley 82 can be adjusted through the adjustment dock 81 to push the transmission member 62 to adjust the tension thereof.
[0030] Referring to FIGS. 2 , 6 and 7 , when the driving wheel 3 is driven by the power source, the motion is transmitted to the actuation wheel 52 through the linking member 54 . Through the actuation shaft 51 , the transmission wheel 61 of the transmission assembly 6 is rotated concurrently to drive the transmission member 62 ; hence the two sets of axle wheels 64 engaged with the transmission member 62 also are driven to rotate in opposite direction at the same time.
[0031] When the linking wheel 53 is removed from the actuation shaft 51 , the driving wheel 3 is connected to the actuation wheel 52 merely through the linking member 54 and drives only one transmission assembly 6 , hence the two axle wheels 64 are driven through a single driving fashion.
[0032] When two sets of the driving mechanisms of the invention are installed, the labeling machine 1 can be driven through a dual driving fashion. In such a circumstance, an extra idler pulley 55 is installed on the base 4 , and the linking member 54 a on the second linking assembly 5 a is adjusted. No adjustment is required for the first set of the linking assembly. The linking member 54 is connected to one actuation wheel 52 and the driving wheel 3 . The linking member 54 a of the second linking assembly 5 a is connected to the linking wheel 53 of the first linking assembly 5 and the linking wheel 53 a of the second linking assembly 5 a. And the linking member 54 a of the second linking assembly 5 a is pushed by the idler pulley 55 to keep the linking member 54 a at a desired tension. Then the two sets of linking assemblies 5 and 5 a can be driven concurrently by the driving wheel 3 . As previously discussed, when the two sets of linking wheels 53 and 53 a of the two linking assemblies 5 and 5 a rotate, a dual driving fashion is formed to drive concurrently the two transmission assemblies 6 and 6 a.
[0033] To do repair and maintenance of the transmission member 62 of the transmission assembly 6 , only the transmission member 62 needs to be removed from the base 4 , and a replacing transmission member 62 can be coupled between the transmission wheel 61 and driven wheel 63 . Then the transmission member 62 can respectively pass through the gap between the axle wheel 64 and pushing wheel 65 on the two sliders 42 with the teeth of the transmission member 62 respectively engaging with the teeth of the axle wheels 64 on the two sliders 42 . Then the idler pulley 82 of the adjustment assembly 8 can be adjusted to control the tension of the transmission member 62 to finish the replacement process. Replacement of the linking member 54 can be accomplished by removing merely the linking member 54 from the actuation wheel 52 or linking wheel 53 and mounting a replacing linking member 54 .
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A driving mechanism for a labeling machine aims to drive a transmission assembly thereof from a power source through a linking member such as a belt. The transmission assembly concurrently drives rotation of an axle assembly so that a feeding wheel coupled on an axle can draw and convey a roll of film. A belt with teeth formed on two sides serves as a transmission member of the transmission assembly to transmit rotation to two axle wheels. The transmission assembly can transmit rotation accurately, rapidly and concurrently. The structure of the transmission assembly is simplified. Wearing can be reduced. Repair and maintenance also are easier.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation of International Application No. PCT/EP2007/063013, filed Nov. 29, 2007, which is hereby incorporated by reference in its entirety.
TECHNICAL FIELD
The technical field relates to airplane assembly. In particular, the technical field relates to a method for mounting a wing of an aircraft to a fuselage of the aircraft, a mounting system, a computer-readable medium, a program element and a processor.
BACKGROUND
When, during aircraft assembly, a wing of the aircraft has to be mounted to the fuselage of the aircraft care has to be taken that both the angle of attack and the sweep are correct. Therefore, the wing is mounted to a moveable positioning unit which is adapted for moving the wing to the fuselage and for adjusting the position of the wing with respect to the fuselage. However, this adjustment procedure is a laborious and time consuming process.
It is therefore at least one object of the invention to provide for an improved wing adjustment. In addition, other objects, desirable features, and characteristics will become apparent from the subsequent summary and detailed description, and the appended claims, taken in conjunction with the accompanying drawings and this background.
SUMMARY
According to an exemplary embodiment of the present invention, a method is provided for mounting a wing of an aircraft to a fuselage of the aircraft, the method comprising the step of determining a difference between a first actual z-position of a first mounting point of the wing and a first target z-position of the first mounting point, wherein the determination of the first difference is performed on the basis of a first measurement device attached to the fuselage and a first positioning device attached to the wing.
Therefore, according to this exemplary embodiment of the present invention, by simply attaching a measurement device to the fuselage and a positioning device to the wing, a mis-adjustment of the wing can be determined during the mounting procedure. This may provide for a fast and effective wing adjustment.
According to another exemplary embodiment of the present invention, the method further comprises the step of determining a second difference between a second actual z-position of a second mounting point of the wing and a second target z-position of the second mounting point, wherein the determination of the second difference is performed on the basis of a second measurement device attached to the fuselage and a second positioning device attached to the wing.
Therefore, according to this exemplary embodiment of the present invention, a second measurement of a mis-adjustment of the wing is performed, for example, at a different location of a contact area between wing and fuselage. Thus, a two-dimensional wing adjustment may be possible.
According to another exemplary embodiment of the present invention, the method further comprises the step of adjusting the wing with respect to the fuselage on the basis of at least one of the first difference and the second difference.
For example, according to this exemplary embodiment of the present invention, after having determined the two differences, a wing adjustment may be performed, resulting in a reduction or minimisation of the differences.
According to another exemplary embodiment of the present invention, the method further comprises the steps of attaching the first measuring device to the fuselage, arranging the first positioning device at a defined position relative to the first measuring device, transferring a hole located at the first mounting point to the first positioning device, resulting in a hole in the first positioning device, and attaching the first positioning device to the wing, such that the position of the hole corresponds to a position of a wing mounting point.
Thus, for example, the exact position of the first mounting point with respect to the measuring device may be transferred to the positioning device, which is then attached to the wing. Therefore, after moving the wing to the fuselage, it may be determined, whether the measuring device and the positioning device are now in the defined position relative to each other or not. If they are not in the defined position relative to each other, a corresponding difference is determined on which basis a further adjustment may be performed.
According to another exemplary embodiment of the present invention, arranging of the first positioning device at the defined position relative to the first measuring device is performed by means of a spacer.
For example, the spacer may be adapted as a lock consisting of, for example, aluminium, titanium or any other metal or metal compound, or any other material, such as a synthetic material. However, the spacer may be of any other form.
According to another exemplary embodiment of the present invention, the method further comprises the step of adjusting the wing on the basis of a crown fitting.
Such a crown fitting may provide for a correct wing adjustment along the y-axis as shown in FIG. 1 .
According to another exemplary embodiment of the present invention, the method further comprises the step of adjusting the wing on the basis of a determination of a contact between a spar and the wing.
This may provide for an exact wing adjustment with respect to the x-axis as shown in FIG. 1 .
According to another exemplary embodiment of the present invention, the determination of the first difference is performed by means of an electronic determination device.
Furthermore, the determination of the second difference may be performed by means of the same or a different electronic determination device. This may provide for a fast and exact difference determination.
According to another exemplary embodiment of the present invention, a mounting system for mounting a wing of an aircraft to a fuselage of the aircraft is provided, the mounting system comprising a determination unit for determining a first difference between a first actual z-position of a first mounting point of the wing and a first target z-position of the first mounting point, wherein the determination of the first difference is performed on the basis of a first measurement device attached to the fuselage and a first positioning device attached to the wing.
According to another exemplary embodiment of the present invention, a computer-readable medium may be provided, in which a computer program of mounting a wing of an aircraft to a fuselage of the aircraft is stored which, when being executed by a processor, causes the processor to carry out the above-mentioned method steps.
Furthermore, according to another exemplary embodiment of the present invention, a program element of mounting a wing of an aircraft to a fuselage of the aircraft is provided which, when being executed by a processor, causes the processor to carry out the above-mentioned method steps.
Furthermore, according to another exemplary embodiment of the present invention, a processor for mounting a wing of an aircraft to a fuselage of the aircraft may be provided, the processor being adapted to carry out the above-mentioned method steps.
The mounting and adjustment process may be embodied as the computer program, i.e., by software, or may be embodied using one or more special electronic optimisation circuits, i.e. in hardware, or the method may be embodied in hybrid form, i.e., by means of software components and hardware components.
The program element, according to an exemplary embodiment of the invention, is preferably loaded into working memories of a data processor. The data processor may thus be equipped to carry out exemplary embodiments of the methods of the present invention. The computer program may be written in any suitable programming language, such as, for example, C++ and may be stored on a computer-readable medium, such as a CD-ROM. Also, the computer program may be available from a network, such as the World Wide Web, from which it may be downloaded into processors or any suitable computers.
These and other aspects of the present invention will become apparent from and elucidated with reference to the embodiments described hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 shows a schematic representation of a section of a fuselage of an airplane to which the wing is mounted;
FIG. 2 shows a schematic representation of the mounting section according to an exemplary embodiment of the present invention;
FIG. 3 shows a schematic representation of the mounting section after having transferred the holes to the positioning devices;
FIG. 4 shows a schematic representation of a wing at which the positioning devices are attached;
FIG. 5 shows a schematic representation of positioning devices arranged at a defined location with respect to mounting devices with the help of spacer units, according to an exemplary embodiment of the present invention;
FIG. 6 shows a mounting system for performing the method according to an exemplary embodiment of the present invention;
FIG. 7 shows a representation of the mounting section of FIG. 1 in a first assembly state according to an exemplary embodiment of the present invention;
FIG. 8 shows a representation of the mounting section of FIG. 1 in a second assembly state according to an exemplary embodiment of the present invention;
FIG. 9 shows a representation of the mounting section of FIG. 1 in a third assembly state according to an exemplary embodiment of the present invention;
FIG. 10 shows a representation of the wing of FIG. 4 in a fourth assembly state according to an exemplary embodiment of the present invention;
FIG. 11 shows a representation of the mounting section of FIG. 1 and the wing of FIG. 4 in a fifth assembly state according to an exemplary embodiment of the present invention;
The illustrations in the drawings are schematic. In different drawings, similar or identical elements are provided with the same reference numerals.
DETAILED DESCRIPTION
The following detailed description of the invention is merely exemplary in nature and is not intended to limit application and uses. Furthermore, there is no intention to be bound by any theory presented in the preceding background or summary or the following detailed description.
FIG. 1 shows a schematic representation of an airplane fuselage 101 with a mounting section 102 at which a wing can be mounted. The mounting section 102 comprises mounting holes 201 , 202 , 204 , 205 . The mounting holes 201 , 202 , 204 , 205 are adapted for positioning the wing with the respect to the fuselage 101 .
The mounting section 102 may further comprise a front spar and a back spar (not depicted in FIG. 1 ). The wing which has to be mounted to the mounting section 102 may comprise a corresponding front spar and a corresponding back spar.
Front spar and back spar each comprise two bore holes 201 , 202 and 204 , 205 . Furthermore, first and second positioning devices 105 , 106 may be attached to the mounting section 102 (and arranged at a defined position with respect to the four bore holes).
The coordinate system at the upper left of FIG. 1 defines the directions of the x, y and z-axes.
FIG. 2 shows a schematic representation of the mounting section 102 after installation of the mounting devices 103 , 104 and the positioning devices 105 , 106 .
At a first step, the first measuring device 103 is attached to the fuselage or mounting section 102 by means of, for example, attachment devices 207 , 208 . Furthermore, at the other side of the mounting section 102 , the measuring device 104 is attached to the mounting section 102 by means of attachment devices 209 , 210 .
Then, in a second step, the first positioning device 105 is arranged at a defined position relative to the first measuring device 103 . Such arrangement may be performed with the help of a spacer 301 (as depicted in FIG. 5 ). Furthermore, the second positioning device 106 is arranged at a defined position relative to the second measuring device 104 .
Then, the positioning holes 201 , 202 are transferred into the first positioning device 105 , resulting in a hole in the first positioning device 105 . Furthermore, holes 204 , 205 are transferred to the second positioning device 106 .
Then, in a next step, the first and second positioning devices 105 , 106 are attached to the wing.
Then, the wing is moved towards the fuselage and the differences between the actual z-positions of the first and second mounting points 211 , 213 of the wing 107 (see FIG. 4 ) means first and second target z-positions 201 , 204 , respectively, are determined.
After that, a wing adjustment may be performed on the basis of the determined differences.
FIG. 3 shows a schematic representation of the mounting section 102 at which the first measuring device 103 and the second measuring device 104 are attached.
FIG. 4 shows a schematic representation of the wing 107 , at which the first positioning device 105 and the second positioning device 106 are attached at the mounting points 211 , 212 and 213 , 214 , respectively.
The mounting points 211 , 212 and 213 , 214 thereby correspond to the target positions 201 , 202 and 204 , 205 which are located at the mounting section 102 of the fuselage 101 .
FIG. 5 shows a schematic representation of the measuring devices 103 , 104 and the positioning devices 105 , 106 , which are arranged with respect to the measuring devices 103 , 104 with the help of respective spacer units 301 , 302 .
The spacer units 301 , 302 may, for example, have a thickness Δz1, Δz2 of, for example, 20 mm. However, the thickness may be bigger or smaller.
After having attached the measuring devices 103 , 104 to the mounting section 102 of the fuselage 101 and after having attached the positioning devices 105 , 106 to the wing 107 , and after having moved the wing towards the fuselage, Δz1 and Δz2 may be measured. In case Δz1 and Δz2 differ from the target value (which is, for example, 20 mm), a further wing adjustment may be performed.
The measuring devices or the positioning devices may comprise grooves or trenches, such that an attachment position can be varied. Therefore, the spacer 301 may always fit in between.
FIG. 6 shows a mounting system for mounting a wing of an aircraft to a fuselage of the aircraft, according to an exemplary embodiment of the present invention. The mounting system depicted in FIG. 6 comprises an output unit 601 , for example a computer screen, and an input unit 602 , for example a keyboard. Furthermore, the system comprises a processor 604 and a storage unit 603 in which a computer program for mounting the wing to the fuselage is stored.
Furthermore, the mounting system comprises a determination unit 605 adapted for determining the differences Δz1 and Δz2. The determination unit 605 may further be adapted for determining, for example a contact between a spar and the wing or for determining a crown fitting.
Further determination units may be provided.
The mounting system further comprises a wing mounting unit 606 , which is adapted for moving and positioning the wing 107 with respect to the fuselage 101 .
The wing mounting and positioning may be performed in a fully automated manner or user guided in a semi-automated manner.
FIG. 7 shows a representation of the mounting section of FIG. 1 in a first assembly state according to an exemplary embodiment of the present invention. As may be seen from the figure, a positioning device 106 is attached to the mounting section 102 of the fuselage.
FIG. 8 shows a representation of the mounting section of FIG. 1 in a second assembly state according to an exemplary embodiment of the present invention. Here, a measurement device 104 is attached to the mounting section 102 of fuselage at a predetermined distance from the measurement device 104 (e.g. by transferring holes from the fuselage to the measurement device 104 ). The distance is determined by spacer 302 .
FIG. 9 shows a representation of the mounting section of FIG. 1 in a third assembly state, in which all three elements 102 , 104 and 104 are assembled at the mounting section.
FIG. 10 shows a representation of the wing of FIG. 4 in a fourth assembly state according to an exemplary embodiment of the present invention. Here, the positioning device 106 is attached to the wing 107 , for example by using the transferred holes.
FIG. 11 shows a representation of the mounting section of FIG. 1 and the wing of FIG. 4 in a fifth assembly state according to an exemplary embodiment of the present invention. As may be seen from the figure, the wing 107 is moved towards the fuselage section 102 for final mounting of the wing 107 . By determining the difference Δz between actual z-position of the positioning device 106 and the z-position of the measurement device 104 (which z-position corresponds to the target z-position minus the height of the spacer 302 ) an adjustment of the wing 107 with respect to the fuselage may be performed on the basis of the difference.
It should be noted that the term ‘comprising’ does not exclude other elements or steps and the ‘a’ or ‘an’ does not exclude a plurality. Also, elements described in association with different embodiments may be combined. Moreover, while at least one exemplary embodiment has been presented in the foregoing summary and detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing summary and detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims and their legal equivalents.
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A method is provided for mounting a wing of an aircraft to a fuselage of the aircraft, in which a difference between a vertical target position and a vertical actual position of a mounting point is determined. Then, on the basis of the determined difference, a readjustment of the wing is performed.
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[0001] This application claims priority from U.S. Provisional Application No. 61/528,748, filed on Aug. 29, 2011, which is hereby incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] The disclosed subject matter of the present invention relates to a method and system for combining an organization's asset related data with multi-dimensional spatial information. In particular, it relates to the provision of real-space visualization of anything that can be associated with a geographical location.
BACKGROUND
[0003] A geographic information system (GIS) is designed to store, manage and present all types of geographically referenced data, and may be used to facilitate decision making. At a high level, a GIS is the merging of cartography and database technology. Spatial areas in a GIS may be jurisdictional, purpose or application-oriented. Traditionally, geographical information systems have inhabited a domain specific knowledge area, requiring specialized skills to use and maintain.
[0004] There is a need to manage environmental assets spread across a wide geographic area. The costs associated with maintaining these assets are high, often requiring specialist resources to be sent to remote locations. Conversely, the cost of failing to monitor and maintain these assets on a regular basis results in millions of dollars worth of fines and levies in North America each year. In many cases, these fines could have been avoided had the organization had a better way of monitoring where and when these assets needed to be maintained. While spreadsheets are great tools for collecting data, they are less effective at presenting information.
SUMMARY OF INVENTION
[0005] The disclosed subject matter of the present invention provides a geographic asset management system representing a scalable, platform agnostic decision support application that combines an organization's asset related data with multi-dimensional spatial information, providing real-world visualization of anything that can be associated with a geographical location. It is designed to integrate this GIS data with a management and reporting application that supports the tracking and visualization of all assets. These ‘assets’ can be anything from capital assets, such as buildings or computers, to commitments, such as land-use permits or research grants.
[0006] The geographic asset management system provides a visual portal to users' information, allowing them to better determine the spatial relationships between the assets that they are monitoring, which is particularly useful when the assets are buildings. This visual representation may, for example, be used to help reduce travel expenses to remote offices, plan locations of medical clinics or stores to optimize coverage in a given area, or compare designs for a new construction project with the existing environment.
[0007] For example, take the case where a university faculty that has been experiencing significant growth is now planning a new building. The planning department receives the request for the new faculty building. They have received two similar requests from other faculties in the past month. While the university lands are extensive, a significant portion has been set aside as park land. In addition, the university has many heritage buildings on campus, and a directive to preserve the architectural image of the campus, which limits the size of building projects. The university has also been promoting sustainable communities, and the planning department knows that any new construction must be clearly aligned with this initiative. The planning department identifies potential sites for the new construction and issues requests for proposals. Interested architects are provided access to the university's three-dimensional (3D) model in the geographic asset management system, and are instructed to upload their digital models into the virtual campus. At the next board meeting, the planning department is able to present all of the submitted models in a single session, and review the new building designs next to the existing university structures.
[0008] Disclosed herein is a geographic asset management system for presenting assets in a three dimensional rendering, comprising: one or more databases storing asset related data comprising: details of a plurality of assets; geographic locations of the assets; geographic orientations of the assets; and one or more three dimensional models each of one or more of the assets; a server for controlling access to the one or more databases; a user terminal connected to said server for requesting at least some of the asset related data; and a geographic information system; wherein the one or more processors are configured to cause display on the user terminal a three dimensional rendering of a landscape retrieved from the geographical information system and one or more of the three dimensional models retrieved from the one or more databases, each displayed model located and oriented in the rendering of the landscape according to its geographic coordinates and orientation.
[0009] Also disclosed herein is a method for presenting assets in a three dimensional model, comprising: storing, by a processor, in one or more databases, asset related data comprising: details of a plurality of assets; geographic locations of the assets; geographic orientations of the assets; and one or more three dimensional models each of one or more of the assets; receiving, by a server, a request to access at least some of the asset related data; transmitting, by the server, said requested asset related data to a user terminal; displaying, on the user terminal, a three dimensional rendering of a landscape retrieved from a geographical information system; and displaying, on the user terminal, one or more of the three dimensional models in the rendering of a landscape, each displayed model located and oriented in the rendering of the landscape according to its geographic coordinates and orientation.
[0010] The invention further relates to one or more computer readable media carrying computer readable instructions, which, when executed by one or more processors cause said processors to: store, in one or more databases, asset related data comprising: details of a plurality of assets; geographic locations of the assets; geographic orientations of the assets; and one or more three dimensional models each of one or more of the assets; receive a request to access at least some of the asset related data; transmit said requested asset related data to a user terminal; display, on the user terminal, a three dimensional rendering of a landscape retrieved from a geographical information system; and display, on the user terminal, one or more of the three dimensional models, each displayed model located and oriented in the rendering of the landscape according to its geographic coordinates and orientation.
BRIEF DESCRIPTION OF DRAWINGS
[0011] The drawings illustrate embodiments of the invention but should not be construed as restricting the scope of the invention in any way.
[0012] FIG. 1 is an overview of the geographic asset management system.
[0013] FIG. 2 is a schematic drawing of the system according to an embodiment of the disclosed subject matter of the present invention.
[0014] FIG. 3 is a flowchart showing how the system displays data.
[0015] FIG. 4 is a map of the architecture of the system.
[0016] FIG. 5 is a schematic diagram of the framework of the system
[0017] FIG. 6 is a schematic diagram of hidden details displayed on a local portable device.
[0018] FIG. 7 is an example of a display showing a 3D view of a building.
[0019] FIG. 8 is a screenshot of a floor of a building showing markings for different types of room.
[0020] FIG. 9 is a schematic representation of a screenshot showing a room and an asset located in the room.
[0021] FIG. 10 is an alternate representation of the architecture of the system
[0022] FIG. 11 is a flowchart of a process for uploading building models to the system.
[0023] FIG. 12 is a partial screenshot showing a map, features marked on the map and a legend.
[0024] FIG. 13 shows a partial screenshot showing a query result.
[0025] FIG. 14 is a menu bar showing the draw option expanded.
[0026] FIG. 15 is a partial screenshot showing a feature drawn on a map.
[0027] FIG. 16 is a partial screenshot showing a search result.
[0028] FIG. 17 is a schematic representation of a screenshot of an assets list.
[0029] FIG. 18 is a schematic representation of a screenshot of an asset's details.
[0030] FIG. 19 is a schematic representation of a screenshot of a form for adding a proposed asset.
[0031] FIG. 20 provides a screenshot showing a form for editing a user's role and organizational unit.
[0032] FIG. 21 provides a screenshot showing a form for adding a user.
[0033] FIG. 22 is a schematic representation of a screenshot of a list of permissions.
[0034] FIG. 23 is a schematic representation of a screenshot of a list of map layers.
[0035] FIG. 24 shows a screenshot for editing a role.
[0036] FIG. 25 shows a menu bar of the 3D component.
[0037] FIGS. 26 and 27 show screenshots with a building model present and absent, respectively.
[0038] FIG. 28 is a schematic representation of an environment settings window.
[0039] FIG. 29 is a schematic representation of a screenshot of a form for adding a new building model to the system.
[0040] FIGS. 30 and 31 respectively show screenshots of a view with underground detail hidden and displayed.
DESCRIPTION
[0041] Throughout the following description, specific details are set forth in order to provide a more thorough understanding of the invention. However, the invention may be practiced without these particulars. In other instances, well known elements have not been shown or described in detail to avoid unnecessarily obscuring the invention. Accordingly, the specification and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
[0042] The detailed descriptions that follow are presented largely in terms of methods or processes, symbolic representations of operations, functionalities and features of the invention. These method descriptions and representations are the means used by those skilled in the art to most effectively convey the substance of their work to others skilled in the art. A software implemented method or process is here, and generally, conceived to be a self-consistent sequence of steps leading to a desired result. These steps require physical manipulations of physical quantities. Often, but not necessarily, these quantities take the form of electrical or magnetic signals, values or parameters capable of being stored, transferred, combined, compared, and otherwise manipulated by one or more processors, each with one or more cores. It will be further appreciated that the line between hardware and software is not always sharp, it being understood by those skilled in the art that software implemented processes may be embodied in hardware, firmware, or software, in the form of coded instructions such as in microcode and/or in stored programming instructions. Furthermore, the processes may be divided into constituent modules or components.
[0043] An overview of the geographic asset management system, generally designated 2 , is shown in FIG. 1 . The geographic asset management system 2 is a combination of a traditional GIS component 4 with an asset management system component 6 . The system 2 may be established according to a client-server architecture. For example, referring to FIG. 2 , a user of the system 2 may access it through a terminal 10 , such as a general purpose computer, desktop computer, portable computer, laptop computer, smartphone, notebook, tablet computer or any suitable computing device that is connectable to a network 14 and has a display 12 or is connectable to a device that has a display. The network 14 may be any data network including, for example only, the Internet, a telecommunications network, a local network, or a combination of one or more of these.
[0044] The user may open up a web browser on terminal 10 and browse to the web site of the system 2 which is hosted on server 16 operably connected to the network 14 via interface 18 . The connections in the network 14 may be wired or wireless, although normally the connection between the network 14 and the server 16 will be wired, whereas the connection of the terminal 10 to the network 14 may commonly be either wired or wireless. The server 16 houses one or more microprocessors 20 , operably connected to a memory 22 , which may include non-volatile and/or volatile memories, electronic memories and/or optical memories. Stored in the memory 22 are computer readable instructions 24 , which when processed by the processor 20 cause the server 16 to implement functions of the components 4 and 6 of the system 2 , as described in detail hereinafter.
[0045] Also connected to the network 14 is a database 26 , in which is stored GIS data 27 and asset data 28 . Asset data 28 may include geographical coordinates of the assets, notes about the assets, times related to the assets, 3D views of the assets, etc. The database 26 alternately may be located in the server 16 , or it may be locally connected to it. In other embodiments, the database 26 may be divided into a public information part, such as general geographic information and coordinates and a private information part, such as details of a user's assets. Such private information may be stored on the user's premises or elsewhere, and may be password protected and/or encrypted.
[0046] Also shown in FIG. 2 is an example of another terminal, or mobile electronic device 30 , which a user may use to interface with the system 2 . Basically, the system 2 is accessible by any web-capable device (Windows, Mac, iOS, Android, etc.). Device 30 may, for example, be a laptop computer that is connected to the network 14 via interface 36 . The device 30 has a display screen 32 in which a web browser can be displayed for interacting with the server 16 and data in database 26 . Device 30 includes one or more processors 34 that connect to and control the components of the device 30 , such as user input component 46 , which may be a keypad, keyboard or even a touch screen combined with display 32 . A memory 38 is included for storing data and programs that can be processed by the processor 34 . The memory 38 may store, for example, a browser application 40 , an optional local module 42 of the system, a location determining program 44 and any of many possible further components and/or modules that may form part of the system 2 .
[0047] Data may be displayed on the screens 12 , 32 as a two-dimensional (2D) rendering, such as in the form of a map, plan or bird's eye view. Data may also be displayed on the screens 12 , 32 as a 3D rendering, such as a perspective view, a view of a landscape, or real-space visualization.
[0048] If a browser is not used, which may be the case in some embodiments, the local module 42 may be installed to facilitate the function of specific components on the client. Even if a browser is used, a local module may still be needed for some modules. Localization of the system will allow it to support multiple languages.
[0049] The location determining program may determine location itself or with the help of external devices. For example, it may be a hardware GPS device. It may operate based on A-GPS or D-GPS, or it may receive signal strengths from Wi-Fi access points that can be used by a remote server to deduce the location of the device 30 . The device 30 may also include an orientation detecting device 48 , which may be a compass that may optionally be combined with accelerometers, allowing the processor 34 to determine the pointing direction of the device 30 and/or changes in the pointing direction. The accelerometers may also be used to determine positional changes of the device 30 to a finer resolution than can be provided with GPS.
[0050] The computer readable instructions 24 may be prepared using a commonly known programming language or toolset, such as VS2010™, .NET 4.0™, Silverlight™ 4.0, nUnit™, IIS 7.5 Express™, SQL, MEF, EF 4.1, etc.
[0051] Referring to FIG. 3 , a flowchart is shown of how the system 2 displays data on a device 30 . As per step 60 the system 2 accepts a user's login identity and credential, such as a password. An organization would set up users at varying security levels, and then develop a library of assets based on the specific items they were most interested in tracking. A user would only be allowed to access those assets for which he has been authorized. All assets would have a relation to a specific geographic location.
[0052] When the user is logged in, the user is presented with a choice of queries that can be made, or the user can define a query. As per step 62 the system 2 receives whatever query the user inputs, and, based on the contents of the query, as per step 64 retrieves GIS information and as per step 66 retrieves further data relating to the assets that are being queried. Data may be retrieved from multiple repositories. The assets can be stored in one or more databases, so long as at least one of the databases is geospatially enabled. As per step 68 the system 2 then compiles the data into an appropriate form, such as a standardized, spatially-enabled form, and then as per step 70 displays the compiled data on the user's screen. A displayed image may include a map with particular assets marked on it.
[0053] FIG. 4 is a map of an example of the architecture of the computer readable instructions 24 of the system 2 . Other architectures may equally be used. The architecture is modularized to provide custom functionality as required by an organization.
[0054] In the present embodiment, the overall architecture 80 has four main parts, these being the non-core components 90 , the core components 100 , the technology 150 and the modules 160 . Note that the division between core and non-core components relates to the architecture of the embodiment, and does not necessarily correspond to a boundary of the invention.
[0055] The non-core components 90 include a library 92 , a contact manager 94 , an alerting system 95 , a notification system 97 and a 3D visualization component 98 . The 3D component 98 may allow for the management of 3D models, such as permitting the upload of a model, upload of a skin, management of names, and management of asset or asset type corresponding to the model. A 3D model may be built into or bundled with a specification of an asset for unity.
[0056] The notification component 97 can be configured to notify a user or group of users based on events related to an asset. Events and their associated actions may be stored as alerts 95 . Events may range from specific dates to actions in system 2 (e.g., a report submitted against an asset). By displaying these events through a graphical interface (in this case, the map), an organization can quickly determine the geographical relationship between these events to assist in optimizing a response.
[0057] The system core 100 is divided into four main parts. The first part is security 102 , the purpose of which is to grant access to system functionality and data subsets by configuring roles for users through the system's administrator interface. Security 102 is based on an additive model. No access is the default and access is added based on roles.
[0058] Security 102 has an authentication component 104 and an authorization component 112 . The authentication component 104 serves to check a user's identification, such as a unique user name and/or unique email address, and credentials, such as a password. Authentication may be achieved externally 106 from the system using LDAP (Lightweight Directory Access Protocol), which is commonly used for accessing and maintaining any organized set of records over an Internet Protocol network. Other systems, such as OpenID and Active Directory may be used. Alternately, the authentication may be achieved internally 108 to the system, or it may be hybrid 110 .
[0059] The authorization component 112 of security 102 deals with the definition of roles 114 and assignment of roles to users. An organizational unit 116 is a logical group for partitioning assets, and may be referred to as an OrgUnit or User Group. An asset only belongs to one organizational unit directly. Organizational units may be aligned with departments, for example, and may be assigned to users. Through the configuration of relationships between organization units, an asset may be made available to other organizational units. A role is a collection of permissions 118 for access to system functionality and/or data. Roles are assigned to users.
[0060] A position is the intersection of a user, organizational unit 116 and role 114 defining the functionality available to a user over an asset. A user can have one or more roles 114 in one or more organizational units 116 via one or more positions. A user may change his personal preferences, such as changing his first and last name, password, email address, etc. However, depending on the embodiment chosen, a user name is not editable by the user.
[0061] There is no unauthenticated access allowed by the system 2 . A guest account may be set up as a special account, like the administrator's account, and can be enabled to support a “public” style login. The account will be granted permissions similar to any other account but users of the account will not be able to modify any of its settings or preferences.
[0062] Security 102 may include both client-side and server-side security, including authentication 104 , authorization 112 and role-based permissions 118 . Permissions represent the abilities of users to interact with various aspects of the system 2 . Such interactions may be the right to create, read, update and delete data. Permissions are assigned to roles.
[0063] A system administration component may be included in the computer readable instructions 24 ( FIG. 2 ) to manage various aspects of the system 2 . For example, in reference to authorization 112 , with respect to users it may be used to add, edit, delete users; manage organizational unit associations; and manage role associations. With respect to User Groups (organizational units 116 ) it may also be used to add, edit, delete User Groups; manage user associations; and manage role associations. With respect to roles 114 it may be used to add, edit, delete roles; manage user associations; and manage User Group associations.
[0064] Assets 120 , or details of them, form the second part of the core 100 of the architecture 80 . Assets 120 may be single or generic 122 depending on the embodiment, and they are specified with a location 124 . The system administration component may also be used to manage asset types. Each asset 120 configured in system 2 inherits security rights, enabling asset data to be restricted by the user's role in system 2 . A base asset class may have the following attributes: ID, Name, Description, User Group, Location, MapService and FeatureID. Specific assets may inherit attributes from the base asset class.
[0065] Custom assets may be defined, such as buildings or trees. If a building is defined as an asset, it may have the following attributes, for example: project, construction year, material, use, underground parking, designer name, building revision date, green status, heritage, floor height, building width, building length, gross area, and floors. If a tree is defined as an asset, it may have the attributes: type, tag, age, height and morphology. Other items with or without geographical locations may also be defined as assets.
[0066] Spatial display (map) 130 is the third part of the core 100 of the architecture 80 . The map 130 may have layers that are configurable by admin and secured by role. GIS tools may be included, such as pan, zoom, extent, identify and feature query. Feature query may display a link to the asset details. Drawing tools may also be included such as point, line and polygon, etc. Screen capture may be enabled. Assets 120 may be displayed on the map with icons, by type of asset, and the icons may be colored according to the attribute of the asset. It may also be configured to add a new asset at a point.
[0067] The fourth part of the core 100 is navigation 140 . The navigation 140 may be driven by a configuration file, which may be managed manually or automatically. The navigation function may include navigation elements that point to core screens, screens within a module assembly or an arbitrary URL. Navigation 140 may send a user to a URL in either a new window or a current window. A navigation element may have the following attributes: name, which is the text to display on the navigation element; URL, which is the destination of navigation action; icon, which is the graphic to display on the navigation element if appropriate; DisplayMode, which is whether to display the text, the icon or both the icon and text; and roles, being the roles required to be able to see the navigation element.
[0068] The local optional modules 160 part of the architecture 80 implement specific and desired asset functionality. For example, there may be a community planning module 162 , a building information management module 164 and a land registry module 166 . Further, optional modules may be added as desired.
[0069] The building information management (BIM) system 164 allows space planning in 3D. Where traditional systems have relied on floor plans, system 2 of the present invention depicts in-scale 3D models with selectable rooms. Facility planners using this BIM module are now able to see not only rooms, but also the proximity of those rooms to each other and other building features (elevators; washrooms; wheelchair ramps, etc.).
[0070] A file manager may be included in the computer readable instructions 24 ( FIG. 2 ) to manage the various files and records in the system 2 . Such a file manager would allow files to be saved to disk; maintenance of meta data attributes; and management of files by asset user interface plugin (asset), by file manager user interface (asset type, organizational unit, unassociated) or by permissions granted to roles.
[0071] The technologies 150 that may be used include presentation applications 152 , databases 154 , a GIS 156 and a platform 158 . The system 2 may be platform agnostic, in that it supports multiple database formats (MS™ SQL, Oracle™, Spatial™ SQL, etc). It may also support multiple mapping services (Online [Google™, Bing™, Yahoo™] ESRI™, AutoCAD™ 3D Map, etc).
[0072] FIG. 5 is a schematic diagram showing an example of a framework of the system 2 . The components of the example architecture 80 described above in reference to FIG. 4 may be located together within the framework or separately, depending on the particular embodiment built. A laptop or other network accessible computing device 200 is used to access, from any suitable global location, the application interface 202 , which includes interfaces for a business process component 204 , a data visualization component 206 and a reporting component 208 . These application interfaces may provide the user with access to a document library 220 and a 3D visualization component 222 , both of which have access to documents and models stored in a model repository 224 .
[0073] The user may also access the web application framework 210 , which includes a module manager 212 , a user interface 214 , a GIS interface 216 and common interface libraries 218 . The GIS interface 216 interfaces with GIS/map services 226 , and the common library interfaces 218 interface with geocoding services 228 .
[0074] The web application framework 210 provides the link to the core framework 240 , which includes a services manager 242 , which in turn includes the security controller 244 . The security controller 244 manages shared data access 246 and local data access 250 . Shared data that is accessed may be provided by subscription data sources 248 .
[0075] Local data access component 250 may link via a database engine 262 to one or more databases 264 , which may be written in MS SQL Server™, Oracle™, MySQL™ or any other database programming and access language. The business logic of data entry forms may be managed by the system 2 using a combination of C# code, for example, and through the use of stored procedures, views and functions within the databases. Databases may be tabular 270 , archival 272 , spatial (i.e. 2D) 274 , temporal 276 or media 278 . The security controller 244 may link to the database(s) 264 via a network domain policies component 260 , which may allow access using an LDAP, OpenID™, WebADE™, Active Directory, etc or a custom protocol.
[0076] Client side output, such as pictures, video, 3D models, reports etc., as displayed on the data visualization component 206 or created in the reporting component 208 , may be fed via link 279 back to the database engine 264 and/or databases 270 - 278 . Likewise, analytics of clients' usage and loyalty may be fed from the users to the database engine 264 and/or databases 270 - 278 . The system 2 may track all transactions that are executed against the database history and metadata tables. These tables can be used to perform audits, repair damaged records and produce reports.
[0077] As mentioned above, different architectures may be used. An example of an add-on module is shown in FIG. 6 . Such an add-on module to the core system will allow users to track assets at a more granular level than traditional GIS systems. For example, Insight NR™ (New Reality) as provided by CloverPoint™ will provide users with the ability to locate and interact with assets that are normally hidden from the naked eye. Using location based services, a user will be able to access information about an asset based on the location and orientation of their Internet-capable mobile device. The end effect will be the virtual ability to look through walls. In FIG. 6 , a wall 280 is shown behind which there are two pipes 282 , 284 , which are not normally visible. A smartphone 286 is placed in proximity to the wall, and its internal orientation detecting devices and location based services allow the server to determine what a user would see if looking though the wall at the position of the smartphone and in the direction the back of the smartphone is facing. In this case, views 290 , 292 of the two pipes are shown on the display screen 288 of the smartphone. This module may also be used for visualizing underground pipes, cables and fibers, etc.
[0078] FIG. 7 shows an example screen shot 300 of a landscape provided by GIS system component 4 ( FIG. 1 ) enhanced according to the system 2 with 3D component 98 ( FIG. 4 ). A user is shown to be logged in 302 as Matt, according to the security setting of the system 2 . A log out button 303 may be present adjacent to the display of the logged in status. At the top right of the screen is a compass 304 indicating the direction of the view. The geographic (x, y) coordinates 306 of the view (or the center point of the view) are also displayed. Alternately, the coordinates given may be that of a cursor that can be tracked over the view. The z coordinate may also be displayed. A search box 305 may be included in the display, for searching for buildings, rooms, space type, or any other item or feature related to the landscape. The view shows contours of a hillside 307 and a group of buildings 308 . A 3D model of a building 310 is also shown. This building may be defined as an asset of the system. The building may be selected, or floors or rooms of the building may be selected, and then navigated to.
[0079] A menu bar 320 allows a user to easily move around the site. For example, the user may switch from a 3D view to a 2D view. The user may toggle the buildings model layer on and off. The user may go to the main page, the settings page or the admin page. The user may go to a library listing all the assets. The menu may be positioned anywhere on the screen, and could be along the top of the screen, for example.
[0080] Navigation display block 330 allows the user to toggle the walk mode 332 on and off, and to toggle the night mode 334 on and off. The speed at which the view is explored may be set by a slider 336 . Below the navigation block there may be a history slider 338 , which can change the view according to date, which may also be displayed alongside the slider. Alternately, dates may be entered explicitly, selected or stepped through, etc. As an organization collects data on assets over time, it can make use of the timescale functionality to track historical trends in order to better configure the notification system (i.e., an equipment failure at plant A will raise the load at plant B to critical levels within 2 days, unless plant C is brought online). Where most traditional GIS systems are reactive in nature, the present system provides users with a decision support system to optimize their future plans.
[0081] The tombstone block 340 displays headings for the asset selected, the values of which are shown in data block 342 . Shown, for example, in block 342 , is the name of the building that is selected, the construction date, and a specific floor if one is selected. A floor may be selected either by clicking on the corresponding floor of the 3D building model 310 or by selecting from the up/down selection arrows. The location of the building may be displayed by showing its geographic coordinates. Any notes that have been added to the system 2 may also be displayed. Depending on the permission granted to the user, the user may be able to add or edit notes relating to the building. In a similar way, a selected portion of the asset may be shown in asset heading block 350 and data block 352 . For example, if a room of the building is selected, the room name or number may be shown, the faculty to which it belongs, the department, the unit, the space type (e.g. lab, office, meeting room, canteen, etc.) and the next scheduled maintenance date. Users may add and remove assets as a way to facilitate the consideration of alternate scenarios.
[0082] Such a client enterprise asset visualization component 98 or 2D view may allow users to drill down functionality to a site, building, or asset's information. It may permit spatial calculations on the fly to instantly report on key aspects, such as, for example, the number of assets in a 5 km radius due for maintenance in the next 15 days, or linear feet of pipe that needs to be replaced.
[0083] FIG. 8 shows an example of a partial screen shot displaying a plan of a floor 370 in a building. In this view, different rooms have been marked according to different classifications 372 , 374 , 376 , 378 . This may be useful, for example, when a hospital is expanding. New buildings may be being built to accommodate certain groups. While the construction is going on, rooms may need to be reallocated. The facilities manager may have received lists of requirements from each of the wards affected by the move. She would then use these parameters to display all of the rooms that meet these criteria, as well as their proximity to supporting infrastructure. Using the system 2 , the facilities manager would be able to prepare a number of simulations of space usage. These simulations, combined with hospital usage metrics, would allow the facilities manager to prepare and present an optimum solution that minimizes the impact to both patients, visitors and staff. Navigation buttons may be included to allow the user to switch from floor to floor in each building stored in the system 2 .
[0084] FIG. 9 is a schematic representation of a screenshot showing a room 380 in a building, and an asset 381 located in the room. In this example, the asset is a fire extinguisher, although other types of assets may be included. To the left of the screenshot is a side bar 382 , which may contain asset number 383 , asset name 384 , purpose 385 of the asset, which in this case would be safety, and date and time last inspected 386 . There may be a button 387 for entering or viewing details of an inspection. There may also be an edit button 388 for editing notes 389 that may be included in the side bar 382 . At the lower right portion of the screen are a further set of buttons, for accessing the controls 390 , the management system 391 and to logout 392 . The controls 390 are for configuration settings for the application. These allow the user to pull new information from the server, search for items, or load a pre-saved configuration (i.e., meeting room tables instead of desks). The controls 390 may be condensed into the toolbar.
[0085] Using this aspect of the system 2 , support staff and contractors can be directed to the exact location of assets requiring maintenance. For example, an electric company may have dispatched an employee to a university to install a high voltage socket. As part of the ticket issued by the university's facilities manager through the system 2 , the contractor would have been provided with a map with a 3D view showing the location of the new socket, which would also display the nearby infrastructure. The facilities manager may also have left specific notes regarding how to interact with the infrastructure at several positions on the map. All of this information may be made available to the electric company employee through a mobile computing device. While the contractor is on site, the facilities manager may receive an alert through the system 2 that there is an electrical problem in a neighboring building. Seeing that the electrical contractor is still checked in at the campus, the facilities manager may place a call to arrange for the contractor to look at the new issue before leaving. Improved information sharing using the system 2 therefore leads to less time spent resolving issues, and lower facility maintenance costs as a result.
[0086] FIG. 10 is an alternate representation of an example of the system 2 . Devices 10 , allow users in the cloud to connect to the system 2 via the Internet 14 . Such a device 10 , 30 may also be used for viewing hidden detail, as described with respect to FIG. 6 . Connection is via a security component 244 and a data filter component 400 . The data filter allows users to read and write to the databases depending on their authorization levels, or roles.
[0087] Reading functions may use one or more load balancers 402 , one or more image caches 404 and one or more data caches 406 to retrieve data 412 from various web sites 408 , and databases 418 and the GIS 416 via a database cache 410 . Writing functions may use one or more load balancers 402 and one or more data caches 406 , and data to be written may be queued 414 before being written to a database 418 . Asset information 412 may be backed up either by mirroring the database(s) or by striping them.
[0088] Building Model Upload
[0089] FIG. 11 is a flowchart of a process for uploading building models to the system 2 . An embodiment of system 2 supports the uploading, in step 420 , of building models from any 3D modeling software that can save to the 0.3DS file format. For example, Studio MAX™, Maya™, and Sketch-Up™ all support this format. The final model should be saved as a single mesh/object, with all interior detail removed, normals of the building surfaces facing outwards, and all points and polygons not associated with the model geometry removed. Depending on the embodiment, the polygon count may be limited to a maximum, for example only, of 60,000. Likewise, the scale may be constrained to have a given conversion, which may be 1 m to 100 units, again as an example only. These files are detected and converted during the upload process, in step 422 , into the .OBJ format, which can then be imported, in step 424 , into the 3D component 98 ( FIG. 4 ).
[0090] Reflecting the realities of large-scale construction, the existing terrain may need to be adjusted to accommodate the new building model. An uploaded building model can therefore be associated with an optional terrain model. This terrain model alters the appearance of the landscape in the existing 3D scene, either increasing or decreasing the elevation based on the parameters of the terrain model that is uploaded.
[0091] In step 426 it is determined whether a terrain model is uploaded in conjunction with the building model. The terrain model should be a separate 3DS file, with similar guidelines applying to it as to the building model file. If so, the software compares the elevations of all points within the boundaries indicated by the uploaded terrain model with the existing terrain. The boundaries of the model are set to match the existing elevation in step 428 , and then all points within the boundaries are adjusted based on their relative coordinates using a ray-cast algorithm, in step 430 . This creates an adjusted terrain, according to the terrain model, that blends seamlessly with the existing landscape and can be used for one or multiple building models. Below is an example of an algorithm that is used in the process of FIG. 11 .
[0000]
private var maxX : float=−10000;
private var maxZ : float=−10000;
private var minX : float=10000;
private var minZ : float=10000;
private var shootHeight : float=500;
private var hitDown : RaycastHit;
private var layM = 1 << 15;
var vertices = terrainObject.GetComponent(MeshFilter).mesh.vertices;
//Sets the bounding Square of points to be used in the heightmap
for(var i = 0; i<vertices.length; i++){
var point = terrainObject.transform.TransformPoint(vertices[i]);
if(point.x > maxX){
maxX = point.x;
}
if(point.z > maxZ){
maxZ = point.z;
}
if(point.x < minX){
minX = point.x;
}
if(point.z < minZ){
minZ = point.z;
}
}
//****This algorithm loops through the terrain pieces of the parent terrain container
and alters each pieces vertice array.
//****It uses the pre-determined point bounds to alter only points within the affected
area.
//****Any point within this area is used as a reference point for shooting a line
raycast onto the imported terrain from the existing terrains reference points.
//****The hitpoint is then applied to the reference points transform essentially
mapping onto the imported terrain.
//****The newly created vertice array is then applied to the existing terrain.
for (var child in terrain.transform) {
var terrVerts : Vector3[ ] = new
Vector3[child.GetComponent(MeshFilter).mesh.vertices.length];
terrVerts = child.GetComponent(MeshFilter).mesh.vertices;
for(var q = 0; q<terrVerts.length; q++){
var terrPoint = child.transform.TransformPoint(terrVerts[q]);
if(terrPoint.x < maxX && terrPoint.x > minX && terrPoint.z <
maxZ && terrPoint.z > minZ){
if (Physics.Raycast
((terrPoint+Vector3(0,shootHeight,0)), Vector3.down, hitDown, Mathf.Infinity, layM))
{
terrVerts[q].y =
child.transform.InverseTransformPoint(hitDown.point).y−0.02;
}
}
}
//This applies the new mesh vertice array and Recalclate its Bounds
child.GetComponent(MeshFilter).mesh.vertices = terrVerts;
child.GetComponent(MeshFilter).mesh.RecalculateBounds( );
[0092] The placement of asset models occurs by two methods: placement of existing structures; and placement of proposed structures with optional terrain changes. Before an asset model can appear in the 3D component 98 it must be associated, in step 432 , with a record in the asset management system 120 . Where this record is conjoined with GIS data, the position of the model will be determined by the position (or footprint) recorded in the GIS. This is most often the case for an existing structure. These models will appear by default in the 3D component 98 , when the data is displayed, in step 434 .
[0093] Where a record does not have a corresponding GIS record, the user can enter the coordinates at which the model should appear in the 3D component 98 . The model will be placed at these coordinates according to its centroid, or pivot point, as determined by the 3D modeling software that was used to create it. The model ought to have a known origin or axes point that is positioned at its center. A rotation with respect to north should also be included. These models, most often referencing proposed structures, can be injected into the 3D component based on the role of the user and the permissions associated with the model. These proposed models may or may not be accompanied by a terrain model.
[0094] Assets may be updated via a mobile process. Based on the asset hierarchy established by the organization's data structure, assets or children of assets with corresponding system records can have these records updated through a web-enabled mobile device. A user of the system can use the mobile device to navigate to a visual representation of the object. This can be determined by the real-world location of the device or manually selected by the user. The user can select the object as it appears in the mobile 3D component 98 , access information about the asset stored in the database 28 , and even edit or update this information without directly accessing the management system.
[0095] Textures for the building models can be uploaded, too. A texture map can be uploaded as a JPG or PNG format file, for example, and may even by a photograph or photographs. If a texture map is not uploaded, a default texture will be applied, such as a concrete texture. Depending on the embodiment, there may be constraints required for texture files, such as a maximum pixel count (e.g. 2048×2048) and the pixel lengths and widths being divisible by 2.
[0096] Further Screenshots of an Exemplary Embodiment
[0097] FIG. 12 shows one of the main sections of the system 2 . At the top is a menu bar 440 that shows how a user may access the various parts of the system 2 . There are four main menu items: Map 442 ; Buildings 444 ; Admin 446 ; and About 448. According to the level of permissions set, only the items available to the user will be displayed in the menu bar. The map section 442 of the system allows users to see maps with various layers added to identify the assets recorded in the system 2 . The map screen may be the default display mode of the system 2 . The buildings section 444 allows users to see lists and details of the buildings recorded in the system's database. The admin section 446 allows an administrative user, or users with administrative permissions, to add and edit users and to assign users to roles and organizational units. The about section 448 provides access to the usual type information that would be found in such a section.
[0098] The screenshot of FIG. 12 shows a map 450 displayed by the system 2 . The map includes a scale 452 , a zoom bar 454 and navigation buttons 456 . The zoom bar 454 may be used to enlarge or shrink the detail of the map. Alternately, a user may double click on a point in the map to zoom in at that point. The navigation buttons 456 can be used to move around the map by clicking and holding one of the arrows. The navigation ring 458 may be clicked and dragged either clockwise or counterclockwise to rotate the view of the map. The home button 460 may be clicked to return the display of the map to its default position.
[0099] A tool bar 462 may be shown, including items labeled Layers 464 , Query 466 , Draw 468 and Print 470 . The view shown of the map 450 is for when the layers item 464 is selected. For example, the buildings layer is selected and displayed, causing the map to show buildings 474 for which there is a record in the system and future buildings 475 . Forested areas 476 are also shown, as well as trees 478 . To the right of the map a side bar 479 is displayed which includes a legend for the various main layers, such as imagery 480 , of the map 450 . Sub-layers may also be included, such as forested areas 482 . The side bar 479 includes check boxes 484 which allow the user to toggle the display of the relevant layer on and off. Slider bars 486 are also included, which can be used by the user to set the display opacity of the respective layer. The legend includes patterns or color boxes 488 for each of the layers, or symbols 490 . A name 492 for each pattern or symbol titles may be displayed. Advanced layer attributes may be accessed by clicking the arrow 494 to the left of the check boxes. Layers are assigned to a role before they can be accessed by users. One of the main layers may, for example, be ‘Context’ 496 . In this example it is a layer that is read from the GIS. The title, in this case ‘Context’, is set by the individual who created the layer. The user who created it intended it to reflect scale. However, it could potentially be anything that a user may want to appear on a map.
[0100] FIG. 13 shows a partial screenshot showing a query result. The query item 466 of the tool bar 462 has been selected and expanded to show various tools for making a query. In this case, the tool options are: selecting by pointing 510 to select a single object; selecting by drawing a line 512 ; selecting by enclosing map objects within a polygon 514 ; selecting objects within a rectangle 516 ; and discarding currently selected objects 518 . In the example shown, various buildings 502 , 504 are marked, and building 504 has been selected using the pointing tool 510 . Details pertaining to the selected map item or items may be shown in one or more query results boxes 519 .
[0101] FIG. 14 is a menu bar showing the draw option 468 of the tool bar 462 expanded. In this case, the tool options for drawing are: placing a point at the position of the cursor 520 ; drawing a line 522 ; drawing a polygon 524 ; drawing a rectangle 526 ; and resetting the map 528 . The draw tool allows shapes to be temporarily drawn on the map. FIG. 15 is a partial screenshot showing a feature drawn on a map, when the draw item 468 from the tool bar 462 is selected. The map shows existing sports fields 530 , with a further sports field 532 drawn over the map. The circle in the center was drawn as a polygon, although a circle draw tool may also be included.
[0102] The print option 470 from the tool bar 462 may be selected to print the screen as it is displayed on the computer in use, complete with any markups that may have been drawn on it.
[0103] FIG. 16 is a partial screenshot of a map showing a search result. The search option allows a user to search the asset database and have the results displayed in a search results window 540 . The search results window contains a list 541 of results, shown on the map as buildings 542 , 544 , 546 , 547 . Each of the results may be selected to cause it to be highlighted on the map. In this case, the result 548 has been selected highlighted as building 542 on the map. Each result in the list 541 may, when selected, or when an associated details button 549 is selected, cause the display of a details window 550 , containing information in the record about the selected building asset 542 .
[0104] FIG. 17 is a schematic representation of a screenshot of a buildings, or assets, list 551 . All assets currently accessible are displayed, but the display of assets may be restricted by permissions. The first column has details buttons 552 for accessing the information about each asset. The second column contains asset numbers 554 . The third column contains asset name and optionally its address 556 . The fourth column contains asset status information 558 , such as the date it was built and whether it is existing, under construction or proposed. A search button 560 allows users to search for buildings, and an add button 562 allows users to add proposed buildings. The search button 560 allows a user to type in a name, asset number, partial address, etc. to filter the items appearing on the buildings list screen.
[0105] FIG. 18 is a schematic representation of a screenshot of a building's detailed information page 570 . Such an information screen may be accessed from the buildings list 551 ( FIG. 17 ) by clicking on a details button 552 . Different fields 572 are visible and/or editable depending on the permissions of the user's role and the status of the building. The fields may include, for example, name, status, address, number of floors, use, green status, number, organizational unit, date built, estimated gross building area (GBA), etc. Gross building area is the sum of areas of all floors in a building, and provides another example of how users can use the system to create user-friendly names. In the information page 570 shown, a files section 573 is shown with icons or buttons 574 , 576 that link to files that have been uploaded and associated with the building. The files section 573 may be collapsed and expanded. There is an add button 578 for adding a further file, a download button 580 for downloading files or information pertaining to the building, an update button 582 and a delete button 584 . By clicking on the summary tab 586 , the user is taken back to the list 551 of buildings shown in FIG. 17 .
[0106] FIG. 19 is a schematic representation of a screenshot of a form 600 for adding a proposed (or conceptual) asset, which can be arrived at by clicking add button 562 in FIG. 17 . This detailed form allow a user to enter information in fields 602 about the proposed building. An area 604 for comments is also included. In order for the new building to be accessible in the 3D component, information about its position (Universal Transverse Mercator coordinates UTM X 606 and UTM Y 608 , height above sea level 610 ) and angle of rotation 612 with respect to a reference should be provided, as well as a model and texture. Only buildings with the status ‘Proposed’ can be added to the system.
[0107] When a proposed building has been approved for construction it is first added to the default building database and has a unique ID assigned to it. Once this has been done, the detailed building record 570 can be opened and the status of the building can be updated. This may be done using a drop down button, for example. The unique ID creates an association between the building record and its corresponding 3D model.
[0108] Once a building status is changed from ‘Proposed’ to a different status, most of the data fields will be automatically populated with the information recorded in the default building database. In order for the building to appear on the map screen, the building footprint should also be added to the appropriate layer in the GIS system 4 . In this embodiment, once the status of a building has been changed from ‘Proposed’, it cannot be reversed. The order in which the status of a building changes is: Proposed; Approved; Under Construction; and Existing.
[0109] FIG. 20 is a screenshot showing a form for editing a user's role and organizational unit within the authorization component 112 ( FIG. 4 ) of the system 2 . The authorization component provides various administrative screens. The edit user form has an area 620 for the user's personal details, such as name and email, and an area 622 for the user's position, the position being defined as a role and an organizational unit. In this example, the role is “User” and the organizational unit is “Organization A”. The role and organization unit may be deleted with the delete button 630 and new ones selected from the pull down lists 632 , 634 , and added to the user's position with the add button 636 . The user's personal details can also be updated as and when required, by entering the new information in area 620 of the form. The status of the user can be changed from active to inactive using the check box 638 . An inactive user will retain all of his assignments, but is not able to log into the system 2 .
[0110] FIG. 21 is a screenshot showing a form for adding a user. Personal details can be added in the vacant fields 640 . The role can be assigned using the drop down list 632 and the organizational unit can be selected using the drop down list 634 , both of which can be added to the user's positions 622 with the add button 636 .
[0111] FIG. 22 is a schematic representation of a screenshot of a list of permissions 650 , accessible within the authorization component 112 ( FIG. 4 ). The administrative screen includes the five sections: users 652 ; roles 654 ; organization units 656 ; permissions 658 ; and map layers 660 . Here, the permissions tab 658 has been selected. From the list 650 of permissions, some are not selected 662 and some are selected 664 , according to the role. Permissions may, for example, be selected from the following: allow users to create new assets; allow users to edit assets; allow users to delete assets; allow users to manage map layers; allow users to manage other users; allow users to manage their own password. Permissions are assigned to a role, which is then assigned to one or more users. Changing the permissions allocated to a role will affect all users that have that role assigned to them. Roles can be edited, added and deleted much in the same way that users can.
[0112] The users tab 652 provides access to a list of users recorded in the system 2 . A search function may be included to allow one to search for a user or users. Users may be deleted from the system directly from the user list.
[0113] Organization units, accessible via tab 656 , are security groups that can be used to restrict access to assets in the system 2 . For example, by default, proposed buildings are only accessible to system administrators and members of the organization unit under which they have been created. Every user in the application is assigned at least an organization unit and a role. Users can belong to more than one organizational unit, and can have different roles in each. As with users and roles, organizational units can be edited, created and deleted. It is preferable for each group responsible for submitting proposed building models to be set up as distinct organizational units
[0114] The map layers tab 660 provides access to a screen shown in FIG. 23 that allows users to add new layers from the associated GIS system 4 for display on the map screen. Layers are shown as a list 670 , each layer defined by a name 672 , a type 674 , a URL 676 and an order 678 in which it is displayed in the layer window of the map. Each layer has a check box 680 allowing a user to delete it. To add a layer it is first created as a web service in the GIS system 4 . By clicking the add layer button 682 , entry fields are displayed for the entry of details defining the new layer. New layers added by clicking the save button 684 . Likewise, layers selected for deletion can be permanently deleted.
[0115] Once a layer has been created it should be assigned to one or more roles in order to be visible. The roles tab 654 can be opened to show a list of roles. The role desired to be given access to the new map layer is selected for editing, resulting in the display of the edit role window of FIG. 24 . The name of the role is displayed in box 690 . The map layer tab 692 is selected, showing checked boxes 694 , 696 for layers that are accessible by the role and an unchecked box 698 for a layer that is not accessible to the role. By clicking on the check boxes 694 , 696 , 698 , the accessible layers can be changed and then saved by clicking the OK button 699 .
[0116] An MXD (Map Exchange Document) is a way of grouping layers, which is itself treated as a layer. We can then assign permissions to the individual layers, or to the MXD ‘master layer’. It may be necessary to create an MXD file for a group, such as utilities. When creating the MXD file, it can be created in any projection but every MXD file should have the same projection. Multiple scale levels will need to be set if the map will be cached (tiles created), otherwise the dynamic tile service may be used. The display field for each layer should be useful and unique, and can be done in the MXD file. The unique display field will be the primary display field in the system 2 . The attribute table should be reviewed to only show desired attributes, to change names to meaningful names, to check whether ID fields are correctly populated, to add a description field if required, and to check that there is a ‘last updated’ timestamp.
[0117] A dynamic or tiled service can be added to the system 2 using the server manager in the administration section. The dynamic service is a real time service driven straight from the map that can be updated quickly and easily. Tiled service is a static service of map images for various pre-set scales. A tiled service is faster in performance, but takes longer to generate if updates are required. The maximum number of instances of the service should be set to one more than the number of cores in the processor on the machine the system 2 is running on.
[0118] Further Screenshots of an Exemplary 3D Component
[0119] The 3D component 98 may be downloaded and installed separately from the core components of the system 2 . Depending on the performance specification of the computer on which the 3D component is to be run, different levels of graphics quality are offered. For example, selecting a ‘Good’ graphics quality will allow the 3D component to run smoothly on an 800×600 resolution screen if the computer has at least: Windows 7™ operating system; Intel Core 2™ or AMD Athlon™ dual core processors; 4 GB of RAM; Nvidia Geforce 9500GT™ graphics card; 512 MB graphics card memory; and 3 GB of free hard disk space. The keys used to navigate around the 3D view in the 3D component 98 may be customizable. For example, the keys could be: W—forward; S—backward; A—left; D—right; Shift—hold to increase movement speed; Tab—toggle mouse selection; and G—toggle gravity.
[0120] FIG. 25 shows a menu bar 700 with the main four components of the 3D component 98 ( FIG. 4 ). The menu items are: Information Window 702 ; Find Building 704 ; Environment 706 ; and Fetch 708 .
[0121] FIGS. 26 and 27 show screenshots with a building model present and absent, respectively, as viewed using the 3D component 98 . FIG. 26 shows a scene 710 with a 3D model of a building 712 that has been clicked on by a user. As a result of clicking on the building model 712 , a marker 714 is displayed that indicates the building model.
[0122] The information window 716 is also displayed, which contains metadata and positional information about the selected building 712 or other object. Information may include building name, address, purpose, type of construction, year and date built, height, etc. At the bottom of the information window 716 there are three buttons. The first button 720 is used to hide and show the currently selected object. The second button 722 is used to show and hide all objects of the same type. The third button 724 is used to zoom to the selected building and rotate the point of view around it. Clicking the button 724 again will stop the rotation.
[0123] FIG. 27 shows the same scene 710 as in FIG. 26 , without the building model 712 , as a result of a user clicking the button 720 or 722 . Instead of the building 712 , the footprint 726 of the building is shown.
[0124] When the user selects the find building item 704 ( FIG. 25 ) from the menu bar 700 , a building search tool is provided to the user. Users can search for a building by name or number by typing all or part of their query into the search box and clicking ‘Go’ (for example) to get a list of possible matches. By clicking on a record in the list, the 3D view zooms to the corresponding building.
[0125] The environment item 706 of the menu bar 700 allows users to toggle layers, adjust settings and conduct shadow studies. When selected, an environment settings window as shown in FIG. 28 is displayed on the screen, either beside the 3D view or overlaid on it. It may be partially transparent if overlaid. The environment setting window includes settings 728 for layers, such as layer 730 , that that can toggled on and off with buttons 732 . Layers may include trees, ortho/painted (Ortho refers to an orthophotograph, which is a geometrically corrected aerial photo that provides the image of the map. A painted ortho is a geometrically corrected aerial photo that has been artistically enhanced with a graphics editing tool—‘painted on’.), buildings, clouds, roads, road names, shadows, etc. A field of view slider 734 may be included to allow a user to adjust the angle of the field of view. A section 736 for setting the solar position may be included, which may include a slider 738 for setting the time of day, a slider 740 for setting the day of the month, and a slider 742 for setting the month of the year. A section 744 for setting user controls may be included, with a slider 746 for adjusting the mouse sensitivity and a slider 748 for adjusting the “flying speed” of the user as his point of view of the 3D scene is changed.
[0126] The fetch item 708 of the menu bar 700 will cause a window to be displayed via which all available buildings and associated terrains from the system 2 can be imported into the 3D component 98 . The buildings available to a user are those that the user has uploaded and those that have been uploaded by other members of his organizational unit. One or more of the available buildings can be selected and downloaded to the 3D component 98 , and placed in it in the desired location. A single terrain model can be used for multiple building models.
[0127] To upload a new building model to system 2 , the desired coordinates need to be known. They can be determined by going to the desired location for the building in the 3D component, selecting an existing building to be replaced, or by clicking on the ground where the new building model is to be located. The 3D component will then provide the UTM X and Y coordinates and the height above sea level, which can be transferred to a new building record in the main system 2 .
[0128] FIG. 29 is a schematic representation of a screenshot of a form 750 for creating a new building record and adding it to the system 2 , arrived at by clicking the add button 562 of FIG. 17 . The form 750 includes: an area 752 for the building name; a drop down selection list 754 for setting the status of the building; an area 756 for the address and details such as the number of floors and whether there is underground parking; an area 758 for further building details such as number, designer name, year built, whether heritage or not, building visitors, drawing revision date, green status, etc; an area 760 for building dimensions; an area 762 for comments; and an area 766 for geographic coordinates and rotation expressed as an angle from north. There may also be a drop down list for setting the organizational unit. Once the details of the building have been entered, a model for the building can be selected by clicking the model button 768 , which will lead the user to a list of available models that can be selected. Similarly, a texture for the building model can be selected by clicking on the texture button 770 . The choices made can then be saved and uploaded by clicking button 772 , or canceled by clicking on button 774 .
[0129] FIGS. 30 and 31 respectively show screenshots of a view with underground detail hidden and displayed. FIG. 30 shows a building such as a hospital 800 , with pillars 802 at its entrance and a road 804 . In the background there is a smaller building 806 and trees 808 . In FIG. 31 , some of the layers have been removed to reveal the footprint 810 of the hospital 800 and underground pipes 812 . The smaller building 806 and pillars 802 are still visible.
[0130] General Information and Variations
[0131] The system 2 allows: ease of management of all electronic assets; enterprise-wide dissemination of relevant data; access to 2D, 3D, tabular, and spatial data from a centralized location; access via mobile devices; access independently of platform; extendable cost recovery via the ability to support resalable data subsets, with extended functionality, via consumables such as mobile applications; the aggregation of electronic information from other data sets via web services; and an excellent level of security.
[0132] The system 2 may reside on a virtual machine infrastructure. This approach provides maximum flexibility in deployment options, as well as the ability to upgrade the hardware platform with minimal impact. Testing, development, and backup are improved by working with systems that are easily replicated and can support parallel operations. Virtualization also lowers the system's total cost of ownership because hardware used for virtual servers can support many systems with different peak load times, allowing a more powerful, fault-tolerant set of hardware to be shared by many applications. In addition, using virtual machines allows the use of processing clusters to help manage demand if the system use expands.
[0133] The overall architecture may be three-tier, these being the client, or user interface, the middleware and the data layers. The server-side architecture may, for example, include a Windows™ server running Internet Information Server™ (IIS), and the .NET Framework™, which is included in all recent versions of the Windows™ operating system. The foundational application may be built primarily in ASP.NET™ using C#, and rendered as HTML, CSS, and JavaScript™ for the web browser. It may use an ESRI ArcGIS™ server. Scripting and configuration may by enabled with XML and/or Python™. Data input forms follow a specification that allow them to be easily integrated with client installations. This approach allows scalability and flexibility to creating end-user applications.
[0134] The software solution operates internally on ODBC-compatible relational databases, and can access and update multiple internal and external data sources. As appropriate, existing databases will be accessed, and new tables created to support any enhanced functions.
[0135] A common web browser and a Unity3D™ graphics engine is the only software required on the users' computers to run the primary functions, minimizing the level of effort to deploy the system to a wide range of users. The system may be loaded by typing in the web address of the application.
[0136] A client information module may be included that allows clients to login through a secure portal, and view information, lists and forms relevant to their sites, buildings, and assets. It may also store, and display, key building data from third-party BIM systems (such as FM Systems™, Tririga™, Archibus™, etc.), and stores, and display schematics. It may provide document management of a library of all related materials, and file management for access to Revit™ drawings that may be viewed online.
[0137] A client compliance monitoring module may allow users to access, maintain, and be notified of key compliance information on their assets, buildings, or sites. It may include a calendar of key dates for each asset such as lease expiry, insurance renewal, capital maintenance and amortization.
[0138] The 3D visualization component 98 may be deployed over the web. However, for maximum performance it is preferably run as a stand-alone application with all of the spatial functions ported into an extensively augmented 3D rendering engine. This enables the highest level of mesh and polygon count with maximum performance gained through compression such as view frustum, back face contribution and occlusion culling. Changes of buildings in Revit™ are reflected in the site model.
[0139] When using mobile devices to access the system 2 , field personnel can add geographically tagged data to the system for future action.
[0140] Modules, components, features etc. of the architecture and/or framework may be grouped differently to the embodiments shown herein. Some may be omitted, and others added. The system may be embodied on multiple servers. Databases may be embodied on one or multiple servers. Databases may be split into multiple constituent databases. Different file types may be used. Different algorithms may be used where appropriate. Different selection, query or drawing tools may be used. Other rules about how the system operates may be incorporated, and different constraints and limits may be employed. Different permissions may be added. Assets may be monitored with respect to time. Where named software applications have been mentioned, others with equivalent relevant functionality may be substituted. As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the scope thereof. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
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A geographic asset management system, in which assets such as buildings, permits and grants are tagged with geographical locations for display on a geographical information subsystem forming a component of the system. In an asset management subsystem, assets may be selected, analyzed or edited according to a user's permission level. Physical assets may be represented as 3D models which may be selected, or of which parts may be selected, in order to provide further information. The geographic relationship between multiple assets is easily visualized. Assets may be stored in relation to time and/or date, and the system is able to retrieve and display asset data in a historical and geographical sense. Scenarios involving changing assets and proposing new assets may be played out by users. Notifications based on the assets may be automatically triggered and sent to users.
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BACKGROUND OF THE INVENTION
The invention relates to a pattern setting arrangement of a knitting machine having a needle bed and a carriage passable over the needle bed, at least one pattern drum carried by the carriage and a plurality of rocking sinkers and directly or indirectly associated needles movably mounted in channels in the needle bed, the position of the rocking sinkers being determined by pressure bars selectable by the pattern drum and operating on feet on rear lever arms of the respective rocking sinkers.
With such pattern setting arrangements the choice of the needles occurs in that the pressure bars are controlled through pattern cams formed in accordance with the pattern and arranged on the periphery of the pattern drum. The pressure bars then select pattern sinkers by way of the rocking sinkers which, for their part, select the needles then actuated by cams on the carriage.
One such pattern device is, for example, shown in German Pat. Specification No. 1 922 289. In this known pattern device springs are located under the rocking sinkers and always hold these in their upper position. In this case needle beds with very deep slits are necessary which must often be manufactured in several parts. As a result of the pressure exerted by the springs it is also not possible to make use of pressure bars which are located very close to each other and, therefore, are very slender and to apply pressure directly on the feet of the rocking sinkers. Such slender pressure bars would give sideways so that there would be many failures.
Pattern devices are also known in which the rocking sinkers are journalled in the needle channels without the use of springs and are held in the needle channels with some degree of position stability by an interference fit. Rocking sinkers built in this way can only be formed with few feet so that a distinct limitation of the pattern possibilities results. If these rocking sinkers are, on the other hand, selected by electrically controlled pressure bars, then the knitting speed is severely restricted. Further the rocking sinkers of this known pattern device must be continuously brought out of their working position into their normal position by pressure applied on their shorter forward lever arms. This in turn means that the rear lever arm, on which the feet are arranged for selection, can not be made as long as desired since the friction load with a large lever ratio can only be overcome with very high specific pressure.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a pattern setting arrangement of the afore-described type with which it is possible to provide a unitary needle bed for the needles and rocking sinkers with relatively shallow needle canals and which renders possible an unlimited, simple and sure selection and actuation of the rocking sinkers selected in accordance with the pattern.
In accordance with the present invention additional feet are provided on the free ends of the rear lever arms and extend longitudinally of the needles and out of the channels in the needle bed and cam element means mounted on the carriage have a portion thereof engageable with the said additional feet of selected ones of the rocking sinkers upon passage of the carriage over the needle bed for pressing said rear lever arms of said selected ones of the rocking sinkers into their respective channels in the needle bed into first, working, positions of the rocking sinkers.
Preferably said cam element means has further portions thereof for engaging said additional feet for holding said selected rocking sinkers in their working positions during a knitting cycle, and preferably also said cam element means has further portions thereof for engaging said additional feet for returning the rocking sinkers to their normal non-working positions at the end of the knitting cycle.
With this arrangement the rocking sinkers are selected in accordance with the pattern and brought into a position in which they can be contacted by the single cam element of the carriage, brought into their working position and held there. After the release of the additional foot of the rocking sinker from the engagement with the one portion of the cam element a further portion of the cam element engages the additional foot of the rocking sinker and presses this back into its normal position.
Advantageously a hook means extending into the needle channel is provided on the rear lever arm of the rocking sinker. This hook holds the rocking sinker against rotation in the needle channel.
Advantageously the hook means is bent out of the horizontal plane of the rocking sinker. Thereby it restrains the rocking sinker in the needle channel and holds the rocking sinker position stable at least in its upper position or normal position.
Further the needle bed advantageously includes a recess running along the needle bed on its underside in the region of the hook means.
With this it is ensured that the hook means can swing freely downwardly without having to form in the needle bed a transverse groove which is difficult to manufacture.
Usefully, a nose is provided on the forward lever arm of the rocking sinker as abutment means for the associated needle or pattern sinker.
Furthermore the rocking sinker is advantageously provided at its pivot point with a protrusion located in a longitudinal groove in the needle bed, while a cover plate is provided over this pivot point. In this way the pivot point of the rocking sinker is fixed in a definite and simple way.
A useful further development of the invention consists in that an upstanding lever arm is formed integrally at one end of the pressure bar and lies laterally against a pattern cam of the pattern drum. In this way the selection drum with its bearings does not have to be moved. The lever arm of the pressure bar preferably lies against the cam under the action of a spring.
In order to hold the pressure bar securely in its position after selection through the pattern drum, there is usefully provided a device for holding the pressure bar in its working position. This device is advantageously a safety catch which comes into engagement with a protrusion on the free end of the pressure bar.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic cross section through a part of a needle bed of a presently preferred embodiment of a knitting machine with a rocking sinker for selection in accordance with the pattern in its normal position,
FIG. 2 is a cross section as in FIG. 1 in which the rocking sinker is however pressed down by a pressure bar and the associated pattern sinker is lifted up partly out of the needle channel,
FIG. 3 is a cross section as in FIG. 1 in which however the rocking sinker is held in its working position by a cam element and the pattern sinker is raised into its working position and held there,
FIG. 4 is a plan view on the rear side of the needle bed of FIG. 1 together with a schematically illustrated carriage showing the cam together with the pattern drum and the orientation of the feet of the rocking sinkers on insertion of the pressure bar, and
FIG. 5 is a plan view as in FIG. 4 however with the pressure bar not inserted.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIGS. 1 to 3 a needle bed 2 is shown in cross section so that a needle channel 1 is clearly to be recognised. A needle 3 is slidably located in the needle channel 1 and has a foot 4 extending up out of the needle bed 2 so that it can be engaged by parts of a cam moved over the needle bed 2. In the needle channel 1 there is also slidably and pivotably mounted a pattern sinker 5 whose foot 6 can extend up out of the needle bed 2 or sink into the needle bed 2 in accordance with the position of the pattern sinker 5. FIG. 1 shows the foot 6 in its position fully sunk into the needle bed.
The pattern sinker 5 is so shaped that it can slide with a forward shank 7 on the floor 8 of the needle channel and that there is room in the channel for a shank 10 of a forward lever arm 11 of a rocking sinker 12 together with a rear shank 9 of the pattern sinker. In addition, a nose 13 is provided on the forward lever arm 11 of the rocking sinker 12 which serves as an abutment for the pattern sinker 5.
The rocking sinker 12 has a protrusion 14 in the region of its pivot point by which it is located in a groove in the needle bed 2. A cover piece 15 covers over and locates the rocking sinker in the region of its pivot point.
The plurality of rocking sinkers have respective rear lever arms on which are provided upstanding feet 17, 17' and 17" spaced with respect to the associated pivot points. The feet 17, 17', 17" of the adjacent rocking sinkers are arranged in staggered form with different spacing from the pivot points.
The rocking sinker 12 has a rear lever arm 16 on which the foot 17 is located at the rearmost end of the rearward lever arm 16.
The rearward lever arm 16 of the rocking sinker 12 is so shaped that it terminates in a turn-under hook 18 which ensures that the rocking sinker 12 cannot rock sideways under sideways pressure. A recess 19 is provided on the underside of the needle bed 2 in the region of the hook 18 in which the hook 18 can move freely if the rocking sinker 12 is pushed out of its normal position shown in FIG. 1 into its working position (FIGS. 2 and 3). Furthermore the rearward lever arm 16 with its hook 18 is so bent and formed that it is an interference fit in the needle channel and a frictional braking effect or restraint exists in the needle channel which holds the rocking sinker 12 stable in each pivoted position.
At the rearward end of the rearward lever arm 16 of the pivoting sinker 12 there is provided a foot 20 extending longitudinally or rearwardly out of the needle bed 2. Pressure bars 21 run over the feet 17, 17', 17" extending upwardly out of the needle bed and these are so selected in accordance with the pattern that, in the course of a pass, they either press the associated foot 17, 17' or 17" hard to the upper face 22 of the needle bed or slide over the associated foot.
Now should the pressure bar 21 press the associated foot 17 of the rocking sinker 12 downwardly, then the rocking sinker 12 swings about its pivot point defined by the protrusion 14 and lifts or swings, with its forward shank 10, the pattern sinker 5, which is uncovered by a cam part 23 on the passage of the carriage, so far that its foot 6 extends half out of the needle bed. Furthermore, the foot 20 of the rocking sinker 12 is swung so far downwardly that it can be engaged by a cam element 24. This cam element 24 on the cam carriage now swings the rocking sinker 12 so far that its shank 20 stands with a slope 25 parallel to the upper surface 22 of the needle bed. Meanwhile the pattern sinker 5 is swung so far that its foot 6 extends wholly out of the needle bed 2 and can therefore be engaged by an associated part of the cam. This position, in which the under edge of the shank 9 of the pattern sinker 5 can slide on the slope 25 of the rocking sinker 12 is illustrated in FIG. 3. A pattern sinker can thus be presented in accordance with the pattern to a cam (not illustrated) and moved by this. In this movement they then bring the needles 3 or their feet 4 in the engagement zone of the knitting lock (equally not illustrated).
In FIGS. 4 and 5 the cam element 24 can clearly be recognised in its outward pass in the direction of movement of the carriage. The rocking sinkers are held in a stable position by means of the cam element 24 engaging their feet extending rearwardly out of the needle bed as long as the pattern sinkers 5 function by reason of their associated cam. Thereafter the rocking sinkers are lifted again into their normal position through the lock elements 26 which engage on the underside of the rearwardly extending feet of the rocking sinkers.
The pressure bars are pivotally mounted about a pivot point 27 on the carriage (not illustrated) and each have a lever arm 31 which is pressed by means of a spring 28 against a pattern drum 29 on the carriage having pattern cams 30. The pattern cams 30 are shaped in accordance with the pattern and allow the lever arm 31 of a pressure bar in one case to lie through its contact face 32 against the tooth 33 of a pattern cam 30, whereby the pressure bar is held in its non-working position as shown in FIG. 5. If the tooth 33 is, on the other hand, broken away in accordance with the pattern, then the lever arm 31 comes by way of its contact face 32 into contact with the bar of the pattern cam 30 as is shown in FIG. 4. In this position the pressure bar 21, for example, is held fast by a safety catch 34 on a protrusion 35 and, during the passage over the needle bed, presses, by its slope 36, the foot 17 of the rocking sinker 12 so far into the needle bed 2 that the cam element 24 can engage the foot 20 of the rocking sinker 12 extending rearwardly out of the needle bed.
The cam element 24 has, in the illustrated example, a slope for engaging the rearwardly extending feet of selected rocking sinkers in both running directions. Furthermore there is provided, on both sides of the lock element 24, a respective cam element 26 for the return pressure of the rocking sinkers into their normal position so that these cam elements can also work during a movement of the carriage in both directions. It is understood that the pressure bars must also include a slope corresponding to the slope 36 on both sides in order to be able to bring the rearwardly extending feet into the region where they can be engaged by the cam element 24 in both directions of passage of the carriage.
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Needles in knitting machines are selected for pattern purposes by a lever system operated by a pattern drum mounted on a carriage passable to and fro over the needle bed. The lever system incorporates locking-sinkers provided with contact feet in staggered relationship so that different force requirements apply to different ones of the rocking sinkers. The present invention provides an additional foot on the end of each rocking sinker and a cam element on the carriage to engage the said additional feet of the rocking sinkers selected by the pattern drum fully to depress the selected rocking sinkers whereby to ensure actuation of the selected needles.
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[0001] This application is a continuation-in-part of U.S. application Ser. No. 13/066,573 filed Apr. 18, 2011. The patent application identified above is incorporated herein by reference in its entirety to provide continuity of disclosure.
BACKGROUND OF THE INVENTION
[0002] The present invention is a cap and a tube for high volume dental suction. One end of the tube is designed to fit the cap.
[0003] High volume evacuation (HVE) suction devices are used during dental procedures to remove saliva and particles, such as plaque, calculus, parts of existing fillings and decayed tooth material. Such HVE suction devices include a suction tube having a distal (upper) suction end and a proximal (lower) discharge end. The discharge end of the suction tube connected via a hose and hose valve to a vacuum source. The distal (upper) end of the suction tube is inserted into a patient's mouth.
[0004] The HVE suction tube is typically made of polyvinyl chloride or polyethylene. Such tips are hard and the edges rather sharp, which can irritate the tissue of a patient's mouth.
[0005] The suction draws material into the opening and down the tube. If the tip contacts the patient's mouth tissue, it can suck the tissue into the tip, obstructing the suction. This is uncomfortable and can cause damage to the patient's mouth and make it more difficult for the dental user. Such HVE suction tubes can require constant manual adjustments to maintain efficient suction while in use and cause unpleasant sensations, bruising and anxiety to patients.
SUMMARY OF INVENTION
[0006] The present invention provides a protective suction cap and the specially designed HVE tube onto which it fits; the invention overcomes the aforementioned difficulties with existing HVE suction tubes.
[0007] The HVE tube of the invention includes a tube having a suction end and a discharge end and which can be used with or without the protective cap attached.
[0008] The invention can also be produced as one piece, with the cap permanently attached to the HVE tube. In a one-piece embodiment, the entire tube and cap may be molded from a plastic material that is resilient or semi-resilient, such as polyethylene.
[0009] The cap provides a gap between the suction end of the HVE tube and the oral tissue to simultaneously allow tissue retraction and suction in the working area of an oral cavity without causing trauma to fragile tissue.
[0010] A dental suction tube including at a distal end a cage-like structure comprising at least four vanes, each vane having a question-mark-like shape with a generally straight proximal section and a curved distal section, the straight section proximal end supported on the end of the dental suction tube and the distal ends of the curved sections of each vane attached to one another.
[0011] A high-volume evacuation tube used in dental procedures including a cap, the cap comprising a crown-shape, cage-like structure including at least three struts, each strut having a generally convex shape, the proximal end of each strut attached to the distal end of the tube and the distal ends of the struts attached to one another. In another embodiment the cap may have three convex curved arms connected at proximal ends to the tube and the distal ends to one another such that the cross-sectional area between the curved arms is greater than the tube cross-sectional area.
[0012] A dental suction tube including at a distal end a cruciate structure comprising two orthogonal cross members, the suction tube distal end edge formed at an acute angle to the longitudinal axis of the tube, the cruciate structure lying substantially in a plane parallel to the distal end edge, each of the cross members extending radially beyond the edge of the tube distal end edge, the radial portion beyond the edge of the tube distal end edge having a round shape, the edge of each round shape of the cross members attached to the two distal end openings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a right side view of the crown-shaped cap;
[0014] FIG. 2 is a right side view of the HVE suction tube of the present invention specially designed to fit onto the crown shaped cap by pressing the cap into the suction end of the HVE tube;
[0015] FIG. 3 is a perspective view of the HVE suction tube with crown shaped tip permanently attached on the suction end as one piece;
[0016] FIG. 3A is a close-up view of FIG. 3 ;
[0017] FIG. 4 is another embodiment of the invention showing an alternative cap construction comprising a cruciate structure;
[0018] FIG. 5 is a first side elevation view of the embodiment shown in FIG. 4 ;
[0019] FIG. 6 is a front elevation view of the embodiment shown in FIG. 4 ;
[0020] FIG. 7 is a rear elevation view of the embodiment shown in FIG. 4 ;
[0021] FIG. 8 is a second side elevation view of the embodiment shown in FIG. 4 ;
[0022] FIG. 9 is a top plan view of the embodiment shown in FIG. 4 ;
[0023] FIG. 10 is a bottom end view of the embodiment shown in FIG. 4 ;
[0024] FIG. 11 is a perspective view of a third embodiment of the invention; and
[0025] FIG. 12 is a side elevation view of the embodiment shown in FIG. 11 .
DETAILED DESCRIPTION OF THE INVENTION
[0026] The present invention in the embodiments shown in the drawings dudes an HVE suction tube 1 having a suction or distal end 1 a (see FIG. 3 ), and a discharge or proximal end 1 b , the end 1 b attached to flexible tubing that attaches to the source of suction. The distal end of the tube has a crown-shaped, cage-like cap or structure 2 . The cap-like structure may be detachably connected to tube 1 at the distal end 1 a as shown best in FIG. 1 . Alternatively, in the embodiment shown best in FIGS. 3 and 3A , the cage-like structure may be integral with the tube 1 , the tube and cap-like structure molded of plastic material such as polyvinyl fluoride or polyethylene, materials well known in the field of dentistry. The tube 1 typically has a length of 4-6 inches and an internal diameter of approximately ¼ inch with a wall thickness of approximately 1/32 inch. The distal end of tube 1 , as seen best in FIGS. 1 and 2 , is terminated to form an edge 1 c in a plane that is acute to the longitudinal axis of the tube 1 . As shown in FIG. 2 , the edge may have steps with corresponding and complementary steps formed in the short attachment section 2 g of the cage-like structure 2 to provide a secure support for the cap 2 on tube 1 .
[0027] The cage-like structure or cap 2 as noted above has a short tubular section indicated at 2 g fitted within the end of tube 1 in frictional engagement therewith. The cage-like structure 2 comprises in the embodiment shown four vanes or struts indicated at 2 a , 2 b , 2 d , and 2 e , although three vanes or struts may be employed depending on the plastic material chosen for forming the cap.
[0028] Each of the vanes or struts 2 a , 2 b , 2 d , 2 e has a question-mark shape which include a short straight or slightly curved proximal section 2 h and curved convex distal section. The proximal end of the proximal sections are attached to and may be integral with the ring portion 2 g of the cap-like structure 2 that attaches to the distal end 1 a of tube 1 as shown in FIG. 1 or at the tube edge as seen best in FIG. 3A . At the distal end of each distal section 2 a , 2 b , 2 d and 2 e , of the vanes or struts the ends are attached to the corresponding end of each of the other vanes or struts at 2 c . It will be understood that each of the vanes may be molded in plastic as an integral structure. Each of the vanes may have a circular cross section as shown in FIG. 1 or a polygonal cross section as shown in FIG. 3A .
[0029] The vanes or struts of the cage-like structure or cap 2 have a diameter, as measured in a plane that is transverse to the axis of the tube that is greater than the inner diameter and/or outer diameter of tube 1 . The cap-like structure or cap 2 extends axially or longitudinally from the distal end 1 a of the tube 1 a distance greater than the inner or outer diameter of tube 1 .
[0030] It will therefore be seen that the area as measured between each pair of vanes or struts, in the aggregate, is greater than the cross-sectional area of tube 1 . It will also be appreciated that the cage-like structure is slightly resilient such that when inserted into the patient's mouth, it may distort slightly but will prevent the oral tissue from blocking the distal open end of tube 1 or from being aggravated. The area is thus large enough for suction uptake of larger particles that may be generated during dental processes.
[0031] In operation, the distal end of the tube 1 with the cage-like cap 2 is inserted into the patient's mouth such that the cap is in contact with the patient's oral tissue. When suction is applied, the cap 2 will prevent or minimize any plugging of the end of the suction tube by tissue while still allowing suction to remove the unwanted materials from the oral cavity. The cap 2 thus eliminates the danger of the tissue being grabbed or forcibly pressed against the end of the tube which is frequent with existing dental suction tubes commonly used in dental practices today.
[0032] The embodiment shown in FIGS. 4-10 illustrates a tube, indicated at 51 that is substantially the same as tube 1 in the earlier embodiments. The tube has a cap indicated at 52 that may be integral with tube 51 or detachable (not shown). Cap 52 is positioned at the distal end 61 and comprises a cruciate structure indicated generally at 53 comprising two orthogonal cross members, struts, or arms 54 , 55 . The members 54 , 55 are arranged orthogonally to one another and connected at their central portions to one another.
[0033] Tube 51 has a proximal end that is attached to a vacuum source through flexible tubing and a valve in a manner ell known to those having ordinary skill in the art. The distal end 61 is terminated at an acute angle to the longitudinal axis of tube 51 as seen best in FIGS. 5 and 8 . The distal end 61 , which may be at an angle of 45 degrees, or less, defines a distal end edge 62 as seen best in FIGS. 6 and 9 . In the embodiment shown in FIGS. 4-10 , the distal tip of the distal end 61 may be cut off or straight at 60 . The structure 53 cross members, arms or struts lie in a plane that is substantially parallel to the plane of distal end edge 62 . Each of the cross members, arms or struts in this embodiment, include a central straight portion 57 on strut 54 and a straight portion 58 on arm or member 55 . Arms or members 54 , 55 have at each opposite end of the central portions 57 , 58 curved or rounded portions as seen at 59 . As seen best in FIGS. 5 , 6 and 9 , 10 the round portions of the arms or members 54 , 55 extend radially outwardly or beyond the cylindrical edge 62 of distal end portion 61 of tube 51 .
[0034] It will be appreciated by those of ordinary skill in the art that the rounded ends of the cross members or arms 54 , 55 will provide a surface that is in contact with the tissue in the oral cavity of the patient but because of the shape will not cause irritation or discomfort. Moreover, the cruciate shape of the cap will prevent the tissue in the patient's mouth from clogging or adhering to the open end of the tube 51 thereby assuring that particles or other detritus to be removed is not impeded. It will also be seen, for example from FIG. 5 , that the central portion 57 of arm 54 is spaced from the plane of the edge 62 of distal end 61 of tube 51 . It should also be noted that the acute angle of the distal end 61 of tube 51 creates a cross-sectional area that is greater than the transverse cross-sectional area of the tube 51 thereby assuring that the area at the distal end 61 of the tube, notwithstanding the presence of the cross members or arms 54 , 55 will not restrict the cross-sectional area of the tube 51 and cap 52 thereby retaining the complete suction (negative) pressure by not restricting the flow area.
[0035] In another embodiment shown in FIGS. 11 and 12 , the cruciate end cap structure 72 of tube 71 also comprises cross members, arms or struts 73 , 74 . Cross member 74 comprises two segments or bars 75 , 76 connected at the intersection with the second cross member 73 , one segment 75 comprising a straight bar lying in the plane parallel to the distal end edge and the other end segment bar 76 lying at an obtuse angle thereto as seen in FIG. 12 . Accordingly, at the intersection of the segment 75 , 76 , there is an apex 77 that assists in holding the tissue of the patient's mouth away from the distal end of the tube so as to prevent clogging or plugging injury due to the patient's tongue, cheek or lips while still allowing suction of larger particles.
[0036] The foregoing description is provided to enable any person skilled in the relevant art to practice the various embodiments described herein. Thus, the claims are not intended to be limited to the embodiments shown and described herein, but are to be accorded the full scope consistent with the language of the claims, wherein reference to an element in the singular is not intended to mean “one and only one” unless specifically stated, but rather “one or more.” All structural and functional equivalents to the elements of the various embodiments described in this disclosure that are known or may become known to those of ordinary skill in the art are expressly incorporated herein by reference and intended to be encompassed by the claims. Nothing disclosed in this application is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.
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A high volume suction tube for use in dentistry to remove detritus during oral procedures, such as providing a tooth filling, including a cap that alleviates tissue obstruction without impeding efficient suction and removal of the detritus.
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TECHNICAL FIELD
The present invention pertains in general to stage lighting and in particular to such lighting which involves the projection of a silhouette of an image on a stage, screen or backdrop.
BACKGROUND OF THE INVENTION
There are many aspects to providing stage lighting. These include spotlights, flood lights, colors and moving lights. A significant aspect of such stage lighting is the projection of images, in the form of a silhouette, onto the stage to a backdrop, a screen or the performers themselves. The conventional light pattern generator for projecting such a silhouette image is termed a "gobo". The typical gobo is made of a sheet of metal which has the desired image cut in the sheet as an opening for shaping a light beam. The metal sheet, with the cut-out image, is placed in the beam from a spotlight so that the portion of the beam that passes through the sheet is shaped to correspond to the image cut in the gobo. The image is typically passed through a lens so that the image can be focused on a desired portion of the stage.
The gobo is mounted directly in the beam of light. Since stage lighting uses intense light beams, the gobo can become very hot. In fact, it is not unusual for a gobo to become so hot that it begins to glow with a cherry red color. To combat the extremely high heat, gobos have been fabricated of heat resistant metals, such as stainless steel. However, even gobos made of this material have a relative short lifetime and require frequent replacement.
The conventional gobo is also limited as to the configurations that can be produced. Since all of the metal elements of a gobo must be supported, there must often be unwanted support members included in the design. As an example, it is impossible to produce a complete ring design because support members must extend from the exterior to support the interior metal.
Therefore, in view of the need for the projection of images as a part of stage lighting and the short lifetime of conventional gobo image producers, as well as the limitations on designs, there exists a need for an improved light pattern generator which can project a desired image, while at the same time withstanding the high temperatures present within a light fixture.
SUMMARY OF THE INVENTION
A selected embodiment of the present invention comprises a light pattern generator for producing an image in a light beam. The generator includes a transparent plate for placement in the light beam. A light reflective layer is bonded to a surface of the plate with the reflective layer having an opening which is in the shape of the image. A portion of the light beam passes through the opening to produce a beam having the shape of the image. The reflective layer serves to reflect a portion of the light beam which does not pass through the opening.
A further aspect of the present invention comprises the addition of a nonreflective layer to the opposite side of the reflective layer from the source of light. The nonreflective layer likewise has an opening corresponding to the shape of the image. The openings in the two layers are aligned. The nonreflective layer serves to absorb any extraneous light, such as light reflected from the lens that serves to focus the shaped beam.
A still further aspect of the present invention comprises a lighting fixture which includes a light source, a transparent plate having a reflective surface and a lens for focusing a beam. The reflective surface is provided with an opening for passing a portion of the light beam through the opening to produce a beam having the shape of the desired image. The reflecting layer serves to reflect unwanted light from the beam away from the plate. The resulting image produced by the beam is focused by the lens.
BRIEF DESCRIPTION OF THE DRAWINGS
For a complete understanding of the present invention and the advantages thereof, reference is now made to the following Detailed Description taken in conjunction with the accompanying Drawings, in which:
FIG. 1 is a perspective illustration of a lamp fixture having a light source, a light pattern generator and a lens for producing a beam having a desired image shape,
FIG. 2 is a light pattern generator, as shown in FIG. 1, which has a desired image formed by layers on the surface thereof, and
FIG. 3 is a sectional view of the light pattern generator shown in FIG. 2 together with ray lines which illustrate the transmission, reflection and absorption of light by the light pattern generator.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1, there is illustrated a light fixture 10 which can be used for the purpose of stage lighting. The fixture 10 has a housing 12 which serves to support and enclose the components of the fixture. Within the housing 12, the fixture 10 has a light assembly 14 which comprises a reflector 16 and a bulb 18. This assembly produces a collimated light beam 20 which is transmitted to a lens 22 which serves to focus the beam.
A pattern wheel 24 is mounted for rotation by a stepper motor 26. Around the periphery of the pattern wheel 24 there are provided a plurality of light pattern generators, such as 28. In the disclosed embodiment each of the generators 28 has a trapezoidal shape to form, as a group, a concentric ring about the periphery of the pattern wheel 24. The details of the pattern wheel 24 are further described in copending application Ser. No. 863,440 filed May 15, 1986 by James W. Bornhorst. The generator 28 is provided with a transparent opening 30 which is in the shape of a desired image that is to be projected toward the stage. The pattern wheel 24 can be provided with a plurality of light pattern generators, such as 28 and it can be provided with color filters for producing different colors for the light beam produced by the fixture 10. Any one of the desired images or colors can be rotated by the motor 26 such that the appropriate color filter or light pattern generator is positioned within the light beam.
The light beam is focused by the lens 22 such that it is sufficiently small to pass through the light pattern generator 28. The beam then expands and is passed through a lens 32. The lens 32 serves to provide focusing for the beam and makes the beam essentially colinear. If necessary, the lens 32 can be moved forward or backward in the fixture 10 to focus the image produced by the beam at any desired distance.
The light beam which passes through the lens 32 is directed onto a stage to produce an image 34 which is in the shape of the opening 30 in the light pattern generator 28. The disclosed embodiment shows the opening 30 to be in the shape of a 5-point star which in turn produces an image 34 which has a corresponding star shape.
The light pattern generator 28 is further illustrated in FIGS. 2 and 3. As noted above, the generator 28 has a trapezoidal shape so that a plurality of such generators, and corresponding color filters, can be placed edge to edge about the periphery of a pattern wheel 24 so that there is neither blocking of light nor the escape of white light between adjacent pattern generators or color filters. The pattern generator 28 comprises a transparent plate 40 which has bonded to one surface a reflective layer 42, which is positioned on the surface of the pattern generator 28 opposite from the light assembly 14. The reflective layer 42 has a mirror finish for reflecting light which strikes the layer. Facing in the direction opposite from the mirror surface of the reflective layer 42 there is provided a nonreflective layer 44 which serves to absorb light which strikes the layer. The layers 42 and 44 are provided with the opening 30 which is in the shape of the desired image. The opening 30 extends through the layers 42 and 44, but does not extend through the transparent plate 40.
The light pattern generator 28 is shown in a section view in FIG. 3. The lenses 22 and 32 are further shown in FIG. 3 together with various light rays which illustrate the transmission, reflection and absorption of the various portions of the light beam 20 which is produced by the light assembly 14. As noted above, the light pattern generator 28 comprises a transparent plate 40 which has a reflective layer 42 bonded to the surface thereof on the opposite side from the lens 18. The surface of the layer 42 facing the lens 18 is a mirror surface which reflects the light that strikes the surface. The layer 44 is bonded to the surface of the layer 42 and has an exposed surface which faces the lens 32. The exposed surface of the layer 44 is light absorbent and is therefore nonreflective. The opening 30 extends through both of the layers 42 and 44 and permits light to pass unimpeded through the generator 28. The beam which passes through the light generator 28 is conformed to the shape of the opening 30.
The light pattern generator shown in FIG. 2 has a trapezoidal shape. For the disclosed embodiment, the base length is 0.8 inch, the sides are 1.5 inches and the top is 1.75 inches. The plate 40 has a preferred thickness of 0.04 inch.
Operation of the light pattern generator 28 is now further described in reference to FIG. 3. The light beam 20 is focused to a smaller diameter by the lens 22 at the region of the light pattern generator 28. Portions 46 of the light beam 20 are reflected by the mirror surface of layer 42 away from the pattern generator 28. Portion 48 of light beam 20 passes through the opening 30 and is in the shape of the opening 30. The portion 48 of the beam 20 is directed to the lens 32 and refocused to be an essentially collimated beam which produces the image 34 at the desired location on the stage. Portions 50 of the light beam 20 are reflected back from the lens 32 as well as from the interior surfaces of the housing 12. The portions 50 which strike the nonreflective layer 44 are absorbed in the surface of layer 44. Should the portions 50 be allowed to reflect back from the light pattern generator 28 into the lens 32, these portions of light would produce spurious images would interfere with the desired image 34. Therefore, the light reflected within the housing between the light pattern generator 28 and 32 is absorbed at the surface of layer 44 to prevent the directing of any interferring light rays through the lens 32 toward the image 34. Should any portion of the extraneous light between the light pattern generator 28 and the lens 32 be directed through the opening 30, it will be either dissipated in the housing 12 or redirected through the opening 30 in the correct shape of the beam.
The method of manufacturing the light pattern generator 28 is now described in reference to FIG. 3. The process begins with a large sheet of the transparent plate 40. The plate 40 is preferably made of PYREX glass with a thickness of 0.04 inch. On one surface of the plate 40 there is deposited a layer of positive photo resist which is in the shape of the desired image. On the surface of the plate and the photo resist layer there is then deposited a layer of aluminum having a thickness of approximately 2,000 Angstroms. There is then deposited on the surface of the aluminum a multilayer dielectric coating which comprises a plurality of layers which together have a thickness of approximately 2,000 Angstroms. The multilayer dielectric coating consists of alternating high and low index of refraction materials which form an interference filter that functions as a "black mirror", which is a nonreflective surface that absorbs light. Examples of materials that have the high and low indexes of refraction are magnesium flouride and zinc sulfide. The plate with the various coatings is then exposed to acetone which dissolves the photo resist and lifts all the layers of material which were deposited immediately over the photo resist. The acetone has no effect on the glass. As a result, there is produced an opening through the deposited layers which is in the desired shape of the image.
This process is carried out concurrently on a large sheet of the material which comprises plate 40. Lines are scribed across the glass sheet which includes the plate 40. The sheet is then broken along the scribed lines to produce the individual light pattern generators, such as generator 28.
In the preferred embodiment of the present invention, the layers 42 and 44 are on the same side of the plate 40. However, it would be equally functional to have the layers on opposite sides of the plate 40, but this would require each layer to be etched separately.
In operation, the light pattern generator 28 passes a portion of the light beam 20 to produce the desired image. The reflective layer 42 reflects in excess of 95% of the light that strikes the layer thereby preventing most of the light from being absorbed by the light pattern generator 28, which would otherwise tend to create heat. The light fixture 10 is provided with air ventilation, not shown, which cools the generator 28. The relatively low amount of heat absorbed by the generator 28 permits it to be cooled by forced air cooling. By keeping the generator 28 at a relatively low temperature, it has a much greater lifetime than the conventional metal design for gobos. The layer 44 serves to absorb light, but the amount of this secondary reflected light is quite small and therefore the actual heat which is generated by the absorption of light by layer 44 is very small.
A further advantage of the present invention is that any desired image shape can be produced without the limitation of support members for holding interior light blocking members in place.
A still further advantage of the light pattern generator 28, as compared to conventional gobos, is that the generator 28 is quite small and can be easily fitted on the wheel 24 to produce a large number of image shapes in a very compact space.
In summary, the present invention comprises a light pattern generator which has a mirror surface that is etched to permit the desired shape of beam to be passed through the generator but which reflects the remainder of the light beam to prevent heat buildup in the light pattern generator itself.
Although several embodiments of the invention have been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it will be understood that the invention is not limited to the embodiments disclosed, but is capable of numerous rearrangements, modifications and substitutions without departing from the scope of the invention.
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A light pattern generator is utilized to produce an image which is projected onto a stage or screen. The image is derived from a beam of light. The light pattern generator comprises a heat resistant glass plate having a reflective layer deposited on one surface thereof. A nonreflective layer is deposited on the surface of the reflective layer. Both of the layers are etched to produce an opening extending through the layers wherein the opening has the shape of the desired image. The beam of light is directed through the transparent plate and the portions not passed through the opening are reflected by the mirror surface of the reflective layer. This prevents the buildup of heat within the light pattern generator. Any extraneous light which is received at the nonreflective layer is absorbed to prevent the escape of unwanted light and its projection to the stage.
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FIELD OF THE INVENTION
This invention relates to aerosol hair spray formulations based on (1) a sulfonate containing, water dispersible or water dissipatible, linear polyester having a glass transition temperature of about 36° C. to about 40° C. and (2) a water soluble, polyvinyl lactam polymer. In addition, the formulations contain water as the liquid vehicle and a propellant. Such aerosol hair spray formulations do not contain any volatile organic compounds other than propellant yet exhibit fast drying times and excellent performance characteristics.
BACKGROUND OF THE INVENTION
Hair spray formulations typically comprise a solution of a polymer, the fixative, in water/alcohol mixtures. The polymeric materials which are typically used in hair spray formulations are soluble in water or water/alcohol mixtures and are derived from N-vinyl-pyrrolidinone or N-vinylpyrrolidinone and one or more other vinyl monomers such as vinyl acetate, acrylate and methacrylate esters and/or styrene compounds. When applied to hair and allowed to dry, the polymeric material provides human hair body, consistency, firm texture, and, in general, maintains the hair in a desired arrangement.
Significant amounts of volatile organic compounds such as alcohols are present in such hair spray formulations to facilitate rapid drying of the polymer solution. Environmental concerns continue to encourage the development of hair spray formulations which contain very little and preferably no volatile organic compounds. Attempts to omit the volatile organic component of hair sprays have failed to produce formulations which have acceptable drying times, particularly when the water level exceeds about 55% by weight of the formulation.
U.S. Pat. No. 4,300,580 describes hair spray formulations containing a water-dispersible or water-dissipatible linear sulfo-polyester fixative in a water/alcohol mixture. Such formulations are fast drying and have good hair holding properties but possess the disadvantage of being very difficult to remove from the hair. For example, prolonged washing is required to completely remove the water dispersible, linear polyester fixative to obtain hair with no tacky or sticky feel. In an effort to overcome the fixative removal problem, U.S. Pat. No. 4,300,580 teaches the addition of certain water soluble polymers to formulations containing the water-dispersible, linear polyester. The use of poly(alkylene glycols) such as poly(ethylene glycol) is disclosed. However, when such formulations containing a combination of the poly(alkylene glycol) and water dispersible, linear polyester are applied to hair and allowed to dry, the fixative causes a matting of the hair. Such matting hinders combing, brushing and styling of hair. It is important to note that U.S. Pat. No. 4,300,580 recommends in column 4, lines 36-38, a "nonaerosol" method of application of the hair spray formulation.
U.S. Pat. No. 4,150,216 discloses grooming formulations containing branched sulfo-polyesters. Difficulty, however, is encountered in maintaining the specified molecular weight range of 600 to 5,000. Slight variations in the condensation temperatures and/or times results in branched polymers having molecular weights which exceed the desired values and which have poor film forming characteristics, i.e. they are hard and brittle, and are not readily water dispersible or soluble as required in hair spray formulations.
Copending commonly assigned U.S. patent application Ser. No. 07/892,297 discloses water based, film forming formulations which contain as the fixative a combination of (1) a sulfonate containing, water-dispersible or water-dissipatible, linear polyester and (2) a water-soluble, polyvinyl lactam polymer. While the glass transition temperature (Tg) of the polyester is not specified, the application lists commercially available polyesters which have a Tg of from 29° C. to 55° C.
The present inventors have unexpectedly discovered that aerosol hair spray formulations wherein the fixative is a combination of two polymeric materials: (1) a sulfonate containing, water dissipatible, linear polyester having a Tg of about 36° C. to about 40° C. and (2) a water soluble, poly-vinyl lactam polymer, exhibit improved properties over aerosol hair sprays containing a sulfo-polyester having a Tg outside of said range. The aerosol hair spray formulations of the present invention do not have the disadvantages described hereinabove, such as tackiness, matting and difficulty in removal. Moreover, the aerosol hair spray formulations do not contain any volatile organic compounds other than propellant.
SUMMARY OF THE INVENTION
Accordingly, it is one object of the present invention to provide an aerosol hair spray formulation having improvements in one or more of the above desirable features.
Accordingly, it is another object of the invention to provide an aerosol hair spray formulation which is not tacky, has a fast drying rate, acceptable body, consistency and firm texture necessary to hold hair in the desired arrangement for a certain length of time and does not contain any volatile organic compounds.
Still another object of the invention is to provide an aerosol hair spray formulation having excellent storage stability and which does not clog or produce foam at the exit port of an aerosol container.
These and other objects are accomplished herein by an aerosol hair spray composition comprising:
(1) about 1 to about 10 weight percent based on the weight of components (1), (2), (3) and (4) of a sulfo-polyester having a glass transition temperature of 36° C. to 40° C. consisting essentially of repeat units from
(a) a dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids, and combinations thereof;
(b) a diol; and
(c) a difunctional sulfomonomer containing at least one sulfonate group attached to an aromatic nucleus wherein the functional groups are hydroxy, carboxy or amino, provided the difunctional sulfomonomer is present in an amount from 4 to 25 mole percent based on 100 mole percent dicarboxylic acid and 100 mole percent diol; and
(2) about 1 to about 7 weight percent based on the weight of components (1), (2), (3) and (4) of a water-soluble, polyvinyl lactam polymer containing at least 50 mole percent of residues of N-vinyl lactams of the formula ##STR1## wherein n is 3 or 4;
(3) about 46 to about 94 weight percent based on the weight of components (1), (2), (3) and (4) of a liquid vehicle consisting essentially of water; and
(4) about 3 to about 40 weight percent based on the weight of components (1), (2), (3) and (4) of a propellant selected from the group consisting of a C 1 -C 4 aliphatic hydrocarbon, dimethyl ether, and mixtures thereof.
DESCRIPTION OF THE INVENTION
The term "hair" as used in the present invention includes treated and untreated human hair, animal hair, and any type of fiber which requires consistency and firm texture necessary to hold it in the desired arrangement for a certain length of time.
The sulfo polyester, component (1), has a glass transition temperature in the critical range of about 36° C. to about 40° C. and contains repeat units from a dicarboxylic acid, a diol and a difunctional sulfomonomer. Dicarboxylic acids useful in the present invention include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, saturated aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, and cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms. Specific examples of dicarboxylic acids are: terephthalic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like. The polyester may be prepared from two or more of the above dicarboxylic acids.
It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid".
The diol component of the polyester includes cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. Examples of such diols are: ethylene glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4-trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, and 2,2-bis-(4-hydroxypropoxyphenyl)-propane. The polyester may be prepared from two or more of the above diols.
The difunctional sulfomonomer component of the polyester may be a dicarboxylic acid or an ester thereof containing a sulfonate group (--SO 3 31 ), a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group. The cation of the sulfonate salt may be Na+, Li+, K+, NH 4 +, and substituted ammonium. The term "substituted ammonium" refers to ammonium substituted with an alkyl or hydroxy alkyl radical having 1 to 4 carbon atoms. The difunctional sulfomonomer contains at least one sulfonate group attached to an aromatic nucleus wherein the functional groups are hydroxy, carboxy or amino. Advantageous difunctional sulfomonomer components are those wherein the sulfonate salt group is attached to an aromatic acid nucleus such as benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl or methylenediphenyl nucleus. Preferred results are obtained through the use of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and their esters. The sulfomonomer is present in an amount from 4 to 25 mole percent, preferably 10 to 12 mole percent, based on 100 mole percent dicarboxylic acid and 100 mole percent diol.
In particularly preferred embodiments, the water dispersible sulfo-containing linear polyester is derived from (a) a mixture of dicarboxylic acids consisting of isophthalic acid (or ester) and 5-sodio-sulfoisophthalic acid, (b) a diol component consisting of diethylene glycol, or a mixture of diols consisting of at least 75 mole percent of diethylene glycol with the remaining diol being either ethylene glycol or 1,4-cyclohexanedimethanol. The sulfo-polyester, component (1), is present in an amount of about 1 to about 10 weight percent, based on the weights of components (1), (2), (3) and (4) of the aerosol hair spray formulation.
Component (2) is a water soluble vinyl polymer or copolymer which contains at least 50 mole percent of the residues of n-vinyl lactam monomer the formula ##STR2## In the above formula, n is 3 or 4. Preferably, n equals three wherein the N-vinyl lactam monomer is N-vinylpyrrolidinone. Examples of other vinyl compounds which may be copolymerized with an N-vinyl lactam to prepare the water soluble polymers include vinyl esters and vinyl aromatic compounds having the structure ##STR3## wherein R 1 is alkyl, e.g., straight-and branched-chain alkyl of up to about 10 carbon atoms; R 2 is hydrogen or methyl; R 3 is alkyl, e.g., straight-and branched-chain alkyl of up to about 10 carbon atoms, and alkyl substituted by hydroxy or by amino including alkylamino and dialkylamino; and R 4 is hydrogen or alkyl of up to about 4 carbon atoms.
The water soluble polymers, component (2), may be prepared according to known procedures wherein a N-vinyl lactam is polymerized, optionally in the presence of one or more other vinyl monomers such as those described above. The N-vinylpyrrolidinone/vinyl acetate copolymers supplied by BASF under the tradename Luviskol VA are typical of the water-soluble polymers which may be used in the aerosol hair spray compositions of the present invention. The preferred water soluble polymers comprise homopolymers of N-vinyl-2-pyrrolidinone and copolymers of N-vinyl-2-pyrrolidinone and up to 50 mole percent vinyl acetate having weight average molecular weights in the range of about 1000 to 100,000. The water-soluble, poly-vinyl lactam polymer, component (2), is present in an amount of about 1 to about 7 weight percent, based on the weights of components (1), (2), (3) and (4) of the aerosol hair spray formulation.
Component (3) of the aerosol hair spray formulations is a liquid vehicle. The liquid vehicle of the formulations may be water or a water/alcohol mixture. Distilled or deionized water are the preferred sources of water since tap water generally contains ions which would precipitate the sulfopolyester, component (1). The alcohol should have two to four carbon atoms. Specific alcohols include, ethanol, isopropanol and t-butanol. A preferred water/alcohol mixture contains 55 to 65 weight percent water and 35 to 45 weight percent alcohol. The preferred alcohol is ethanol. The liquid vehicle is present in an amount of about 46 to about 94 weight percent, based on the weights of components (1), (2), (3) and (4) of the aerosol hair spray formulation.
Component 4 is a propellant selected from the group consisting of a C 1 -C 4 aliphatic hydrocarbons and dimethyl ether. The aliphatic hydrocarbons may be branched or straight chain and include methane, ethane, propane, n-butane, isobutane, or mixtures thereof. A preferred aliphatic hydrocarbon propellant is a mixture containing about 83 percent isobutane and about 17 percent propane. The propellant is present in an amount of about 3 to about 40 weight percent, based on the weights of components (1), (2), (3) and (4) of the aerosol hair spray formulation. In the case where a C 1 -C 4 aliphatic hydrocarbon is used as the propellant, generally about 3 to about 10 weight percent, preferably 4 to 7 weight percent, is employed. In the case where dimethyl ether is used as the propellant, generally, about 30 to about 40 weight percent, preferably, 30 to 35 weight percent, is employed.
Other conventional additives such as preservatives, fragrances, antifoaming agents, hair conditioners, plasticizers, etc. may be added in such quantities as desired, up to about 5.0% by weight of the total formulation. Although the film forming formulations described herein are particularly useful as aerosol hair sprays for the grooming of hair, it is possible that the formulations, with or without modification, may be used in other types of personal care products.
It is unexpected, based on the prior art, that the combination of a sulfo-containing water dispersible polyester having a Tg of 36° C. to 40° C. with a water soluble vinyl polymer would give aerosol hair spray formulation improvements over either of the single component systems or a dual component system at other glass transition temperatures, particularly in washability/rinsability, tackiness, humidity resistance and film elasticity.
The materials and testing procedures used for the results shown herein are as follows:
DYMEL A (CTFA Adopted Name: Dimethyl Ether) available from DuPont, is a dimethyl ether and is used as a propellant.
LUVISKOL VA 73W PVP/VA (CTFA Adopted Name: PVP/VA Copolymer), available from BASF, is a water soluble vinyl copolymer of 70 mole percent of N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids), and is used as a fixative.
GLYDANT (CTFA Adopted Name: DMDM Hydantoin) available from Lonza, Inc. is 1-(hydroxymethyl)-5,5-dimethyl hydantoin, and is used as a antimicrobial.
Inherent viscosity (I.V.) was measured at 23° C. using 0.50 grams of polymer per 100 ml of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
Preparation of tresses involved natural brown, European virgin hair. About two grams of hair, root end, were glued to a 2" by 2" plastic tab. The tresses were cut so that the length of hair hanging below the tabs was six inches.
The invention will be further illustrated by a consideration of the following examples, which are intended to be exemplary of the invention. All parts and percentages in the examples are on a weight basis unless otherwise stated.
EXAMPLE I
Preparation of a water-dispersible sulfo-polyester
A 500 mL round bottom flask equipped with a ground-glass head, an agitator shaft, nitrogen inlet and a side arm was charged with 74.0 grams of isophthalic acid, 16.0 grams of 5-sodiosulfoisophthalic acid, 106.0 grams of diethylene glycol, sufficient titanium isopropoxide to provide 50 ppm of titanium, and 0.45 grams of sodium acetate tetrahydrate. The flask was immersed in a Belmont bath at 200° C. for two hours under a nitrogen sweep. The temperature of the bath was increased to 280° C. and the flask was heated for one hour under reduced pressure of 0.5 to 0.1 mm of Hg. The flask was allowed to cool to room temperature and the copolyester was removed from the flask. The copolyester had an I.V. of about 0.45 and a glass transition temperature of about 30° C. as measured using a differential scanning calorimeter (DSC). The copolyester was extruded and pelletized.
EXAMPLE II
Preparation of an aerosol hair spray formulation
The copolyester prepared in Example I, 7.14 grams, was dispersed in 52.15 grams of distilled water by heating and stirring until a temperature of about 85° C. was reached. After cooling to 40° C. any water lost during heating was replaced and 5.71 grams of a water soluble vinyl copolymer consisting of 70 mole percent of N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids) was added at 40° C. The mixture was stirred and filtered to remove any residual material. The pH was adjusted to 5.5±0.5 followed by the addition of 35.0 grams of ethanol.
To 61.88 grams of the composition was added 15.4 grams of a mixture containing about 83 percent isobutane and about 17 percent propane. The formulation was applied in the form of an aerosol hair spray to hair tresses. The test results are summarized in Table I.
EXAMPLE III
Preparation of a water-dispersible sulfo-polyester
A 500 mL round bottom flask equipped with a ground-glass head, an agitator shaft, nitrogen inlet and a side arm was charged with 74.0 grams of isophthalic acid, 16.0 grams of 5-sodiosulfoisophthalic acid, 83.0 grams of diethylene glycol, 16.0 grams of 1,4-cyclohexanedimethanol, sufficient titanium isopropoxide to provide 50 ppm of titanium, and 0.45 grams of sodium acetate tetrahydrate. The flask was immersed in a Belmont bath at 200° C. for one hour under a nitrogen sweep. The temperature of the bath was increased to 230° C. for one hour. The temperature of the bath was increased to 280° C. and the flask was heated for 45 minutes under reduced pressure of 0.5 to 0.1 mm of Hg. The flask was allowed to cool to room temperature and the copolyester was removed from the flask. The copolyester had an I.V. of about 0.36 and a glass transition temperature of about 38° C. as measured using a differential scanning calorimeter (DSC). The copolyester was extruded and pelletized.
EXAMPLE IV
Preparation of an aerosol hair spray formulation
The copolyester prepared in Example III, 17.85 grams, was dispersed in 217.9 grams of distilled water by heating and stirring at 80-85° C. for 15 minutes. The mixture was cooled to 40° C. Water lost during heating was replaced by adding distilled water. A water soluble vinyl copolymer consisting of 70 mole percent of N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids), 14.3 grams, was added and the mixture was stirred and filtered to remove residual material The pH was adjusted to 5.5±0.5 and 0.2 weight percent of 1-(hydroxymethyl)-5,5-dimethyl hydantoin was added. Good storage stability of the formulation was observed after aging at 40° C. for one week in an oven.
To 70.0 grams of the above hair spray formulation was added 30.0 grams of dimethyl ether. The all aqueous aerosol formulation showed good clarity and storage stability. The formulation was applied in the form of an aerosol hair spray to hair tresses. The test results are summarized in Table I.
EXAMPLE V
Preparation of an aerosol hair spray formulation
The copolyester prepared in Example III, 7.14 grams, was dispersed in 52.15 grams of distilled water by heating and stirring until a temperature of about 85° C. was reached. After cooling to 40° C. any water lost during heating was replaced and 5.71 grams of a water soluble vinyl copolymer consisting of 70 mole percent of N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids) was added at 40° C. The mixture was stirred and filtered to remove any residual material. The pH was adjusted to 5.5±0.5 followed by the addition of 35.0 grams of ethanol.
To 61.88 grams of the composition was added 15.4 grams of a mixture containing about 83 percent isobutane and about 17 percent propane. The formulation was applied in the form of an aerosol hair spray to hair tresses. The test results are summarized in Table I.
EXAMPLE VI
Preparation of a water-dispersible sulfo-polyester
A 500 mL round bottom flask equipped with a ground-glass head, an agitator shaft, nitrogen inlet and a side arm was charged with 136.0 grams of isophthalic acid, 53.0 grams of 5-sodiosulfoisophthalic acid, 155.0 grams of diethylene glycol, 78.0 grams of 1,4-cyclohexanedimethanol, sufficient titanium isopropoxide to provide 50 ppm of titanium, and 1.48 grams of sodium acetate tetrahydrate. The flask was immersed in a Belmont bath at 200° C. for one hour under a nitrogen sweep. The temperature of the bath was increased to 230° C. for one hour. The temperature of the bath was increased to 280° C. and the flask was heated for 45 minutes under reduced pressure of 0.5 to 0.1 mm of Hg. The flask was allowed to cool to room temperature and the copolyester was removed from the flask. The copolyester had an I.V. of about 0.33 and a glass transition temperature of about 55° C. as measured using a differential scanning calorimeter (DSC). The copolyester was extruded and pelletized.
EXAMPLE VII
Preparation of an aerosol hair spray formulation
The copolyester prepared in Example VI, 17.85 grams, was dispersed in 217.9 grams of distilled water by heating and stirring at 80-85° C. for 15 minutes. The mixture was cooled to 40° C. Water lost during heating was replaced by adding distilled water. A water soluble vinyl copolymer consisting of 70 mole percent of N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids), 14.3 grams, was added and the mixture was stirred and filtered to remove residual material The pH was adjusted to 5.5±0.5 and 0.2 weight percent of 1-(hydroxymethyl)-5,5-dimethyl hydantoin was added. Good storage stability of the formulation was observed after aging at 40° C. for one week in an oven.
To 70.0 grams of the above hair spray formulation was added 30.0 grams of dimethyl ether. The sulfo polyester precipitated. Dimethyl ether was replaced with ethane and the sulfo-polyester precipitated. Thus, the sulfo polyester having a Tg of about 55° C. was not compatible with any of the
propellants which are necessary in aerosol hair spray formulations.
EXAMPLE VIII
In order to evaluate the effect of the glass transition temperature of the linear sulfo-polyester in a aerosol hair spray formulation, tresses were treated with the aerosol hair spray formulations of Examples II and V. The aerosol hair spray formulation of Example II contains a sulfo-polyester having a Tg of about 30° C. while the aerosol hair spray formulation of Example V contains a sulfo-polyester having a Tg of about 38° C. Other than the glass transition temperature, the formulations were essentially identical. One tress per treatment was used. The tresses were sprayed with the respective aerosol hair spray for 10 seconds each which was enough time to completely cover each of the tresses. Individual tresses were dried under heat while subjective feel tests were conducted on the wet tresses. The subjective evaluations were conducted by a panel of ten people. The evaluators rated the tresses on a scale of 1 to 10. The lower values indicate hair that was more tacky or sticky when touched. The average of these results by each evaluator for each of the aerosol hair sprays are summarized in Table I.
TABLE I______________________________________Effect of Tg in Aerosol Hair Spray Formulations Subjective EvaluationsEvaluator 30° C. Tg Hair Spray 38° C. Tg Hair Spray______________________________________A 4.0 8.5B 3.0 9.0C 3.0 8.0D 3.5 8.0E 4.5 8.5F 4.0 8.0G 2.5 9.0H 3.0 7.0I 4.0 8.0J 3.5 9.0AVERAGE 3.5 8.3______________________________________
The results in Table I clearly indicate that the aerosol hair spray formulation containing the sulfo-polyester having a Tg of about 38° C. proved to be significantly superior in terms of being less tacky or sticky than the hair spray formulation containing the sulfo-polyester having a Tg of about 30° C. The average values of 3.5 and 8.3 on the scale of 1 to 10 indicates a significant deviation in tacky or sticky feel to hair treated with the different aerosol hair spray formulations. In addition, the hair spray formulation containing the sulfo polyester having a Tg of about 38° C. had good rinsability/washability and humidity resistance.
Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious modifications are within the full intended scope of the appended claims.
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This invention relates to aerosol hair spray formulations based on (1) a sulfonate-containing, water-dispersible or water-dissipatible, linear polyester having a glass transition temperature of about 36° C. to about 40° C. and (2) a water-soluble, polyvinyl lactam polymer. In addition, the formulations contain water as the liquid vehicle and a propellant. Such aerosol hair spray formulations do not contain any volatile organic compounds other than propellant yet exhibit fast drying times and excellent performance characteristics.
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BACKGROUND OF THE INVENTION
The present invention pertains generally to compound archery bows which utilize tensioned cables and bowstrings carried by pulleys at the bow ends.
Bowstrings, as used in current compound bows, are of synthetic material and are subject to creep or stretching after a period of use resulting in a number of problems, any one of which adversely affects bow accuracy. For example, the bending rates of bow limbs may be altered, the rotation of the bow pulleys or wheels may be out of synchronization, the nock position may be dislocated. While some manufacturers have attempted to solve the bowstring elongation problem, their efforts to date have provided for only very limited bowstring adjustment, perhaps an inch or so take up. A remaining solution is the costly purchase and installation of a new bowstring which will subsequently stretch as a result of forces applied thereto. Extreme temperatures and humidity also adversely affect bowstrings.
Another bowstring problem occurs when an archer desires to vary the draw length of a bow which typically requires the purchase and installation of a new bowstring. The capability of existing bow mounted pulleys or wheels to alter bowstring length is very limited and is in relatively large increments which prevents precise tensioning of the bowstring during installation.
In the prior art, U.S. Pat. No. 4,926,832 discloses pulleys 42 in place on a compound archery bow with each pulley provided with multiple knobs for attachment thereto of a tension cable end with an additional set of knobs for selective attachment thereto of the ends of a bowstring. Such an arrangement permits only modest changes in the effective length of the tensioned members.
SUMMARY OF THE PRESENT INVENTION
The present invention is embodied within a compound bow mounted pulley having an adjustable take-up feature capable of being indexed about an axis and locked in place to permit precise adjustment of a tensionable bow member.
The present pulley assembly is equipped with or includes a rotatable and lockable member having multiple tracks on which tensionable bow members are entrained. Typically on compound bows rotatable members, termed pulleys, cams, cam wheels, etc., are mounted in an eccentric manner to lessen the force required to hold a drawn arrow. In the present pulley assembly a take-up spool is mounted in a manner permitting periodic, arcuate positioning, relative the pulley proper, for altering the effective length of a bowstring and/or a cable of the bow. While shown and described as being utilized to vary bowstring length, it will be understood that the present invention may also be utilized to adjust a bow cable. Provision is made in the present pulley assembly for indexing of a take-up spool and subsequent locking of same to a rotatable bow member in a convenient manner.
Important objectives of the present invention include the provision of a take-up spool in place on a compound bow pulley for the purpose of permitting a tensioned member of the compound bow to be lengthwise altered; the provision of a take-up spool carried by a compound bow pulley permitting the tensionable member of the bow to be adjusted in fine increments to dispense with the necessity of changing the tensionable member; the provision of a take-up spool in the form of a spool which may be indexed about an axis to reduce or increase the length of a tensionable bow member; the provision of a take-up spool in combination with a pulley for a compound bow to provide incremental indexing means enabling precise adjustment of a tensionable bow member; the provision of a take-up which permits binding securement of a bowstring or cable end segment without formation of a loop on the bowstring or the attachment of a lug to a cable end.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a side elevational view of a compound bow;
FIG. 2 is an enlarged side elevational view of a pulley assembly of the bow shown in FIG. 1;
FIG. 3 is a side elevational view of the unseen side of the pulley assembly shown in FIG. 2;
FIG. 4 is a perspective exploded view of the pulley shown in FIGS. 2 and 3 with a take-up spool shown detached from the pulley assembly;
FIG. 5 is a vertical sectional view taken along line 5--5 of FIG. 2;
FIG. 6 is an elevational view of the take-up shown in FIG. 4;
FIG. 7 is an elevational view of a modified form of take-up shown with a fragment of a supporting pulley assembly;
FIG. 8 is a perspective view of one side of a modified take-up; and
FIG. 9 is a vertical sectional view similar to FIG. 5 but showing the take-up shown in FIG. 8 in place on the pulley assembly.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With continuing attention to the drawings, wherein applied reference numerals indicate parts similarly hereinafter identified, the reference numeral 1 indicates generally a compound archery bow.
The bow includes a riser 2 from which project upper and lower limbs 3 and 4. A hand grip is indicated at 5. Tensionable bow members of the bow include cables 6 and 7 which are further tensioned by displacement of a bowstring at 12 during drawing of same. Typical rigging of a compound bow includes the ends of cables 6 and 7 being secured to devises 8, 9 with the remaining end of each cable 6 and 7 being entrained and secured thereto about a portion of a pulley assembly of the type indicated generally at 10. During drawing of a bow, pulley assemblies are partially rotated about pivot pins such as at 13, 14 carried by the bow limbs with the effective length or run of each cable being reduced to impart inwardly directed forces to each limb end. The foregoing description of cable rigging is intended to be typical as it is understood that variations of such rigging may be found in the wide variety of makes and models of compound bows including some having a bowstring as an extension of a cable. While the following description of the invention is in conjunction with a single pulley assembly indicated generally at 11, both pulleys of a bow could utilize the present invention to increase the range of lengthwise adjustment of a tensionable bow member. A knob K on pulley 11 attaches the looped end of cable 7.
A take-up spool 15 is carried by pulley assembly 11 and is shown having wraps 16 of bowstring 12 thereon. The take-up spool is received within an inset area 17 of pulley assembly 11. A radially directed opening 18 in a sidewall 20 of the spool facilitates attachment of tensionable member 12 to the take-up as by wrapping thereabout. As shown in FIG. 6, the remaining sidewall at 21 of the take-up or spool may be continuous.
For preventing rotation of take-up spool 15 relative to the pulley, locking means are provided which, in addition to locking the take-up spool in place, permits indexing of the take-up spool in increments fully about an axis A in parallel with the axis of a pulley pivot pin 14, in fine increments, for take up or letting out of member 12. A preferred locking means is disclosed in FIGS. 4, 5 and 6 wherein sidewall 21 of take-up 15 includes a member 22 projecting axially from wall 21 and provided with an irregular perimeter 23 for mating with a corresponding edge 24 formed on pulley 11. One suitable irregular perimeter 23 is that formed by a series of scallops or arcuate walls which permit incremental take-up spool positioning about axis A and re-engagement with pulley edge 24. A fastener 25 extends axially through a bore 27 for engagement within a threaded opening 26 of the pulley. An internally threaded sleeve may be utilized in the pulley to receive fastener 25 threads.
A modified take-up spool is shown in FIG. 7 which includes sidewalls 30 and 31 with perimeters at 30A and 31A of irregular configuration to constitute locking members engageable with a pulley 34 formed with a correspondingly shaped inner edge 34A. The locking members 30A and 31A engage pulley edge 34A to prevent take-up spool rotation relative the pulley and permit dispensing with the axial projection of the type shown at 22 in FIG. 4. Accordingly, a bow pulley may be of lesser cross-section or depth. A fastener 35 terminates in threaded engagement with a threaded bore formed in the pulley wall of reduced thickness.
FIGS. 8 and 9 disclose still another modified take-up spool having sidewalls 40 and 41 with the former having a radially extending slot 42 permitting attachment of a bowstring end about a hub 43 in FIG. 9 if desired. Locking members 44 are embodied in a circular array of pins uniformly spaced from one another and from an axis A of the take-up spool for selective engagement with corresponding sockets 45 formed within a pulley 46. A fastener 47 extends through a bore 48 in the take-up for threaded engagement with a threaded pulley bore 50.
Bowstring adjustment entails loosening of fastener 47, at least partial unseating of the take-up to disengage the locking means, incremental rotation of the take-up spool to reduce or increase the effective length of the bowstring and reseating of the take-up spool in the pulley. During such bowstring adjustment the tensioning of the bowstring will be reduced as by temporarily flexing of the bow limbs.
It will be understood that the locking means, while shown as having arcuate or curved surfaces in some forms of the present invention, may be of other irregular configuration including a toothlike edge similar to gear teeth for adjustable engagement with a corresponding edge of a pulley.
The take-up spool permits securement of an end segment of a tensionable member by wrapping same about the take-up spool with the wraps binding one another against slipping about the take-up. Accordingly costly loop forming of a bowstring end is avoided as well as the affixing of a lug to a cable end for securement purposes.
While I have shown but a few embodiments of the invention, it will be apparent to those skilled in the art that the invention may be embodied still otherwise without departing from the spirit and scope of the invention.
Having thus described the invention, what is desired to be secured by a Letters Patent is:
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A pulley assembly for a compound bow is provided with a take-up of spool configuration to receive a segment of a tensionable bow member wound thereabout. The take-up is engageable with the pulley proper member in a manner preventing relative movement between take-up and pulley assembly. To alter length of a tensionable member of the bow, the take-up is positionable about an axis parallel to an axis of the pulley assembly and lockable thereto. Modified forms of the take-up disclose various locking arrangements.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an apparatus for controlling filament wrapping of a spun core yarn.
2. Description of the Prior Art
In the prior art there has been increasing interest for the production of filament wrapped core-spun yarns and methods development related to said yarn production. Grosicki and Chylewska, Textile Institute and Industry Journal 17, pages 288-289, August 1979 are among the more recent researchers reporting their work in the field of core-spun yarns. These researchers utilize an air-vortex system to produce a core-spun yarn whereby the core is continuous filament yarns with a sheathing of natural fibers. While the benefits of their type yarn are cited the apparatus requires major mill modifications and uses vacuum in production which are undesirable for spinning mills equipped with ring spinning frames. Audivert and Fortuny, in the same issue as the cited work of Grosicki and Chelewska, discuss production of another means to produce a core-wrap type yarn called Differential Twist Yarns. The advantages of producing such yarn were enhanced tenacity and high production rate but the method requires a false-twist tube and is highly dependent on twist imparted to the yarn. Differential Twist Yarns are produced by first combining filament and staple fibers in the drafting zone then twisting further in the balloon zone with another filament. Three components are essential to the method of yarn production.
Audivert, U.S. Pat. No. 3,722,202, describes a method for producing blended yarns containing a staple fibrous core and a continuous man-made filament that is achieved on a ring spinning frame. In the Audivert process, feeding tension on the filament is important to the extent that not more than 0.5 g/tex should be employed. In the Audivert method, apparatus employed to obtain or control tension is not described nor are means to adjust tension described to achieve desired effect in the resultant composite wrapped yarn. Audivert, nevertheless claims a feeding tension is required in his method to produce desired effect of blending to obtain a wrapped yarn. To obtain tension on the filament, obviously a drag force must be used. Tensioning devices are inherent and require constant monitoring to assure binding effects are obtained with no part of the filament sinking into the fibrous core. Furthermore, Audivert teaches erroneous feeding methods which result in filament processed into the internal structure of the core yarn.
In contradistinction to prior devices, Parker, U.S. Pat. No. 2,552,210, avoided tensioning devices by merely feeding filament tension free. Parker accomplished tension free feeding through use of an upside down cone containing the filament yarn and points out tension is inevitable where a spun or twisted thread must turn a bobbin or spool for delivery. By employing the teachings of Parker, utilizing a tension free process, the filament goes into and out of the core as it is being spun thus partially covering the filament yarn.
An additional problem in the practice of the prior art is the point of combination of the filament with the core yarn. It is critical for the combination to occur at a sufficient distance from the exit of the nip of the front rolls of the drafting system of a ring spinning frame to preclude the filament from going into and out of the core as it is being spun, which is the object of Parker's teachings. The prior art teaches that the filament is combined with the staple fibers just as the two emerge from the front rolls of the spinning frame. Alternatively, the filament is passed through the apron rolls then through the front rolls. When passage through apron rolls occurs, the rolls must have a recessed center for slip drafting. None of the prior art can be practiced without considerable control and monitoring of tension. Further, no teachings of the prior art address the inherent problem of intertwining of the filament while the core is being spun because of the location of the combination point of the filament and the core yarn at the nip of the front rolls.
SUMMARY
We have now found that by suitably combining core yarn with filament at a critical thread guide contact point just prior to the ballon zone of core yarn formation where core yarn formation is essentially complete, we can significantly enhance external wrapping of filament around the core yarn. We have also found that separate filament feed rolls provide a means to assure a uniform flow of filament and maintain that flow without tensioning devices or constant monitoring.
Essentially, means is provided for drafting fiber into core yarn. This core yan is then fed through a contact guide and into a conventionally ring sprinning means. The ring spinner receives the core yarn, and spins and rotates it on its longitudinal axis. Simultaneously, filament is over-fed into the same contact guide as the core yarn where the filament is contacted with the outer surface of the core yarn cohesively. The result is a helical wrapping of the filament around the surface of the core yarn as the two are fed together into and through the spinning means.
Thus several problems associated with the prior art can be overcome. One problem of the prior art was the point of contact of the filament with the core yarn. It is critical for the combination to occur at a sufficient distance from the front rolls of the drafting system to preclude the filament from going into and out of the interior of the core as it is being spun. The prior art teaches that the filament is twisted around the staple fiber yarn as it emerges from the spinning frame. This is accomplished by passing the filament through the front draft rolls with the staple fiber but the point of combination of fiber core to filament is unknown and not controlled. Alternatively, in the prior art, the filament is passed through the apron rolls then through the front rolls. When passage through apron rolls occurs, the rolls must have a recessed center for slip drafting. None of the prior art can be practiced without considerable control and monitoring of tension. Further, no teachings of the prior art address the inherent problem of intertwining of the filament while the core is being spun because of the location of the combination point of the filament and the core. Internal wrapping of filament in the core yarn will definitely occur when combining the filament with uncompleted core yarn as is taught by all of the prior art.
In the instant invention, drafting of a staple core yarn is complete at the nip of the front rolls of the fiber drafting means. Twist or rotation around the longitudinal axis of the core yarn is put on an essentially completed core yarn just after leaving the drafting zone and prior to any contact with the filament. The filament is contacted only after completed formation of the core yarn thus internal wrapping of the filament into the core yarn is avoided. The prior art describes combinations of core yarn with filament either prior to the front drafting rolls or at the latest at the front drafting rolls: always prior to the critical point of entry of the thread guide. In the instant invention continuous filament is fed from preselected diameter feed rolls. The diameter of the filament feed rolls is 10% larger than the diameter of the core yarn feed rolls when both the yarn feed and filament feed rolls are on the same shaft axis. Thus the speed of feed of the filament is adjusted sufficiently greater to the speed of feed of the staple core yarn and allows for over-feed of the filament just enough to accomplish proper helical wrapping of the filament around the core yarn staple as the core yarn rotates on its longitudinal axis. The filament feed thus controls and assures uniform helical wrapping.
When the feed rolls of the filament feed and the feed rolls of the staple core yarn feed are on separate shaft axis, then the diameter of feed rolls of the filament can be the same or different from the feed rolls for the staple yarn feed, since the over-feed can be accomplished by speeding up the rotation of the filament rolls and thus the speed of the filament feed relative to the speed of the feed of the staple core yarn.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. I is a schematic front view of a ring spinning frame and illustrates one embodiment of the instant invention wherein the filament over-feed rollers and the feed rollers for the spun core yarn are on the same shaft axis.
FIG. II is an isometric detail showing the front rolls of FIG. I.
FIG. III is a diagrammatic side view of a second embodiment of the instant invention wherein the filament over-feed rollers and the feed rollers of the staple spun core yarn are on separate shaft axes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In general, the instant invention consists of drafting a roving into a yarn and simultaneously wrapping a filament uniformly around the outer surface of the yarn during the ring spinning process. There are several critical aspects of the instant invention which must be adhered to in order to accomplish a uniform filament wrap of a spun yarn core. First, the proper diameter of yarn core to weight of filament must be correctly chosen in order to yield the optimum composite weight. Secondly, the point at which the filament is fed into the spinning process and combined with the yarn core is critical to assure uniform wrapping of the outer surface and avoid the filament from ever entering the actual staple yarn core. Third, the speed of the feed of filament must be balanced with the speed of the feed of the core yarn, by proper selection of the diameter of the roller which feeds the filament to the thread guide in order to achieve proper filament feed speed.
Referring now to FIGS. I and II wherein a staple yarn core is fabricated by introducing unspun staple fibers 1 into trumpet 2 which is mounted on a traversing bar 3 then into a drafting zone 23 consisting of back rolls 4, middle rolls 5, aprons 6, and then front rolls 7. The action on staple fibers 1 by drafting zone 23 is to form a staple fiber core 20. This is accomplished by stretching out or drawing staple fibers 1 and reducing the diameter of the staple fibers prior to passing through front rolls 7 and out at nip 8 which is the immediate exit of front rolls 7 to achieve properly formed staple core yarn 20. Nip 8 is critical to the process because it is at this point which twist of staple core yarn 20 begins. The twisting process begins at nip 8 of front rolls 7 and is typical for ring spinning processes. Staple core yarn 20 is essentially complete as it enters thread guide 13 where it balloons out and passes through balloon zone 14, through revolving traveler 10 which travels on ring 9 thus forming spinning means 24. The yarn is then spunt onto a bobbin (not shown).
Simultaneously, during the above described process for making staple core yarn 20, filament or multi-filament 15 is fed from a filament wound on a pirn or packaged mounted on a stationary or revolving spindle attached to the frame (not shown). Filament 15 is fed through trumpet 16 which is mounted on traversing bar 3, and bypasses rolls 4, 5, and aprons 6 and enters between top filament feed roller 17a and lower filament feed roller 17b (FIG. II). Lower filament feed roller 17b is designed with a diameter larger than front rolls 7 to increase the filament feed velocity and thus control uniform overfeed of filament 15 relative to the feed of staple core yarn 20. In this embodiment of the invention, lower roll 7b and lower filament feed roll 17(b) rotate on the same shaft and axis 18 and consequently both rotate at the same revolutions per minute. Lower feed roll 17(b) is optimally 10% larger in diameter than roll 7b in order to effect the correct rate of filament feed speed in relation to the core yarn feed speed and thus achieves uniform filament wrapping around the outer surface of staple core yarn 20. Thus, shaft axis 18 is driven by an external means (not shown) just as back rolls 4, and middle rolls 5. Filament 15 then passes through filament thread guide 19, (FIG. I) and then through thread guide 13 which is the critical point at which filament 15 cohesively contacts the outer surface of spun core yarn 20 and also the point at which wrapping of filament 15 around yarn 20 begins to take place. Filament thread guide 19 is thus located between the nip of rolls 17 and thread guide 13 which is the contact guide. Filament 15 then passes through revolving traveler 10 which travels on ring 9, and is then spun onto a bobbin (not shown) simultaneously with spun core 20. Helical wrapping of filament 15 uniformly around staple core yarn 20 occurs between contact thread guide 13 and the bobbin (not shown). This results from the optimum combination of critical parameters affecting the relationship of filament and spun core at this location. These critical parameters are the ratio of speed feed of staple core yarn 20, and twist of staple core yarn 20 in relation to speed of filament 15 feed. Therefore, the above results in a composite uniformily filament wrapped staple yarn on a bobbin accomplished during the conventional ring spinning process.
Referring now to FIG. III wherein a second embodiment of the invention is described. In this embodiment of the invention the yarn core producing apparatus is identical to the device described above. The main differences are in filament feed rollers 21a and b. Filament feed rollers 21a and b are located on a different axis from front rolls 7. Thus, roll 21b is driven (not shown) independently from front rolls 7. The first purpose for this embodiment is to accomplish greater flexibility and variation on the kinds and types of filament 15 which can be fed into the system. The second purpose is to vary the speed of filament feed roller 21b in relation to core yarn lower feed roller 7b. 7a is the core yarn upper feed roller. Thereby, one is able to produce a wider variety of composite filament wrapped yarns.
In this second embodiment, filament or multi-filament 15 is over-fed into the system by means of filament rolls 21a and 21b. Rolls 21a and b are mounted on shafts for an axis 22. It is important to note that shaft axis 22 for roller 21b, unlike the first embodiment, is different from that of roller 7b which is shaft axis 18. In this embodiment of the instant invention, filament feed roller 21b can be the same or larger in diameter than core yarn feed roller 7b. The overfeed is accomplished by means of adjusting the speed of rotation of roller 21b in relation to the revolutionary speed of roller 7b. This revolutionary speed differential between rollers 21b and 7b provides the optimum filament over-feed with respect to the core yarn feed. The result is uniformly wrapped filament 15 around staple core yarn 20.
Filament thread guide 19 is provided between the filament feed means 21 and contact guide 13 to feed filament 15 properly into contact guide 13 where filament 15 cohesively contacts the outer surface of core yarn 20 to allow for helical wrapping of filament 15 around yarn 20. The second embodiment of the instant invention works the same as the first in all aspects of the invention with the exception of this filament 15 feeding means.
In general, referring now to the figures, it should be noted that: A is the direction of feed of roving 1. B is the direction of feed of filament yarn 15. C is the direction of longitudinal rotation of staple core yarn 20. E and F are rotational directions for front rolls 7b and 7a. G and H are rotational directions for filament feed rolls 21b and 21a.
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An apparatus to uniformly wrap filament around the surface of a spun core yarn is disclosed. Means for fabricating a core yarn is provided. At the critical point of yarn fabrication, the spun core is simultaneously twisted or rotated on its longitudinal axis by means of ring spinning and contacted with a filament introduced by means of over-feed rollers. Helical wrapping of the filament around the surface of the staple core yarn takes place as the filament cohesively contacts the twisting core yarn to form a composite filament wound yarn.
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FIELD OF THE INVENTION
[0001] The present disclosure relates to a vaccine against Mycoplasma spp.; especially to a subunit vaccine against Mycoplasma spp.
BACKGROUND OF THE INVENTION
[0002] Mycoplasma spp. is currently known the tiniest bacteria capable of self-replication outside host cells. Although swine enzootic pneumonia would not cause swine death, it will reduce feeding efficiency and cause growth retardation, inflammation, and immunosuppression as well as make swine more vulnerable to infection of other pathogens, which therefore become economic damage of the industry.
[0003] So far, swine enzootic pneumonia is prevented by three major strategies, including: medicine administration, environment management, and vaccination. Seeing the bad prevention efficiency of antibiotics to Mycoplasma hyopneumoniae , medicine administration can only used for treatment purposes and is hard to meet prevention needs. Furthermore, considering that drug abuse may lead to a larger infection causing by drug-resistant bacteria, medicine administration needs cautious plans and exists a lot of limitations.
[0004] Environment management forms the basis of prevention of Mycoplasma spp. infection. Good piggery sanitation and management would be helpful to reduce occurrence of infection. On the other hand, prevention could be more comprehensive through vaccination.
[0005] The conventional vaccines in the field use inactive/dead bacteria as the active ingredient thereof. However, the price of the conventional vaccines is too high because Mycoplasma spp. is fastidious bacteria and is difficult to be cultured in the laboratory. In order to reduce the cost of Mycoplasma spp. vaccines, scientists continuously try to develop vaccines of different types, such as: (1) attenuated vaccines, (2) vector vaccines, (3) subunit vaccines, and (4) DNA vaccines. Among them, subunit vaccines show the most potential because the advantages of ease in production and high safety.
[0006] To date, there are several potential candidate proteins that could be used for M. hyopneumoniae vaccines; however, there is no further report verifying the proteins suitable for M. hyopneumoniae vaccines.
SUMMARY OF THE INVENTION
[0007] In light of the foregoing, one of the objects of the present invention is to provide antigens suitable for being used in M. hyopneumoniae vaccines and thereby producing novel M. hyopneumoniae vaccines so that the cost of prevention can be reduced.
[0008] Another object of the present invention is to provide a combination of antigens that suitable for being used in M. hyopneumoniae vaccines and thereby provide subunit vaccines with better performance; therefore, there would be more options for prevention tasks.
[0009] In order to achieve the aforesaid objects, the present invention provides a recombination protein for preparing a vaccine for preventing Mycoplasma spp. infection, comprising an amino acid sequence of SEQ ID NO: 08, SEQ ID NO: 09, SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14, or a combination thereof.
[0010] The present invention also provides a vaccine for preventing Mycoplasma spp. infection, comprising: an active ingredient, comprising a protein of PdhA, XylF, EutD, Mhp145, P78, P132, Mhp389, or a combination thereof; and a pharmaceutically acceptable adjuvant.
[0011] Preferably, said active ingredient is of a concentration of 50 to 3500 μg/mL based on the total volume of said vaccine.
[0012] Preferably, said active ingredient comprises at least two proteins selected from a group consisting of PdhA, XylF, EutD, Mhp145, P78, P132, and Mhp389.
[0013] Preferably, said active ingredient comprises PdhA and P78.
[0014] Preferably, said active ingredient comprises XylF and Mhp145.
[0015] Preferably, said pharmaceutically acceptable adjuvant is a complete Freund's adjuvant, an incomplete Freund's adjuvant, an alumina gel, a surfactant, a polyanion adjuvant, a peptide, an oil emulsion, or a combination thereof.
[0016] Preferably, said vaccine further comprises a pharmaceutically acceptable additive.
[0017] Preferably, said pharmaceutically acceptable additive is a solvent, a stabilizer, a diluent, a preservative, an antibacterial agent, an antifungal agent, an isotonic agent, an absorption delaying agent, or a combination thereof.
[0018] The present invention further provides a vaccine for preventing Mycoplasma spp. infection, comprising: an active ingredient, comprising an amino acid sequence of EQ ID NO: 08, SEQ ID NO: 09, SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14, or a combination thereof; and a pharmaceutically acceptable adjuvant.
[0019] Preferably, said active ingredient is of a concentration of 50 to 3500 μg/mL based on the total volume of said vaccine.
[0020] Preferably, said active ingredient comprises at least two amino acid sequences selected from a group consisting of SEQ ID NO: 08, SEQ ID NO: 09, SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12, SEQ ID NO: 13, and SEQ ID NO: 14.
[0021] Preferably, said active ingredient comprises amino acid sequences of SEQ ID NO: 08 and SEQ ID NO: 12.
[0022] Preferably, said active ingredient comprises amino acid sequences of SEQ ID NO: 09 and SEQ ID NO: 11.
[0023] Preferably, said pharmaceutically acceptable adjuvant is a complete Freund's adjuvant, an incomplete Freund's adjuvant, an alumina gel, a surfactant, a polyanion adjuvant, a peptide, an oil emulsion, or a combination thereof.
[0024] Preferably, said vaccine further comprises a pharmaceutically acceptable additive.
[0025] Preferably, said pharmaceutically acceptable additive is a solvent, a stabilizer, a diluent, a preservative, an antibacterial agent, an antifungal agent, an isotonic agent, an absorption delaying agent, or a combination thereof.
[0026] The present invention more provides an expression vector for preventing Mycoplasma spp. infection, comprising: a plasmid; wherein said plasmid comprises: a nucleotide sequence comprising at least one sequence selected from a group consisting of SEQ ID NO: 01, SEQ ID NO: 02, SEQ ID NO: 03, SEQ ID NO: 04, SEQ ID NO: 05, SEQ ID NO: 06, and SEQ ID NO: 07; and a regulatory element.
[0027] Preferably, said regulatory element comprises a promoter and a ribosome binding site.
[0028] Preferably, said plasmid is pET-MSY, pET-YjgD, pET-D, or pET-SUMO.
[0029] Preferably, said plasmid further comprises a gene encoding a fusion partner.
[0030] Preferably, said fusion partner is msyB of E. coli , yjgD of E. coli , protein D of Lambda bacteriophage, or SUMO of S. cerevisiae.
[0031] Preferably, said expression vector is used for an E. coli gene expression system.
[0032] To sum up, the present invention is related to antigens that are suitable for being used as the active ingredient of a M. hyopneumoniae subunit vaccine and a M. hyopneumoniae subunit vaccine/composition prepared by using the same. The present subunit vaccine not only can be effectively used in prevention task for lowering down the cost thereof, the disclosure of the present invention also shows that a “cocktail” subunit vaccine (i.e. having at least two antigens as active ingredients) using at least two antigens of the present invention has improved induction of immune response.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] FIG. 1 shows the result of the two-dimensional gel protein electrophoresis conducted in the 1 st example of the present invention.
[0034] FIG. 2 shows the result of the color reaction of the Western blot conducted in the 1 st example of the present invention.
[0035] FIG. 3 shows the result of the electrophoresis of the PCR products obtained in the 2 nd example of the present invention.
[0036] FIG. 4 shows the records of the challenge experiments conducted in the 3 rd example of the present invention.
DESCRIPTION OF REFERENCE SIGNS IN THE FIGURES
[0000]
1 XylF (xylose-binding lipoprotein)
2 XylF (xylose-binding lipoprotein)
3 XylF (xylose-binding lipoprotein)
4 PdhA (pyruvate dehydrogenase E1-alpha subunit)
5 Mhp145 (periplasmic sugar-binding protein)
6 EutD (phosphotransacetylase)
7 EutD (phosphotransacetylase)
8 Mhp389
9 P78 (lipoprotein)
10 P132
DETAILED DESCRIPTION OF THE INVENTION
[0047] One of the core concepts of the present invention is to survey potential candidate antigens suitable for subunit vaccines by using two-dimensional gel protein electrophoresis along with immunological screening technology and to identify the antigens by mass spectrometer. Then, the performance of the present subunit vaccines were verified by animal model experiments.
[0048] Briefly, the progress of the development of the present invention is:
[0049] (1) Inducing immune response of experiment pigs by injecting a conventional M. hyopneumoniae vaccine and obtaining serum containing anti- M. hyopneumoniae antibodies. (2) Obtaining total proteins of M. hyopneumoniae for two-dimensional gel protein electrophoresis. (3) Conducting hybridization of the result of the two-dimensional gel protein electrophoresis of step (2) by using the serum of step (1) as 1 st antibody, and then collecting proteins showing positive (i.e. candidate antigens) from the gel after amplification by a 2 nd antibody and the following development procedure. (4) Identifying the candidate antigens obtained in step (3). (5) Expressing said candidate antigens in large amounts by using an E. coli gene expression system. (6) Examining the efficacy of the present subunit vaccines in reducing pathological traits in lung by swine challenge experiments and thereby verifying the value of said candidate antigens in being used as active ingredient of a subunit vaccine.
[0050] The present vaccine for preventing Mycoplasma spp. infection comprises an active ingredient and a pharmaceutically acceptable adjuvant.
[0051] In an embodiment of the present invention, said active ingredient may be PdhA, XylF, EutD, Mhp145, P78, P132, or Mhp389. In an alternative embodiment, as long as the antigenic determinant of any of the aforesaid protein is not interfered, said active ingredient may be a fusion protein of any two of the aforesaid proteins. In another alternative embodiment, said active ingredient comprises at least two of the aforesaid proteins; that is, so called a “cocktail” vaccine of the present invention.
[0052] In another embodiment of the present invention, said active ingredient may comprise an amino acid sequence of SEQ ID NO: 08, SEQ ID NO: 09, SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14, or a combination thereof. In an alternative embodiment, as long as the antigenic determinant formed by folding of a peptide of said amino acid sequence is not interfered, said active ingredient may be a fusion protein with at least two said sequences. In another alternative embodiment, said active ingredient comprises two or more proteins respectively comprising one of the aforesaid amino acid sequences; that is, so called a “cocktail” vaccine of the present invention.
[0053] Said pharmaceutically acceptable adjuvant is used for improving the immune effect of said active ingredient, stabilizing said active ingredient, and/or increasing the safety of vaccines. Said pharmaceutically acceptable adjuvant of the present invention includes, but not limits to: a complete Freund's adjuvant, an incomplete Freund's adjuvant, an alumina gel, a surfactant, a polyanion adjuvant, a peptide, an oil emulsion, or a combination thereof.
[0054] The vaccine of the present invention may have one or at least two said active ingredients (i.e. a cocktail vaccine). In an example of the present vaccine, said active ingredient is of a concentration of 50 to 3500 μg/mL based on the total volume of said vaccine. In a preferable embodiment of the present invention, when said vaccine comprises only one said active ingredient, said active ingredient is of a concentration of 50 to 500 μg/mL based on the total volume of said vaccine. In an alternative embodiment of the present invention, the present vaccine comprises at least one said active ingredient; wherein the total concentration of said active ingredient(s) contained in said vaccine is 50 to 1000 μg/mL, 50 to 1500 μg/mL, 50 to 2000 μg/mL, 50 to 2500 μg/mL, 50 to 3000 μg/mL, or 50 to 3500 μg/mL based on the total volume of said vaccine.
[0055] Another aspect of the present invention is to provide an expression vector for preventing Mycoplasma spp. infection. Specifically, said expression vector may be used for an E. coli gene expression system. Nevertheless, without being apart from the spirit of the present invention, those having ordinary skill in the art can modify said vector based on the disclosure of the present invention and make said vector suitable for different gene expression system while still belongs to the scope of the present invention.
[0056] Said expression vector comprises a plasmid. Said plasmid comprises: a nucleotide sequence comprising at least one sequence selected from a group consisting of SEQ ID NO: 01, SEQ ID NO: 02, SEQ ID NO: 03, SEQ ID NO: 04, SEQ ID NO: 05, SEQ ID NO: 06, SEQ ID NO: 07, and a combination thereof; and a regulatory element.
[0057] Said vector is used in an E. coli gene expression system and for producing the antigens of the present invention via E. coli . In other words, said nucleotide sequence can be translated into the amino sequence of the present antigen via an E. coli gene expression system and then the amino acid sequence can fold into the present antigen.
[0058] In an alternative embodiment, as long as the operation of the E. coli gene expression system is not hindered and the production of said nucleotide sequence and the folding of the consequent amino acid sequence thereof are not interfered, said plasmid may comprise two or more said nucleotide sequences.
[0059] Said regulatory element is referred to an element required for initiating the transcription and translation in the expression system. Said regulatory element shall at least comprise a promoter, and a ribosome binding site. Preferably, said regulatory element may further comprise: an operator, an enhancer sequence, or a combination thereof.
[0060] In a preferable embodiment of the present invention, said plasmid further comprises a gene encoding a fusion partner. Said fusion partner includes but not limits to msyB of E. coli , yjgD of E. coli , protein D of Lambda bacteriophage, or SUMO of S. cerevisiae . Said MsyB is rich in acidic amino acid and might be favorable for improving the solubility of the proteins to be produced.
[0061] The following examples recite the trials and experiments of the present invention in order to further explain the features and advantages of the present invention. It shall be noted that the following examples are exemplary and shall not be used for limiting the claim scope of the present invention.
Example 1
Screening for Candidate Antigens Suitable for being Used as Active Ingredient of a Subunit Vaccine
[0062] Preparation of Serum Containing Anti-Swine Mycoplasm Spp. Antibody.
[0063] According to researches, there are seven Mycoplasm spp. can be isolated from swine: Mycoplasm hyopneumoniae, Mycoplasma hyorhinis, Mycoplasma hyosynoviae, Mycoplasma flocculare, Mycoplasma hyopharyngis, Mycoplasma sualvi, Mycoplasma bovigenitalium (Gourlay et al., 1978; Blank et al., 1996; Assuncao et al., 2005). Among them, M. hyopneumoniae is the major pathogen of swine enzootic pneumonia with an infection rate of 25 to 93%. Therefore, the present invention used M. hyopneumoniae (PRIT-5 strain) for immune proteomics studies and as sources of genes encoding antigens. Friis medium (Friis et al., 1975) as used for culturing M. hyopneumoniae . According to the experiment design, a proper amount of antibiotic or agar of 1.5% was added to formulating a solid medium.
[0064] Three SPF pigs of 4-week old were brought from Agricultural Technology Research Institute and fed with same feed and kept at same environment and growth condition in piggery before experiments.
[0065] After the pigs were fed to 32-day, 46-day, and 60-day old, the pigs were administrated 2 mL of Bayovac® MH-PRIT-5 ( M. hyopneumoniae PRIT-5) vaccine via intramuscular injection. Then, the pigs were continuously fed to 74-day old and blood was collected from a jugular vein thereof. The collected blood was placed in room temperature for 1 hour and stored in 4° C. In the next day, the collected blood was centrifugated at 1,107×g for 30 minutes and the supernatant was removed to a clean tube and stored in −20° C.
Two-Dimensional Gel Protein Electrophoresis of the Total Protein of Mycoplasm Spp.
[0066] ReadyPrep™ protein extraction kit (total protein) (Bio-Rad, CA, USA) was used for extracting the total protein of Mycoplasm spp. Afterward, the concentration of the protein collected was determined by using a Bio-Rad RC DC Protein Assay Kit (CA, USA). The detailed protocol can be referred from the product description or can be modified from well-known protocols in the field.
[0067] The two-dimensional gel protein electrophoresis was conducted in two steps: isoelectric focusing (IEF) and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). IEF was to separate proteins in the sample in view of isoelectric point thereof; SDS-PAGE was to separate proteins accordance with molecular weight thereof. Please see FIG. 1 , which shows the result of the two-dimensional gel protein electrophoresis.
Hybridization
[0068] The serum obtained in step (1) was used as 1 st antibody to hybridize with the result of the two-dimensional gel protein electrophoresis in step (2). After being amplified by 2 nd antibody and developed by the following development procedure, proteins showing positive were collected. Those proteins were recognized by the anti- Mycoplasm spp. antibody and therefore would be suitable as candidate antigens for active ingredient of subunit vaccines.
[0069] The hybridization was conducted by Western blotting. Briefly, the 2D gel after electrophoresis was transferred to a PVDF membrane. Then, the membrane was incubated and hybridized sequentially with 1 st antibody (the serum containing anti- Mycoplasm spp. antibody) and 2 nd antibody (AP-conjugated anti-pig IgG). Afterward, a color reaction was conducted by using NBT/BCIP solution.
[0070] The result of the color reaction of Western blotting was shown in FIG. 2 ; wherein 10 proteins positive to the immuno-hybridization with anti- Mycoplasm spp. antibody were marked as candidate antigens for being used as active ingredients of subunit vaccines.
Identification of the Candidate Antigens Obtained
[0071] According to the color reaction of the Western blotting, the gel corresponding to the positive location on the membrane was cut by micropeptide and analyzed by mass spectrometry. The obtained data of the mass spectrometry was then matched with amino acid sequence and protein database to identify those proteins.
[0072] Please see the following table 1, said 10 proteins positive to the immune-hybridization with anti- Mycoplasm spp. antibody were listed.
[0000]
TABLE 1
the 10 proteins positive to the immune-hybridization with
anti- Mycoplasm spp. antibody and amino sequence thereof.
Candidate
Name
SEQ ID NO
1
XylF (xylose-binding lipoprotein)
SEQ ID NO: 09
2
XylF (xylose-binding lipoprotein)
SEQ ID NO: 09
3
XylF (xylose-binding lipoprotein)
SEQ ID NO: 09
4
PdhA (pyruvate dehydrogenase E1-alpha
SEQ ID NO: 08
subunit)
5
Mhp145 (periplasmic sugar-binding
SEQ ID NO: 11
protein)
6
EutD (phosphotransacetylase)
SEQ ID NO: 10
7
EutD (phosphotransacetylase)
SEQ ID NO: 10
8
Mhp389
SEQ ID NO: 14
9
P78 (lipoprotein)
SEQ ID NO: 12
10
P132
SEQ ID NO: 13
* XylF and EutD have different charge states in cells and therefore become 3 and 2 positive location on the membrane.
Example 2
Expressing of Said Candidate Antigens in Large Amount by E. coli Gene Expression System
[0073] Escherichia coli JM109 was used as the host cells for cloning and Escherichia coli BL21 (DE3) was used as the host cells for protein expression. The Escherichia coli cells were cultured in LB medium (Luria-Bertani; Difco, Mich., USA). According to the experiment design, a proper amount of antibiotic or agar of 1.5% was added to formulating a solid medium.
Amplification of the Genes Encoding the Candidate Antigens
[0074] After the candidate antigens were identified, the genes encoding those antigens were searched in the NCBI database (National Center for Biotechnology Information). Specific primers targeting the antigen genes were designed accordingly. Then, the antigen genes were amplified by using the specific primers and the chromosome of M. hyopneumoniae PRIT-5 as template. The specific primers used were listed in the following table 2.
[0000]
TABLE 2
Primer set.
Candidate
Sequences of the primer set
PdhA
PdhAF (SEQ ID NO: 15)
5′-GATATAGGATCCATGGACAAATTTCGCTATGTAAAGC
CT G-3′
PdhAR (SEQ ID NO: 16)
5′-CAATATGTCGACTTATTTTACTCCTTTAAAAAATTCA
AGCGCTTC-3′
XylF
XylFF (SEQ ID NO: 17)
5′-GATATAGGATCCATGAATGGAATAAATTTCTTGGCTT
AGGCTTAGTTTTTC-3′
XylFR (SEQ ID NO: 18)
5′-CAATATGTCGACTTAATTTTTATTAATATCGGTAATT
AGTTTGTCTAAGC-3′
EutD
EUTDF (SEQ ID NO: 19)
5′-GATATAGGATCCATGACATACCAAGAATATCTTCAAG
CAAG-3′)
EUTDR (SEQ ID NO: 20)
5′-CAATATGTCGACCTATTTACCTTCTTCAAC
TTGTAGAGCGCT-3′)
Mhp145
Mhp145F (SEQ ID NO: 21)
5′-GATATAGGATCCATAGCTTCAAGGTCGAA
TACAACTGC-3′
Mhp145R (SEQ ID NO: 22)
5′-CAATATGTCGACTTAATTTACCTTTTGGAG
TATCCCATTTTC-3′
P78
P78F (SEQ ID NO: 23)
5′-GATATAGGATCCTTATCCTATAAATTTAGG
CGTTTTTTCC-3′
P78R (SEQ ID NO: 24)
5′-CAATATGTCGACTTATTTTGATTTAAAAGCAGGACCT
AA AT-3′
P132
P132F (SEQ ID NO: 25)
5′-GATATAGGATCCATTGGACTAACAATTTTTGAGAAAT
CATTTAG-3′
P132R (SEQ ID NO: 26)
5′-CAATATGTCGACTTATTCCTAAATAGCCCC
ATAAAGTG-3′
Mhp389
Mhp389F (SEQ ID NO: 27)
5′-GATATAGGATCCATGGACAAATTTTCACGA
ACTGTTCT-3′
Mhp389R (SEQ ID NO: 28)
5′-CAATATGTCGACCTAGATTTTAAAGGATTTTTTTAAT
TCAATAATATAATC-3′
[0075] Polymerase chain reaction (PCR) was conducted with the primer sets listed in the table 2 above to amplify the genes of the candidate antigens. The amplified genes were then used in the E. coli gene expression system. The PCR condition was: 5 minutes in 98° C. (one round); 30 seconds in 94° C., 30 seconds in 55° C., X seconds in 68° C. (35 rounds); 5 minutes in 68° C. (one round). Said X was the elongation time for the DNA polymerase and was set depending on the size of the fragment to be amplified. After the PCR reaction, an electrophoresis was conducted to verify if the PCR products contained the DNA fragments of expected size. Please see FIG. 3 , which shows the electrophoresis result of the PCR products; wherein lane 1 was eutD gene; lane 2 was pdhA; lane 3 was xylF; lane 4 was P78 gene; lane 5 was P132 gene; lane 6 was mhp145; lane 7 was mhp389.
Cloning of the PCR Products
[0076] The cloning was conducted by using a CloneJET PCR Cloning Kit, and the ligation mixture was transformed into E. coli ECOS™ 9-5 (Yeastern, Taipei, Taiwan). The detailed protocol can be referred from the product description or modified from the well-known protocol in the field.
[0077] After transformation, the bacteria were cultured on a solid LB medium containing ampicillin (100 μg/mL) until colony thereof formed. Then, colony PCR was conducted to screen strains success in transformation. The PCR condition was: 5 minutes in 95° C. (one round); 30 seconds in 95° C., 30 seconds in 55° C., X seconds in 72° C. (25 rounds); 7 minutes in 72° C. (one round). Said X was the elongation time for the DNA polymerase and was set depending on the size of the fragment to be amplified. The elongation speed of Taq DNA polymerase (Genomics, Taipei, Taiwan) is 1 kb/min; therefore, if Taq DNA polymerase is used for amplifying a 1 kb DNA fragment, said X shall be set as 1 minute.
[0078] The plasmids of strains, whose recombinant plasmids were verified having the insert DNA, were then proceeded to DNA sequencing (Total Solution Provider of Systems Biology and Chemoinformatics Ltd.). Plasmids containing eutD, pdhA, xylF, P78 gene, P132 gene, mhp145, and mhp389 were named as pJET-eutD, pJET-pdhA, pJET-xylF, pJET-P78, pJET-P132, pJET-mhp145, pJET-mhp389, respectively.
Point Mutation and Cloning of the Antigen Genes of M. hyopneumoniae
[0079] Before amplifying the candidate antigens in an E. coli gene expression system, the codon usage in different organisms shall be considered. That said, if the gene contains codon that would be encoded ambiguously between the original organism therefrom and E. coli , the gene shall be modified by point mutation.
[0080] The M. hyopneumoniae antigen genes, pdhA, xylF, P78 gene, P132 gene, mhp145, and mhp389, contain TGA codon (eutD does not have the concern in codon usage like others). The TGA codon was translated into tryptophan in Mycoplasma spp. but translated as stop codon in E. coli . In order to prevent from not being able to produce the entire protein in an E. coli gene expression system, primers targeting the TGA site were designed and point mutation replacing TGA with TGG was conducted by using overlapping extension polymerase chain reaction. As a result, the genes to be expressed in the E. coli gene expression system can be truthfully translated into the candidate antigen of the present invention. Besides, the cutting sites of BamHI of P78 gene, P132 gene, and mhp389 were undergone silent mutation for the convenience of cloning.
[0081] The primers used for point mutation was designed to locate the site of point mutation at the central part of the primer and to have a Tm value of higher than 78° C. The Tm value of the primers for point mutation was calculated by using the formula provided by Invitrogene Co.: Tm=81.5+0.41 (% GC)−675/N-% mismatch; wherein % GC is referred as the percentage of GC in view of the total nucleotides contained in the primer concerned; N is referred as the length of the primer concerned; % mismatch is referred as the percentage of the base to be mutated in view of the total nucleotides contained in the primer concerned. The primer sets used for the aforesaid genes were listed in the following Table 3 to Table 8.
[0000]
TABLE 3
The primer sets for point mutation of pdhA.
Primer
DNA sequence (5′ to 3′)
PdhAF
GATATAGGATCCATGGACAAATTTCGCTATGTAA
SEQ ID NO: 29
AGCCTG
PdhAM1
GCTAACAAAAGATGACTGGTTTGTCCCAGCTTTT
SEQ ID NO: 30
CG
PdhAM2
CGAAAAGCTGGGACAAACCAGTCATCTTTTGTTA
SEQ ID NO: 31
GC
PdhAM3
CTTGCAAATGCAATATTGGAATGGTAGCGAAAAA
SEQ ID NO: 32
GG
PdhAM4
CCTTTTTCGCTACCATTCCAATATTGCATTTGCA
SEQ ID NO: 33
AG
PdhAM5
CGAGGCGCTAAATATTGCAAGTATTTGGAAATGG
SEQ ID NO: 34
CCAGTTGTTTTTTGCGTAAATAAC
PdhAM6
GTTATTTACGCAAAAAACAACTGGCCATTTCCAA
SEQ ID NO: 35
ATACTTGCAATATTTAGCGCCTCG
PdhAM7
GTTTTTTGCGTAAATAACAATCAATGGGCAATTT
SEQ ID NO: 36
CAACCCCAAATAAATATG
PdhAM8
CATATTTATTTGGGGTTGAAATTGCCCATTGATT
SEQ ID NO: 37
GTTATTTACGCAAAAAAC
PdhAM9
GTTGAGTTTGTAACTTGGCGTCAAGGTGTTCATA
SEQ ID NO: 38
CC
PdhAM10
GGTATGAACACCTTGACGCCAAGTTACAAACTCA
SEQ ID NO: 39
AC
PdhAM11
GAGAACACGAAAAATGGGAACCAATGCACCGG
SEQ ID NO: 40
PdhAM12
CCGGTGCATTGGTTCCCATTTTTCGTGTTCTC
SEQ ID NO: 41
PdhAM13
CCGAAAAACAAAAAATTTGGGATGAAGCGCTTGC
SEQ ID NO: 42
GATTG
PdhAM14
CAATCGCAAGCGCTTCATCCCAAATTTTTTGTTT
SEQ ID NO: 43
TTCGG
PdhAR
CAATATGTCGACTTATTTTACTCCTTTAAAAAAT
SEQ ID NO: 44
TCAAGCGCTTC
[0000]
TABLE 4
The primer sets for point mutation of xylF.
Primer
DNA sequence (5′ to 3′)
XylFF
GATATAGGATCCATGAAATGGAATAAATTTCTTG
SEQ ID NO: 45
GCTTAGGCTTAGTTTTTC
XylFM1
CATTTAACCAATCAAGTTGGGAGGCAATTCAACA
SEQ ID NO: 46
ACTTGG
XylFM2
CCAAGTTGTTGAATTGCCTCCCAACTTGATTGGT
SEQ ID NO: 47
TAAATG
XylFM3
CTAATACCAACAAAAATGTTTGGGTACTTTCTGG
SEQ ID NO: 48
TTTTCAACACG
XylFM4
CGTGTTGAAAACCAGAAAGTACCCAAACATTTTT
SEQ ID NO: 49
GTTGGTATTAG
XylFM5
CGGTGATGCGATCACAAAATGGTTAAAAATCCCT
SEQ ID NO: 50
GAAAATAAGC
XylFM6
GCTTATTTTCAGGGATTTTTAACCATTTTGTGAT
SEQ ID NO: 51
CGCATCACCG
XylFM7
TTATCATACTCGGAATTGACTGGACTGATACTGA
SEQ ID NO: 52
AAATGTAATTC
XylFM8
GAATTACATTTTCAGTATCAGTCCAGTCAATTCC
SEQ ID NO: 53
GAGTATGATAA
XylFM9
GAAGAAGCCGGATGGCTTGCAGGATATGC
SEQ ID NO: 54
XylFM10
GCATATCCTGCAAGCCATCCGGCTTCTTC
SEQ ID NO: 55
XylFM11
GGTTATCTAGCCGGAATTAAAGCTTGGAATCTAA
SEQ ID NO: 56
AAAATTCTGATAAAAAAAC
XylFM12
GTTTTTTTATCAGAATTTTTTAGATTCCAAGCTT
SEQ ID NO: 57
TAATTCCGGCTAGATAACC
XylFR
CAATATGTCGACTTAATTTTTATTAATATCGGTA
SEQ ID NO: 58
ATTAGTTTGTCTAAGC
[0000]
TABLE 5
The primer sets for point mutation of P78 gene.
Primer
DNA sequence (5′ to 3′)
P78F
GATATAGGATCCTTATCCTATAAATTTAGGCGTTTT
SEQ ID NO: 59
TTCC
P78M1
CAATTAATAAAGTTTTGTTTGGTTGGATGATTAATA
SEQ ID NO: 60
AAGCACTTGCTGATCC
P78M2
GGATCAGCAAGTGCTTTATTAATCATCCAACCAAAC
SEQ ID NO: 61
AAAACTTTATTAATTG
P78M3
GATATTAAAGAAATTGAAAGAATCTGGAAAAAATAT
SEQ ID NO: 62
GTCTCCGATGATCAAGG
P78M4
CCTTGATCATCGGAGACATATTTTTTCCAGATTCTT
SEQ ID NO: 63
TCAATTTCTTTAATATC
P78M5
GCCCTTTCAGGAGGCTCCACTGATTCGGCA
SEQ ID NO: 64
P78M6
TGCCGAATCAGTGGAGCCTCCTGAAAGGGC
SEQ ID NO: 65
P78M7
GCCGCAAAAGCTTTTGTTAAATGGCTTTTGACAGAA
SEQ ID NO: 66
AAAATAGTCT
P78M8
AGACTATTTTTTCTGTCAAAAGCCATTTAACAAAAG
SEQ ID NO: 67
CTTTTGCGGC
P78R
CAATATGTCGACTTATTTTGATTTAAAAGCAGGACC
SEQ ID NO: 68
TAAAT
[0000]
TABLE 6
The primer sets for point mutation of P132 gene.
Primer
DNA sequence (5′ to 3′)
P132F
GATATAGGATCCATTGGACTAACAATTTTTGAGAAA
SEQ ID NO: 69
TCATTTAG
P132M1
CTAACTTCTCTAAAAGGTTGGAAAGAAGAAGATGAT
SEQ ID NO: 70
TTTG
P132M2
CAAAATCATCTTCTTCTTTCCAACCTTTTAGAGAAG
SEQ ID NO: 71
TTAG
P132M3
CTTTCTATTACTTTTGAACTCTGGGACCCAAATGGT
SEQ ID NO: 72
AAATTAGTATC
P132M4
GATACTAATTTACCATTTGGGTCCCAGAGTTCAAAA
SEQ ID NO: 73
GTAATAGAAAG
P132M5
CCCTGAAGGAGATTGGATAACTTTAGGGAG
SEQ ID NO: 74
P132M6
CTCCCTAAAGTTATCCAATCTCCTTCAGGG
SEQ ID NO: 75
P132M7
CTACCAGGAACTACCTGGGATTTCCATGTTGAAC
SEQ ID NO: 76
P132M8
GTTCAACATGGAAATCCCAGGTAGTTCCTGGTAG
SEQ ID NO: 77
P132M9
GGACAACTAATTTGGAGCCAGTTAGCTTCC
SEQ ID NO: 78
P132M10
GGAAGCTAACTGGCTCCAAATTAGTTGTCC
SEQ ID NO: 79
P132M11
GGAACAAAAAAGGAATGGATTCTTGTAGGATCTGG
SEQ ID NO: 80
P132M12
CCAGATCCTACAAGAATCCATTCCTTTTTTGTTCC
SEQ ID NO: 81
P132M13
CCAATACGCAAATATGGATAACCCGTCTAGGAAC
SEQ ID NO: 82
P132M14
GTTCCTAGACGGGTTATCCATATTTGCGTATTGG
SEQ ID NO: 83
P132M15
CCAAGGGGAAGTTCTCTGGACTACTATTAAATCCAA
SEQ ID NO: 84
AC
P132M16
GTTTGGATTTAATAGTAGTCCAGAGAACTTCCCCTT
SEQ ID NO: 85
GG
P132M17
CAAAAAACTTCACCTTTGGTGGATTGCTAATGATAG
SEQ ID NO: 86
C
P132M18
GCTATCATTAGCAATCCACCAAAGGTGAAGTTTTTT
SEQ ID NO: 87
G
P132R
CAATATGTCGACT TATTCCTAAATAGCCCCATAAA
SEQ ID NO: 88
GTG
[0000]
TABLE 7
The primer sets for point mutation of mhp145.
Primer
DNA sequence (5′ to 3′)
Mhp145F
GATATAGG ATCCAT AGCTTCAAGGTCGAATACAA
SEQ ID NO: 89
CTGC
Mhp145M1
AATAATTGCAGAAAAAATTCTTAAAGATCAATGGAA
SEQ ID NO: 90
AACAAGTAAATATTCTGATTTTTATTCACAAT
Mhp145M2
ATTGTGAATAAAAATCAGAATATTTACTTGTTTTCC
SEQ ID NO: 91
ATTGATCTTTAAGAATTTTTTCTGCAATTATT
Mhp145R
CAATATGTCGACTTA ATTTACCTTTTGGAGTATCC
SEQ ID NO: 92
CATTTTC
[0000]
TABLE 8
The primer sets for point mutation of mhp389.
Primer
DNA sequence (5′ to 3′)
Mhp389F
GATATAGGATCCATGGACAAATTTTCACGAACTGTT
SEQ ID NO: 93
CT
Mhp389M1
CAATAGTGACAATGGACCCCCCAAATGTTGGTCG
SEQ ID NO: 94
Mhp389M2
CGACCAACATTTGGGGGGTCCATTGTCACTATTG
SEQ ID NO: 95
Mhp389M3
GATAAAGGCGCATCATGGCTTGCGCTTGCACCAAC
SEQ ID NO: 96
Mhp389M4
GTTGGTGCAAGCGCAAGCCATGATGCGCCTTTATC
SEQ ID NO: 97
Mhp389M5
GGAAAACTTAAAGGTAAATGGACTTTTGGACTAACC
SEQ ID NO: 98
TATTT
Mhp389M6
AAATAGGTTAGTCCAAAAGTCCATTTACCTTTAAGT
SEQ ID NO: 99
TTTCC
Mhp389R
CAATATGTCGACCTAGATTTTAAAGGATTTTTTTAA
SEQ ID NO: 100
TTCAATAATATAATC
[0082] The method for the point mutation was briefly explained as follows. The chromosome of M. hyopneumoniae PRIT-5 was used as template and DNA fragments was amplified by using the primer sets set forth in the table 3 to table 8 above.
[0083] The 50 μL PCR reaction mixture comprised 1×GDP-HiFi PCR buffer, 200 μM of mixture of dATP, dTTP, dGTP, and dCTP, 1 μM of primers, 100 ng of chromosome of M. hyopneumoniae PRIT-5, and 1 U of GDP-HiFi DNA polymerase. The PCR condition was: 5 minutes in 98° C. (one round); 30 seconds in 94° C., 30 seconds in 55° C., X seconds in 68° C. (35 rounds); 5 minutes in 68° C. (one round). Said X was the elongation time for the DNA polymerase and was set depending on the size of the fragment to be amplified. The elongation speed of GDP-HIFI DNA polymerase (GeneDirex, Las Vegas, USA) is 1 kb/15 seconds; therefore, if GDP-HIFI DNA polymerase is used for amplifying a 1 kb DNA fragment, said X shall be set as 15 seconds. After the PCR reaction, an electrophoresis was conducted to verify if the PCR products contained the DNA fragments of expected size. Then, the PCR product was recycled by using a Gel-M™ gel extraction system kit.
[0084] Afterward, the PCR product was used as template and amplified by using the primer sets set forth in the table 2 above. The PCR condition was: 2 minutes in 98° C. (one round); 30 seconds in 94° C., 30 seconds in 55° C., X seconds in 68° C. (35 rounds); 5 minutes in 68° C. (one round). Said X was the elongation time for the DNA polymerase and was set depending on the size of the fragment to be amplified. The elongation speed of GDP-HIFI DNA polymerase (GeneDirex, Las Vegas, USA) is 1 kb/15 seconds; therefore, if GDP-HIFI DNA polymerase is used for amplifying a 1 kb DNA fragment, said X shall be set as 15 seconds. After the aforesaid amplification step, a full length sequence of the candidate antigen genes with point mutation can be obtained.
[0085] Then, the PCR product was recycled by using a PCR-M™ Clean Up system kit (GeneMark, Taichung, Taiwan) and the cloning thereof was conducted by using a CloneJET PCR Cloning Kit. Colony PCR was conducted to confirm the strains after transformation containing plasmid having the insert DNA and then the plasmids therein were isolated for DNA sequencing (Total Solution Provider of Systems Biology and Chemoinformatics Ltd.). Plasmids containing mutated candidate antigen genes were named as pJET-pdhAM, pJET-xylFM, pJET-P78M, pJET-P132M, pJET-mhp145M, pJET-mhp389M, respectively.
[0086] According to the result of sequencing, the DNA sequences of the candidate antigen genes after point mutation were as shown in SEQ ID NO:01 (pdhA), SEQ ID NO:02 (xylF), SEQ ID NO:03 (eutD, was not point-mutated), SEQ ID NO:04 (mhp145), SEQ ID NO:05 (P78 gene), SEQ ID NO:06 (P132 gene), SEQ ID NO:07 (mhp389).
Construction of the Expression Vectors for Expressing the M. hyopneumoniae Antigens
[0087] In this part of experiments, plasmid pET-MSY was used as backbone for constructing an expression vector for expressing M. hyopneumoniae antigen. pET-MSY is a derivative of pET29a and has a E. coli msyB. Therefore, the expressed recombinant antigen thereby would have a fusion partner MsyB. MsyB is rich in acidic amino acid and is able of increasing the solubility of the protein expressed.
[0088] After pJET-eutD, pJET-pdhA, pJET-xylF, pJET-P78, pJET-P132, pJET-mhp145 and pJET-mhp389 being digested by BamHI and SalI, DNA fragment obtained was inserted into pET-Msy digested previously with the same restriction enzymes by ligase. Then, the pET-Msy with the DNA fragment was transformed into E. coli ECOS 9-5. Colony PCR was conducted to confirm the strains after transformation containing plasmid having the insert DNA and then the plasmids therein were isolated for DNA sequencing (Total Solution Provider of Systems Biology and Chemoinformatics Ltd.). Plasmids verified with correct DNA sequence were named as pET-MSYEutD, pET-MSYPdhA, pET-MSYXylF, pET-MSYP78, pET-MSYP132, pET-MSYMhp145, and pET-MSYMhp389, respectively. Those plasmids obtained were examples of the expression vectors for preventing Mycoplasma spp. infection of the present invention.
Expression and Isolation of the M. hyopneumoniae Antigens
[0089] The vectors for antigen expression were transformed into E. coli BL21 (DE3). Single colony of consequent strains after transformation was inoculated in LB liquid medium containing kanamycin (working concentration: 30 μg/mL). After culture overnight at 37° C., 180 rpm, the suspension of the bacteria was diluted at ratio of 1:100 and inoculated again in another LB liquid medium containing kanamycin (working concentration: 30 μg/mL). The bacteria were cultured at 37° C., 180 rpm until OD 600 therefore achieving about 0.6 to 0.8. Then, 0.1 mM of IPTG was added to induce expression. After induction for 4 hours, pellet was collected by centrifugation (10000×g, 10 minutes, 4° C.) and the expression was examined via protein electrophoresis.
[0090] Afterward, immobilized-metal affinity chromatography (IMAC) was used for protein isolation through the covalent bonding between the His tag of the N-terminal of the recombinant protein and nickel ions or cobalt ions. The protocol of protein isolation was in accordance with the product description of the QIAexpressionist™ (fourth edition, Qiagen). The pellet was suspended in a lysis buffer (50 mM NaH 2 PO 4 , 300 mM NaCl, 10 mM imidazole, pH 8.0) and disturbed by an ultrasonic processer. After centrifugation (8,000×g, 15 minutes), the supernatant was collected to introduce into a column of 1 mL Ni-NTA resin. The recombinant antigens would adhere on said resin. Then, 15 mL wash buffer (50 mM NaH 2 PO 4 , 300 mM NaCl, 20 mM imidazole, pH 8.0) was introduced into the column to wash the resin so that nonspecific proteins adhering thereon can be removed. Lastly, 20 mL elution buffer was added (50 mM NaH 2 PO 4 , 300 mM NaCl, 250 mM imidazole, pH 8.0) to wash off the recombinant antigens on the resin; wherein the imidazole of high concentration can compete the binding site on the resin with the recombinant proteins and thereby cause the recombinant proteins being washed off. The result of isolation was then examined by protein electrophoresis.
[0091] The candidate antigens of the present invention collected by isolation can then be used for the following immune trials to confirm their ability to be used as active ingredient of anti- Mycoplasm spp. subunit vaccines.
Example 3
Swine Immune Challenge Experiments of the Candidate Antigens of the Present Invention
[0092] In this example, the candidate antigens of the present invention were used as active ingredient for preparing subunit vaccines and tested for immune effects thereof in live swine.
Vaccine Preparation
[0093] One isolated recombinant antigen or several isolated recombinant antigens were mixed with alumina gel as an adjuvant to prepare a subunit vaccine or a cocktail subunit vaccine. Every dose of the prepared vaccine was of 2 mL in volume and each kind of antigen contained therein was of 100 μg.
[0094] The following table 9 listed the samples prepared in this example for immune challenge experiments.
[0000]
TABLE 9
Samples of vaccine prepared in Example 3
Sample
Active Ingredient (Antigen)
1
PdhA
2
XylF
3
EutD
4
Mhp145
5
P78
6
P132
7
Mhp389
8
PdhA + P78
9
XylF + Mhp145
[0095] The swine immune challenge experiments would be conducted by using Bayovac® MH-PRIT-5 (made by using M. hyopneumoniae PRIT-5, as a positive control group), subunit vaccines (samples 1-7 of the present invention), and cocktail vaccines (samples 8 and 9 of the present invention).
[0096] 33 SPF pigs of 4-week old were brought from Agricultural Technology Research Institute and fed with same feed, environment, and growth condition in piggery before experiments.
[0097] After the pigs were fed to 35-day and 49-day old, the pigs were administrated 2 mL of vaccine above via intramuscular injection.
Challenge Experiments
[0098] The aforesaid pigs being induced immune response were challenged by Mycoplasm spp. at 109-day old to confirm the immune effect of the aforesaid vaccines.
[0099] First of all, a lung collected from pigs infected by Mycoplasm spp. was ground in 20 mL of Friis medium and centrifugated at 148.8×g for 10 minutes. The supernatant was removed to a clean tube and centrifugated again at 7,870×g for 40 minutes. Then, the supernatant was discarded and the precipitation was suspended in 6 mL of Friis medium to obtain a suspension. Afterward, the suspension was filtered by membrane of 5 μm and 0.45 μm sequentially to obtain bacteria solutions required for the challenge experiments.
[0100] The bacteria solution (5 mL) was administrated to narcotized pigs via trachea thereof. After 28 days from administration, the pigs were sacrificed and dissected to collect lung thereof. The immune effect was examined by observing the lung and recorded according to the following criteria: any of meddle upper lobes and upper lobes of any side of the lung observed of pathological trait was scored as 10 points; any of meddle upper lobe and diaphragmatic lobes of any side of the lung observed of pathological trait was scored as 5 points. The full score was 55 points. The observation records were shown in FIG. 4 .
[0101] In comparison with the results of non-injected pigs, the seven candidate antigens of the present invention were able to provide equivalent immune effects as conventional vaccine (Bayovac® MH-PRIT-5). If the higher safety of subunit vaccines is taking into consideration, the vaccines containing the candidate antigens of the present invention shall be valued more.
[0102] On the other hand, it was not common to use two or more antigens that would induce immune effects in one vaccine because the two or more antigens may not provide doubled immune effect. In fact, there is higher chance that the two or more antigens may interfere or against each other and consequently reduce the immune effect of the vaccine. According to the result of this example, sample 8 and sample 9 of the present invention (i.e. cocktail vaccine) unexpectedly provide significant increase in the immune effect. That said, the subunit vaccines of the present invention not only have high safety but also provide better immune effect when the candidate antigens of the present invention are used in combination.
[0103] Those having ordinary skill in the art can readily understand any possible modifications based on the disclosure of the present invention without apart from the spirit of the present invention. Therefore, the examples above shall not be used for limiting the present invention but intend to cover any possible modifications under the spirit and scope of the present invention according to the claims recited hereinafter.
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Provided in the present invention are anti- Mycoplasma spp. subunit vaccines, especially proteins suitable for being used as the active ingredient of the Mycoplasma spp. subunit vaccines, and a vaccine prepared therefrom. Upon experimenting, it is confirmed that the proteins can elicit an immune response having sufficient strength to avoid the infection of Mycoplasma spp. in pigs. The vaccine can comprise one of the aforementioned proteins as an active ingredient, or can comprise two or more of the proteins to form a form of cocktail vaccine. The vaccine of the present invention is not only more safe than conventional vaccines, but also has equivalent or even better immune effects.
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BACKGROUND OF THE INVENTION
This invention relates to a variable bearing assembly. More specifically, the subject invention relates to an apparatus for providing a variable vertical and lateral bearing for a support leg of an offshore jack-up platform.
In the past, offshore platforms or towers have been extensively utilized around and upon the continental shelf regions of the world. Examples of offshore platform facilities include supports for radar stations, light beacons, scientific and exploration laboratories, chemical plants, power generating plants, mining stations, etc. Principally, however, offshore platforms have been utilized by the oil and gas industry in connection with drilling, production and/or distribution operations.
In conducting such offshore activity, several platform designs have been utilized by the industry. In deep water applications, semi-submersibles or drillships, which are dynamically positioned and/or turret moored over a well site, have been effectively employed. Although semi-submersibles and drillships are highly mobile and widely utilized in deep water applications, the initial cost and subsequent operating expense reduces the desirability of such units for use in shallow water or intermediate depth applications.
In shallow water situations, fixed length towers or platforms have been extensively utilized. Such platforms are normally fabricated on shore and transported in a generally horizontal posture to an offshore site upon a barge or buoyancy chambers within the platform legs. On site, the platform is pivoted into an upright posture and the base is positioned into firm bearing engagement with the seabed. A platform deck is then fabricated upon the erected tower for conducting offshore operations. Such fixed platforms, although economical in relatively shallow water, require considerable time to assemble and once in position are difficult to relocate.
One platform design which combines many of the advantages of floating and fixed equipment is known as a "jack-up" platform. In this connection a jack-up platform typically comprises a barge or self propelled hull operable to function in a conventional flotation capacity during transportation and as a working deck on location. The hull is fitted with one or more legs which are operable to be vertically extended downward from the deck and into supporting engagement with the seabed.
In operation a jack-up platform is either towed or navigated to a desired offshore site with the jack-up legs extending through wells fashioned through the hull. On site the legs are jacked downward into firm bearing engagement with the seabed. Further jacking serves to raise the hull/deck with respect to the surface of the body of water. Once the lowermost portion of the deck is elevated above a statistical storm wave height, jacking is discontinued and drilling and/or production operations are begun from the elevated deck. Upon completion of the desired offshore operations the deck is jacked down to the surface of the body of water and the legs are jacked up. The platform is then towed or navigated to another working station and the process is repeated. Because of its mobility and versatility, jack-up platforms have emerged as one of the most desirable forms of platform design in the industry.
The subject invention is specifically directed to a jack-up platform variable bearing assembly wherein a novel lost motion footing assembly provides enhanced vertical and lateral stability to a platform leg and in addition facilitates transportation of the platform to a working site and retrieval of the platform legs following working at the site.
The seabed is composed of variant soils and deposits but typically the seabed has a relatively soft upper surface with varying layers of firmer soil strata as the upper layer is penetrated. In some instances relatively loose soils extend downwardly several feet from the surface and in other locations rock or very firm soils lie rather shallow beneath the surface of the seabed.
In order to securely support a jack-up platform in the open sea it is desirable in one sense to provide a fairly large footing at the end of each leg so that vertical loads can be spread over an enlarged area to prevent the leg from penetrating too deeply into the seabed and becoming imbedded. At the same time it is desirable to provide at least a degree of vertical penetration of the leg to enhance lateral stability of the bearing arrangement. Still further it is desirable to be able to tow a platform to a working site in a condition wherein the legs do not project downwardly from the platform hull and thus provide an undesirable hydrodynamic drag.
A significant advance in the art of supporting jack-up platforms was achieved by the conception and development of a tank footing such as disclosed in Moore et al. U.S. Pat. No. 3,628,336 assigned to the assignee of the subject invention. The disclosure of this Moore et al. patent is incorporated herein by reference as though set forth at length. Briefly, however, the Moore et al. patent discloses a tank footing which is releasably connected within a well recessed into the platform hull around each leg. According to the Moore et al. disclosure if the bottom surface is firm the tank footings are not used and they remain connected to the hull. If, however, looser soils are encountered the tank footings are connected to the platform legs in a position above the end of the legs to provide a combination effect of penetration by the leg for lateral stability and vertical bearing over an enlarged footing area. Following operations the leg and footing are jacked back to the hull for transport to a new working site.
Notwithstanding the advantages provided by the foregoing Moore et al. design, room for significant improvement remains. In this regard it would be highly desirable to provide a variable bearing assembly for a jack-up platform that could advantageously be used with a variety of seabed soils while providing enhanced lateral stability for the bearing assembly. Further it would be advantageous to provide a bearing assembly for a jack-up platform which would facilitate removal of the platform leg from the seabed following site operations.
The difficulties suggested in the preceding are not intended to be exhaustive, but rather are among many which may tend to limit the effectiveness and satisfaction with prior platform bearing systems. Other noteworthy problems may also exist; however, those presented above should be sufficient to demonstrate that prior jack-up platform bearing assemblies will admit to worthwhile improvement.
OBJECTS OF THE INVENTION
It is therefore a general object of the invention to provide a novel jack-up platform bearing assembly which will obviate or minimize difficulties, while concomitantly achieving desired advantages, of the type previously described.
It is a specific object of the invention to provide a novel jack-up platform bearing assembly which will operably accommodate a variety of seabed soil bearing conditions.
It is a related object of the invention to provide a novel jack-up platform bearing assembly which will permit a variable degree of vertical leg penetration within a seabed while providing enhanced lateral stability of the bearing assembly.
It is another object of the invention to provide a novel jack-up platform bearing assembly wherein the depth of vertical leg penetration may be advantageously limited in loose seabed soils.
It is yet another object of the invention to provide a novel jack-up platform bearing assembly wherein retrieval of the platform leg following site operations will be enhanced.
It is still another object of the invention to provide a novel jack-up platform bearing assembly wherein hydrodynamic drag of jack-up platform legs is minimized during transport of the platform to a working station.
BRIEF SUMMARY OF A PREFERRED EMBODIMENT OF THE INVENTION
A preferred embodiment of the invention which is intended to accomplish the foregoing objects comprises a variable bearing assembly for a jack-up platform having a hull, at least one support leg and jacking means to effect relative verticial movement between the hull and leg.
The variable bearing assembly includes a bearing member or pad which is carried by and surrounds the distal end of the platform support leg. A guide member is mounted upon the bearing member and surrounds the support leg for providing a sliding guidance of the bearing member along the distal end of the support leg. An interconnecting assembly extends between the guide and support leg and provides a degree of longitudinal lost motion between the guide and support leg such that the bearing member operably enhances the lateral stability to the support leg and in most instances exhibits vertical bearing capability as the support leg penetrates into the seabed to the limit of the lost motion connection.
Another aspect of the subject invention is the provision of a release assembly mounted upon the bearing member which includes a mechanical advantage unit which is operable to selectively disengage the interconnecting member extending between the guide and distal end of the platform leg such that in instances where the bearing member has been silted over during platform operations and/or has become otherwise firmly imbedded within the loose soil formation of the seabed the interconnecting member may be withdrawn and the platform leg drawn up through the bearing member for retrieval while leaving the bearing pad portion of the variable bearing assembly imbedded within the seabed.
THE DRAWINGS
Other objects and advantages of the present invention will become apparent from the following detailed description of a preferred embodiment thereof taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is an axonometric view of an offshore jack-up platform of the type operable to advantageously utilize the subject invention;
FIG. 2 is a partial cross-sectional view of the offshore platform wherein a variable bearing assembly, in accordance with the invention, is shown drawn into a recess within the platform hull during a transport operation;
FIG. 3 is a partial cross-sectional view of a jack-up platform wherein a variable bearing assembly, in accordance with the invention, is mounted at a distal end of a support leg of the platform and is operably stationed upon a seabed;
FIG. 4, note sheet 2, is a detailed plan view of a preferred embodiment of the subject variable bearing assembly;
FIG. 5 is an enlarged, partial, cross-sectional view taken along section lines 5--5 in FIG. 4 and discloses a lost motion interconnecting assembly between a bearing member and a platform leg in accordance with the invention;
FIG. 6 is a partial, cross-sectional view taken along section line 6--6 in FIG. 5 and discloses a rack and pinion actuating member;
FIG. 7 is a partial, cross-sectional view taken along section line 7--7 in FIG. 5; and
FIG. 8 is a detailed view taken along section line 8--8 in FIG. 6.
DETAILED DESCRIPTION
Context of the Invention
Referring now to the drawings and particularly to FIG. 1 there will be seen an axonometric representation of a jack-up offshore platform of the type operable to advantageously utilize the subject variable bearing assembly. Although the subject invention may be employed with a plurality of jack-up platform designs the platform depicted in FIG. 1 is believed to be representative and includes a hull 12 which carries a plurality of legs 14 normally extending through the hull and a jacking assembly 16 which is operable to effect relative vertical motion of the legs 14 with respect to the hull. A number of different jacking assemblies 16 may be utilized to raise and lower the leg 14 with respect to the hull. One jacking assembly which has been advantageously utilized in the past is disclosed in a Bradbury U.S. Pat. No. 3,401,917, assigned to the assignee of the subject invention.
The hull 12 is typically fitted with a number of pieces of equipment to conduct drilling operations. Representative equipment includes a derrick 18 and draw works 20 which is mounted upon a centilever assembly 22 extending outwardly from the deck of the hull 12. A generator house 24 is mounted upon one lateral portion of the deck and a hydraulic power and fresh water system 26 is mounted upon a corresponding lateral location of the deck. A large 28 and small 30 crane is pedistal mounted upon the deck for handling equipment, drill pipe, casing and the like. Further, crew quarters 32 are provided at a forward end of the platform beneath a heliport 34. Without unduly belaboring the above by a complete recitation of the operating equipment on a conventional jack-up platform, it should be appreciated that an operating platform carries thousands of tons of equipment and supplies above the surface of a body of water for an extended period of time and must be securely supported by the legs 14 which extend through an underlying body of water 36 and into the seabed 38.
In order to carry the tremendous loads of a working offshore platform, a variable bearing assembly 40 is mounted at a distal end of each leg 14. Turning to FIG. 2 the hull 12 is fashioned with a recess or well 42 around each leg location and operably receives the variable bearing assembly 40 such that the bottom portion of the assembly is approximately flush with a lowermost portion of the hull 12 during transportation. Accordingly, hydrodynamic drag on the platform during flotation is minimized. On site the jacking asssemblies 16 are actuated and each support leg 14 including its variable bearing assembly 40 is jacked downwardly through the body of water 36 and into supporting engagement with the seabed 38 as depicted in FIG. 3.
Variable Bearing Assembly
Turning now to FIGS. 4 and 5, note sheet 2, there will be seen various views of a variable bearing assembly 40 in accordance with a presently preferred embodiment of the invention. More specifically the variable bearing assembly includes a bearing member or pad 42 which may be square in peripheral configuration, as depicted in FIG. 4, round or fashioned with an intermediate orthogonal exterior as desired. The bearing member 42 includes a central aperature 44 for intimately receiving a platform leg 14. In the subject embodiment the platform support leg 14 has been depicted as a hollow cylindrical member. Other leg configurations may be utilized, however, and in such cases it should be appreciated that the aperature 44 will be fashioned to conform to the exterior contour of those various support leg designs.
A guide member 46 is mounted upon the bearing member 42 and includes an interior surface which is compatible with the exterior surface of the support leg 14; which in the instance of the instant disclosure is a cylindrical member. As depicted in FIG. 5 it will be appreciated that the guide 46 has a longitudinal dimension and extends upwardly from the bearing member 42 to slidingly, yet intimately, surround the platform support leg 14. This guide 46 operably permits the bearing assembly to longitudinally translate along the distal end of the support leg. In the embodiment depicted in FIGS. 4 and 5 the guide member is supported with respect to the bearing member 42 by a plurality of bracing plates 48. The particular configuration of the bracing assembly is not considered to be critical and other forms of brace arrangements suitable to maintain the structural integrity of the guide 46 with respect to the bearing member 42 will be recognized by those skilled in the art.
An interconnecting assembly 60 is mounted upon the bearing member and advantageously is utilized to releasably connect the bearing member 42 and guide 46 with the support leg 14. The interconnecting assembly 60 includes a load bearing pin 62 which is mounted for horizontal translation within a transverse guide 64. The load pin 62 extends through an aperature 66 within the guide member 46 and into an elongate aperature or recess 68 cut into the distal end of the platform leg 14. Although a preferred embodiment of the invention discloses a recess in the support leg 14 and a load bearing pin 62 carried by the bearing assembly this structural relationship may be reversed with a recesse fashioned into the guide 46 of the bearing assembly which would be operable to receive a load bearing pin or protrusion extending radially outwardly from the support leg 14.
As seen in FIG. 4 a plurality of interconnecting assemblies 60 are preferably mounted about the bearing member and symmetrically and selectively interconnect the variable bearing assembly with the platform support leg 14. In a preferred embodiment the pin 62 is generally rectangular in cross-section, note FIG. 5, and the aperature 68 has a compatible configuration and includes a longitudinal degree of travel or lost motion "X". The length of the recess, and thus lost motion, may vary but is generally defined at its lower limit by the distance of the guide member below the load pin 62 and at its upper end by the maximum desired distance it is determined that the particular support leg configuration should be permitted to cut into the seabed. In instances where relatively loose bearing material is encountered the bearing member 42 will engage the seabed 38 and the support leg 14 will slide along the guide 46 downwardly a further distance of lost motion "X" and cut into the seabed as depicted in phantom at 70 in FIG. 5.
In order to selectively actuate the load pin 62 the interconnecting assembly 60 includes, in a presently preferred embodiment, a mechanical advantage actuating mechanism 72. This actuating mechanism includes a rack 74 which mates with a compatible pinion gear 76 mounted for rotation about a threaded connector 78. The connector 78 in turn is pivotally mounted as at 80 to a remote end of the engaging pin 62. The pinion gear 76 is mounted for coaxial rotation as at 82 by an upright frame 83 and is fashioned with an internally threaded hub portion 84 to receive the link 78. The rack itself is constrained within a vertical guide 86 and upon mechanical pulling action in the direction of arrow A, note FIGS. 5 and 6, the pinion gear 76 will rotate and withdraw the load pin 62 from engagement with recess 68 in the supporting leg 14. When the pin is withdrawn it will be appreciated by those skilled in the art that the leg 14 will be free to be pulled up through the variable bearing assembly and to the platform deck; leaving the bearing assembly imbedded within the seabed.
Although the presently preferred embodiment discloses a rack and pinion mechanical advantage release mechanism other assemblies which provide mechanical leverage for release of the load pin 62 are contemplated. Moreover, hydraulic, air or explosive release assemblies may be utilized with the subject variable bearing assembly to selectively release the load bearing pin 62.
SUMMARY OF MAJOR ADVANTAGES OF THE INVENTION
After reading and understanding the foregoing description of a preferred embodiment of the invention, in conjunction with the drawings, it will be appreciated that several distinct advantages of the subject variable bearing assembly for a jack-up platform are obtained. Without attempting to set forth all of the desirable features of the instant invention as specifically and inherently disclosed above, at least one illustrative advantage comprises a unique combination of a bearing member and a lost motion connection assembly between a guide mounted upon the bearing member and the distal end of an offshore platform leg. By the provision of this lost motion connection the platform leg can cut into the seabed a varying distance depending upon the point of refusal of the soil and the lateral bearing member will provide an enhanced degree of lateral stability during the lost motion segment. In those instances when the entire lost motion segment is taken up before the bottom of the support leg reaches the point of soil bearing refusal the bearing member advantageously spreads the vertical load over an enlarged bearing area.
The variable bearing assembly is releasably connected to the distal end of the platform leg so that in the event that the bearing assembly becomes silted over or imbedded within an upper surface of the seabed it may be faciley left on site by retracting the connecting load pins and allowing the platform support leg to be withdrawn to the surface with relative ease.
The load bearing pin assembly may be advantageously retracted by a mechanical advantage actuating assembly which in a preferred embodiment comprises a rack and pinion mechanism.
In describing the invention, reference has been made to a preferred embodiment and illustrative advantages of the invention. Those skilled in the art, however, and familiar with the instant disclosure of the subject invention, may recognize additions, deletions, modifications, substitutions and/or other changes which will fall within the purview of the subject invention and claims.
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A variable bearing assembly (40) for a jack-up platform having a hull (12), at least one support leg (14) and jack means (16) to effect relative vertical movement between the hull and support leg wherein the variable bearing assembly (40) includes; a bearing pad or foot (42) surrounding the distal end of the support leg (14) and a lost motion assembly (62, 68) interconnecting the bearing pad and support leg such that the support leg may vertically penetrate the seabed to refusal while the bearing pad is essentially supported on the surface of the seabed.
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RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 09/446,930 filed Dec. 29, 1999, which claims priority of PCT Patent Application No. PCT/GB99/00093 filed Jan. 24, 1998, United Kingdom Patent Application No. 9801494.7 filed Jan. 24, 1998, and United Kingdom Patent Application No. 9811852.4 filed Jun. 2, 1998, which are incorporated herein by reference.
FIELD OF THE INVENTION
This invention relates to a downhole tool, and in particular to a casing or liner shoe.
BACKGROUND OF THE INVENTION
In oil and gas exploration and production operations, bores are drilled to gain access to subsurface hydrocarbon-bearing formations. The bores are typically lined with steel tubing, known as tubing, casing and liner, depending upon diameter, location and function. Bores may also be lined with a filtration medium, such as slotted pipe or tube, or filtration media comprising a combination of two or more of slotted pipe or tubing, slotted screens or membranes and sand-filled screens. Embodiments of the present invention may be useful in some or all of these applications, and for brevity reference will generally made to “tubing”. The tubing is run into the drilled bore from the surface and suspended or secured in the bore by appropriate means, such as a casing or liner hanger. For casing, cement may then be introduced into the annulus between the tubing and the bore wall.
As the tubing is run into the bore the tubing end will encounter irregularities and restrictions in the bore wall, for example ledges formed where the bore passes between different formations and areas where the bore diameter decreases due to swelling of the surrounding formation. Further, debris may collect in the bore, particularly in highly deviated or horizontal bores. Accordingly, the tubing end may be subject to wear and damage as the tubing is lowered into the bore.
These difficulties may be alleviated by providing a “shoe” on the tubing end. Proposals for casing shoes of various forms are described in Canadian Patent No. 1,222,448, U.S. Pat. Nos. 2,334,788 and 4,825,947 and International Patent Application WO96\28635.
SUMMARY OF THE INVENTION
It is among the objectives of embodiments of the present invention to provide an improved tubing shoe.
According to the present invention there is provided a tubing shoe comprising a body for mounting on the lower end of rotatable tubing, and a rigid reaming portion comprising reaming members extending helically around the body towards the leading end thereof in an opposite direction to the intended direction of rotation of the tubing.
According to another aspect of the present invention there is provided a method of reaming a bore in preparation for receiving tubing, the method comprising the steps of:
mounting a tubing shoe on the lower end of tubing, the tubing shoe comprising a body and reaming members extending helically around the body towards the leading end thereof in one direction; and
running the tubing into a bore while rotating the tubing in the opposite direction to said one direction.
In use, these aspects of the present invention facilitate running in of tubing such as casing or liner which is supported or mounted such that it may be rotated as it is run into a bore: liner is typically run in on drill pipe, which may be rotated from surface as necessary; casing may be rotated using a top drive. In the interest of brevity, reference will be made herein primarily to liner. By providing reaming members which extend helically around the body in the opposite direction to the rotation of the liner, the reaming members do not tend to “bite” into obstructions in the bore wall; in conventional shoes provided with helical blades or flutes which extend in the same direction as the rotation of the liner the blades tend to engage obstructions, in a similar manner to a screw. In contrast, in the present invention, the members will tend to ride on or over any obstruction as the members ream the bore to the desired diameter to allow the liner to pass. This minimises the possibility of the shoe and liner becoming stuck fast in the bore due to the shoe becoming locked with a bore obstruction.
While the body and reaming portion are preferably substantially cylindrical, the leading end of each reaming member may define a pilot reaming portion defining a smaller diameter than a subsequent reaming portion. Most preferably, the reaming portions include a cutting or rasping surface or inserts on an outer surface of the portions, such as blocks or inserts of tungsten carbide, diamond or other hard material welded or otherwise fixed to the body or reaming members. The pilot and subsequent reaming portions of each reaming member may be helically aligned, or may be staggered. In a preferred embodiment, the reaming members are provided with inserts of hard material, such as tungsten carbide; testing has shown that such inserts provide more effective cutting and members provided with such inserts are harder wearing. It is believed that the ability to press the inserts into interference fit holes or slots avoids the stresses and other material property changes induced by welding blocks of tungsten carbide in place, and the inserts are spaced apart on the reaming members and are effectively self-cleaning, unlike traditional welded tungsten carbide blocks which require cleaning and often become “clogged”.
Each reaming member may include a stabilising portion, which may extend rearwardly of a reaming portion. Most preferably, the stabilising portion has a relatively smooth and hard wearing outer surface, for example of machined tungsten carbide. Alternatively, or in addition, a torque reducing sleeve or centraliser may be provided on the body rearwardly of the reaming portion. Preferably, the centraliser is spaced rearwardly of the reaming portion. Most preferably, the centraliser is rotatable relative to the body. In the preferred embodiment, the centraliser defines a bushing or sleeve, and one or more fluid conduits may carry fluid to provide lubrication between the bushing and the shoe body. In other embodiments the fluid conduits may be omitted. The centraliser may define raised helical flutes or blades. Preferably, the blades extend in the same direction as the intended direction of rotation of the shoe, that is in the opposite direction to the reaming members. In other embodiments the centraliser blades may extend in the same direction as the reaming members. The centraliser blades may include one or both of axial lead in and lead out portions, the portions facilitating relative axial movement of the centraliser relative to the bore wall. In other embodiments, the centraliser blades may be “straight”, that is extend solely axially.
Alternatively, or in addition, further torque reducing sleeves or centralisers may be provided rearwardly of the shoe or on the liner itself.
The trailing edge of each reaming member may define a back reaming portion, which back reaming portions may include a cutting or rasping surface, such as blocks or inserts of tungsten carbide or other hard material welded, located in bores, or otherwise fixed to the body. This feature is useful in shoes having a reduced diameter portion in which material may gather or become trapped, hindering retraction or withdrawal of the shoe. In the preferred embodiment of the invention there is little or no reduction in shoe body diameter following the reaming members, such that it is not necessary to provide the back reaming feature. Most conveniently, the shoe tapers towards the leading end thereof.
The body may define a fluid transmitting conduit in communication with fluid outlets located between the reaming members; due to the orientation of the members, the rotation of the shoe will not tend to clear cuttings and other material from the channels or flutes between the members, and passing fluid into the channels facilitates maintaining the channels clear of cuttings and the like. Most preferably, the fluid outlets are arranged to direct fluid rearwardly of the leading end of the shoe. Conveniently, at least adjacent fluid outlets are longitudinally offset, to minimise weakening of the shoe body. In other embodiments, such fluid outlets may be provided on a nose portion on the body, the outlets being arranged to direct fluid rearwardly towards or between the reaming members.
Preferably also, the body includes a nose portion, preferably an eccentric nose portion, that is the leading end of the nose portion is offset from the shoe axis. Most preferably, the nose portion is of a relatively soft material, for example an aluminium or zinc alloy, or indeed any suitable material, to allow the nose to be drilled out once the liner has been located in a bore. The nose portion may define one or more jetting ports, depending upon the desired flow rate of fluid from the nose portion. One or more jetting ports may be provided toward a leading end of the nose portion; in one preferred embodiment, a jetting port may be provided aligned with the shoe axis. One or more jetting ports may be provided toward a trailing end of the nose portion; in one preferred embodiment a plurality of spaced jetting ports are provided around a base of the nose portion and, in use, direct fluid rearwardly towards the reaming members. The one or more ports provided on the nose portion may open into respective recesses in the nose portion surface, to facilitate in the prevention of the jetting ports becoming blocked or plugged. In the preferred embodiment, the nose portion is rotatable relative to the body, to facilitate passage of the shoe over ledges and the like. Most preferably, the nose is rotatable only to a limited extent, for example through 130°; this facilitates the drilling or milling out of the nose. Of course, if the nose portion is not required to be drillable, the nose portion may be freely rotatable relative to the body. The nose may be biased towards a particular “centred” orientation by a spring or the like.
According to a further aspect of the present invention there is provided a tubing shoe comprising: a fluid transmitting body for mounting on the lower end of tubing; reaming members on the body; and fluid outlets for directing fluid towards or between the members.
Preferably, the fluid outlets are arranged to direct fluid rearwardly of the leading end of the shoe.
Preferably also, at least adjacent fluid outlets are longitudinally offset.
The fluid outlets may be provided in a nose located on the leading end of the shoe.
According to a still further aspect of the present invention there is provided a method of reaming a bore in preparation for receiving tubing, the method comprising the steps of:
mounting a tubing shoe on the lower end of tubing, the tubing shoe comprising a fluid transmitting body, reaming members on the body, and fluid outlets for directing fluid towards or between the members;
running the tubing into a bore; and
passing fluid through said outlets.
According to another aspect of the present invention there is provided a tubing shoe comprising a body for mounting on the lower end of tubing, and reaming members on the body, the leading end of each reaming member defining a pilot reaming portion defining a smaller diameter than a subsequent reaming portion.
Preferably, the reaming members each define a cutting or rasping surface, such as blocks or inserts of tungsten carbide or other hard material welded, held in bores or slots or otherwise fixed to the body. Most preferably, the reaming members extend helically around the outer surface of each member. Preferably also, the cutting or rasping surfaces of the reaming members combine to provide substantially complete coverage around the circumference of the body. Thus, even if there is no rotation of the shoe as it is advanced into a bore, there is cutting or rasping capability around the circumference of the bore and the bore is reamed to at least a minimum diameter corresponding to the diameter defined by the cutting or rasping surface.
According to another aspect of the present invention there is provided a tubing shoe comprising: a body for mounting on the end of a tubing string; and reaming members extending longitudinally and helically around the body, the reaming members providing substantially complete circumferential coverage of the body whereby, in use, when the tubing shoe is advanced axially into a bore, the reaming members provide reaming around the shoe circumference.
According to a further aspect of the present invention there is provided a method of clearing a bore to receive tubing, the method comprising:
mounting a tubing shoe on the end of a tubing string, the shoe having reaming members extending longitudinally and helically around the body, the reaming members providing substantially complete circumferential coverage of the body; and
advancing the tubing shoe axially into the bore, the reaming members provide reaming around the shoe circumference.
These aspects of the invention are of particular application in tubing shoes which are not subject to rotation during running in to a bore.
The inclination of the reaming members to the longitudinal axis of the shoe may be constant or may vary over the length of the members, for example the members may include portions parallel of perpendicular to the shoe longitudinal axis.
According to a further aspect of the present invention there is provided a tubing shoe comprising: a body for mounting on the end of a tubing string; and a nose rotatably mounted on the body.
Preferably, the nose is rotatable about a longitudinal axis.
Preferably also, the degree of rotation of the nose relative to the body is restricted, to facilitate drilling or milling through the nose.
According to a still further aspect of the present invention there is provided a tubing shoe comprising: a body for mounting on the end of a tubing string; and a torque reducing sleeve or centraliser on the body.
Preferably, the centraliser is rotatably mounted on the body. Most preferably, the body defines a fluid conduit and a bearing area between the centraliser and the body is in fluid communication with the conduit, to supply lubricating fluid to the bearing area.
Preferably also, the centraliser defines external blades or flutes. The blades may extend helically, and may include one or both of substantially axial lead in and lead out portions. Where the shoe includes reaming members, the centraliser blades may extend in the same or the opposite direction to the reaming members.
According to a yet further aspect of the present invention there is provided a tubing shoe comprising:
a body for mounting on the end of a tubing string; and
a rigid reaming portion comprising reaming members extending helically around the body and comprising inserts of relatively hard material on bearing surfaces of the reaming members.
The various aspects of the invention as described above may be manufactured and assembled by various methods. For example, the body and reaming members may be machined from a single billet. However, it is preferred that the body is formed of a single part on which a sleeve defining the reaming members is mounted. A centralising sleeve may also be provided for mounting on the body. Conveniently, the body defines a reduced diameter portion on which one or more sleeves are mounted. A rotating sleeve, such as a centraliser, may be retained by a locking ring or the like. A fixed sleeve, such as carries the reaming members, may be pinned to the body, and the pin may also serve to retain a nose portion on the body.
The various aspects of the invention as described above may be provided singly or in combination with one or more of the other aspects. Further, if desired the various aspects of the invention may be provided in combination with one or more of the optional or preferred features of the other aspects of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 illustrates a liner shoe in accordance with a first embodiment of the present invention;
FIG. 2 illustrates a liner shoe in accordance with a second embodiment of the present invention;
FIGS. 3 and 4 are side and end views of the nose of the shoe of FIG. 2;
FIG. 5 illustrates a liner shoe in accordance with a third embodiment of the present invention;
FIG. 6 is an exploded view of the shoe of FIG. 5; and
FIG. 7 is an end view of a retaining ring of the shoe of FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference is first made to FIG. 1 of the drawings, which illustrates a liner shoe in accordance with a first embodiment of the present invention. The shoe 10 has a hollow cylindrical body 12 adapted for mounting on the lower end of a length of bore liner (not shown). Typically, such mounting will be achieved by a conventional threaded box and pin type arrangement.
The body carries four reaming members extending helically around the body 12 towards the leading end of the body in the opposite direction to the intended direction of rotation of the liner: in the Figure, arrow A illustrates the direction of the reaming members 14 , while arrow B illustrates the direction of rotation of the shoe 10 in use.
The leading end of each reaming member 14 comprises a pilot reaming portion 16 and a following larger diameter reaming portion 18 . Rearwardly of the reaming portions 16 , 18 each reaming member 14 defines a stabilising portion 20 . Further, the trailing edge of each reaming member 14 defines a back reaming portion 22 . The reaming portions 16 , 18 , 22 are provided with an aggressive surface formed of blocks of tungsten carbide welded to the body 12 . However, each stabilising portion 20 has a relatively smooth outer surface formed of machined tungsten carbide.
As noted above, the body 12 is hollow and thus may carry a drilling fluid which is pumped from surface through the liner. Rearwardly directed jetting ports 24 communicate with the body bore such that, in use, drilling fluid is directed rearwardly, in the direction of arrow C, to clear cuttings from between the reaming members 14 .
A jetting port 26 is also provided in an eccentric nose portion 28 which is threaded onto the end of the body 12 . The nose portion 28 is formed of relatively soft aluminium alloy, such that it may be drilled out of the body 12 once a liner is in place, to provide a clear bore through the liner and the shoe 10 .
In use, the shoe 10 is mounted on the lower end of a length of liner, which is then run into a bore. The upper section of the bore will have been previously lined with steel casing, such that initial passage of the shoe and liner into the bore should be relatively straightforward. However, as the shoe 10 and the leading end of the liner move into the lower unlined part of the bore, the shoe 10 is likely to encounter ledges, deposits of cuttings, and other obstructions. These may be dislodged or pushed aside by the shoe 10 , or the fluid passing from the shoe 10 . However, on occasion it may be necessary to rasp or ream past an obstruction using the reaming members 14 . This may be achieved by rotating the liner and shoe 10 in the direction B such that the pilot reaming portions 16 and the reaming portions 18 rasp or ream the obstruction to an extent that the shoe 10 and the liner may pass. Due to the mass and dimensions of a typical section of liner, and the fact that the liner is suspended on relatively flexible drill pipe, it is often not possible to apply a significant torque to the shoe 10 . However, the action of the reaming portions 16 , 18 will normally be sufficient to overcome any obstructions. Further, the orientation of the reaming portions 16 , 18 ensure that the reaming members 14 ride over any obstructions and do not bite into the obstructions, as might occur if the members 14 were to extend in the opposite direction. In this example it may be observed that the reaming members 14 are “left handed”, that is the members 14 extend counter clockwise around the body 12 , as the shoe 10 is to be rotated in a clockwise direction. In some situations it may be sufficient to reciprocate the liner and shoe 10 axially to rasp or ream past an obstruction.
The provision of a pilot reaming portion 16 , and also the provision of a cutting or rasping surface over the surface of the reaming portions 16 , 18 , further minimise the possibility of the reaming members 14 jamming or locking against an obstruction.
As the configuration of the reaming members 14 is such that the rotation of the shoe 10 will not tend to dislodge cuttings and other debris from between the members 14 , the jetting ports 24 ensure that the channels between the members 14 remain clear.
Reference is now made to FIGS. 2, 3 and 4 of the drawings, which illustrate a casing shoe 30 in accordance with a second embodiment of the present invention. The shoe 30 has a generally cylindrical tubular body 32 adapted for mounting on the lower end of a string of casing or liner (not shown). A nose cone 34 is mounted on the leading end of the body 32 , and directly behind the nose on the body are a series of six reaming members 36 (the number of reaming members will typically be determined by the shoe diameter, that is, the larger the diameter the greater the number of members). A centraliser 38 is mounted on the body 32 rearwardly of and longitudinally spaced from the reaming members 36 .
The nose cone 34 is of generally frusto-conical form, with the nose leading end 40 being offset from the longitudinal axis of the shoe 42 . A central fluid conduit 44 in the nose communicates with the interior of the body and, in use, directs fluid to two smaller diameter conduits 46 , 48 which terminate at longitudinally and circumferentially spaced outlet ports 50 , 52 . The nose cone 34 is axially fixed but is rotatable through 146° relative to the body 32 , around the axis 42 . The nose cone 34 is located relative to the body 32 by pins 54 , each pin 54 having a threaded outer portion 56 for engaging a corresponding threaded bore 56 in the body 32 and an inner portion 58 for location in an annular groove 61 defined by a reduced diameter rear portion of the nose cone 60 . The groove 61 also accommodates springs (not shown) which tend to centre the cone in a predetermined position relative to the body 32 .
If reference is made in particular to FIG. 4, it will be noted that the interior of the rear portion of the nose cone 34 defines a series of radial slots 59 , which slots assist in the milling out of the nose cone 34 once the liner is in place; the relatively soft aluminium alloy from which the nose cone has been machined may tend to “smear” over a milling tool, and the slots facilitate the break-up of the cone and reduce the likelihood of such smearing.
The reaming members 36 are formed of an aggressive cutting material, such as tungsten carbide blocks, welded to the leading end of the body to define reaming blades. Each blade 36 comprises a leading pilot portion 63 which defines a taper extending rearwardly and helically from the nose cone 34 . Rearwardly of each pilot portion 63 is a larger diameter reaming portion 62 with tapering leading and trailing ends 64 , 66 , each reaming portion being spaced from but helically aligned with the respective pilot portion 63 . It should be noted that, as the leading end of each blade 36 overlaps longitudinally the trailing end of an adjacent blade 36 , the blades 36 collectively provide 360° coverage of the body.
Like the first described embodiment, fluid outlet ports 68 , which communicate with the interior of the body, are provided between the blades 36 . In this embodiment it will be noted that adjacent ports 68 are longitudinally offset, to minimise weakening of the body 32 .
The centraliser 38 is located at the longitudinal centre of the shoe 30 and comprises a bushing 70 defining five blades 72 , although the number of blades may be varied as desired. The bushing 70 is rotatable on the body and is located between a body shoulder 74 and a lock ring 76 . In use, two fluid conduits (not shown) carry fluid from the body interior to lubricate the bearing surfaces between the bushing 70 and the body 32 . The blades 72 each comprise a main helical portion 78 and axial leading and trailing portions 80 , 82 .
In use, the shoe 30 is mounted on the lower end of a casing string and run into a well bore. As the shoe 30 passes through the bore the nose 34 will tend to push aside any sand, cuttings and the like which have gathered in the bore, to allow the liner to pass. Any irregularities and intrusions in the bore wall will be rasped or reamed to the required diameter by the blades 36 . Due to the overlapping blade configuration, such rasping and reaming may be achieved solely by axial movement of the shoe 30 through the bore, and may be enhanced by rotating the shoe. As described above with reference to the first described embodiment, the blade configuration and orientation is such that, if the shoe is rotated, the blades 36 will tend to ride over and rasp or ream away any obstructions, rather than bite into the obstruction.
Rotation of the shoe, and the following liner string, is facilitated by the provision of the centraliser 38 , which acts as a rotary bearing between the shoe 30 and the bore wall. The configuration of the centraliser blades 72 also facilitates fluid flow past the shoe.
In the event of the shoe encountering a ledge or the like, the ability of the eccentric nose cone 34 to rotate relative to the body 32 facilitates negotiation of the ledge, as the nose 34 may “roll off” the ledge, particularly where the shoe itself is not rotating.
If, for any reason, it is deemed necessary to retract or withdraw the shoe 30 , the tapering of the shoe towards its leading end and the absence of any reduced diameter portions rearwardly of nose, such as occur rearwardly of the stabiliser portions 20 in the first described embodiment, facilitate such withdrawal. Retraction of the shoe should be possible without back reaming, which of course is not possible in applications where there is no facility to rotate the liner string.
Reference is now made to FIGS. 5, 6 and 7 of the drawings, which illustrate a casing shoe 100 in accordance with a third embodiment of the present invention. The shoe 100 has a generally cylindrical tubular body 102 having a reduced diameter leading end portion 104 which carries a centraliser 106 , a reamer sleeve 108 and a nose 110 , as will be described.
The centraliser 106 is substantially similar to the centraliser 38 described above, and will therefore not be described in any detail.
The reamer sleeve 108 comprises five helical reaming blades or members 112 of substantially constant radial extent. Each member 112 defines a row of blind bores 114 which retain a respective tungsten carbide insert 116 , in the illustrated example each member 112 having eight inserts 116 . The bores 114 are sized such that the inserts 116 may be pressed in, without requiring any welding and thus avoiding the corresponding stresses and material changes which welding induces.
A threaded pin 118 is used to lock the sleeve 108 to the body 102 , the inner end portion of the pin serving to retain the nose 110 on the end of the body 102 .
The nose 110 , like the nose cone 34 described above, is rotatable to a limited extent relative to the body and has a leading end offset from the shoe axis 119 . However, the configuration of the fluid outlet ports 120 , 122 of this embodiment are different, there being a single outlet port 120 aligned with the axis 119 for directing fluid forwards, and a series of circumferentially spaced ports 122 around the base of the nose 110 , the ports 122 opening into a circumferential groove 124 . In use, ports 122 direct fluid rearwardly over the reaming members 112 , to assist in maintaining the members 112 clear of debris.
It will be apparent to those of skill in the are that the configuration of the body 102 , sleeves 106 , 108 and nose 110 will facilitate manufacture and assembly of the shoe 100 , and provide for flexibility in manufacture, in that a single form of body 102 may accommodate centralisers and reamer sleeve having, for example, blades of different configurations, as desired.
It will be clear to those of skill in the art that the above-described embodiments are merely exemplary of the present invention, and that various modifications and improvements may be made thereto, without departing from the scope of the present invention.
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A tubing shoe ( 30 ) comprising: a body ( 32 ) for mounting on the end of a tubing string; and reaming members ( 36 ) extending longitudinally and helically around the body, the reaming members providing substantially complete circumferential coverage of the body whereby, in use, when the tubing shoe is advanced axially into a bore, the reaming members ( 36 ) provide reaming around the shoe circumference. A rotatable torque reducing sleeve or centraliser ( 38 ) may also be mounted on the body, rearwardly of the reaming members.
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CROSS-REFERENCE TO EARLIER FILED APPLICATION
[0001] The present application is a continuation-in-part of U.S. application Ser. No. 09/602,684 filed Jun. 26, 2000, which is now U.S. Patent No. TO BE ADDED.
FIELD OF THE INVENTION
[0002] The present invention relates generally to an improved process and equipment for converting feedstock into useful materials, and more specifically, to an anaerobic fermentative process for bioconverting animal waste, sewage sludge or other biodegradable feedstock into methane gas, carbon dioxide gas, ammonia, carbon black, organic acid, charcoal, a fertilizer and/or an insecticidal mixture.
BACKGROUND OF THE INVENTION
[0003] Animal waste poses a significant problem in the poultry, swine and cattle industries. Animal waste from animal raising or processing operations is responsible for a significant amount of underground water contamination and methods are continually being developed for handling animal wastes. One known method is the bioconversion of animal waste into useful products.
[0004] Methods for the anaerobic digestion or treatment of sludge, animal waste, synthesis gas or cellulose-containing waste are disclosed in U.S. Pat. Nos. 5,906,931 to Nilsson et al., No. 5,863,434 to Masse et al., No. 5,821,111 to Grady et al. No. 5,746,919 to Dague et al., No. 5,709,796 to Fuqua et al., No. 5,626,755 to Keyser et al., No. 5,567,325 to Townsley et al., No. 5,525,229 to Shih, No. 5,464,766 to Bruno, No. 5,143,835 to Nakatsugawa et al., No. 4,735,724 to Chynoweth, No. 4,676,906 to Crawford et al., No. 4,529,513 to McLennan, No. 4,503,154 to Paton, No. 4,372,856 to Morrison, No. 4,157,958 to Chow, and No. 4,067,801 to Ishida et al. These patents disclose different processes and equipment for the bioconversion, either by microbial digestion or enzymatic conversion, of those materials into methane and other useful materials.
[0005] The equipment used for the anaerobic digestion or fermentation of waste into fuel, such as methane, varies greatly and is generally tailored to specific applications. Equipment that is suitable for a first type of feedstock generally has to be modified before it can be used for a second different type of feedstock.
[0006] Chemical and biochemical reactions that create a gas are generally conducted at low to sub-atmospheric pressures due to the tendency of the product gas to function as feedback inhibitor that inhibits further formation of the gas. The art recognizes that variations in the pressure of an anaerobic digester can be used to effect different biochemical and productivity results. U.S. Pat. No. 4,409,102 to Tanner discloses an anaerobic digestion conducted at sub-atmospheric pressures that unexpectedly affect an increase in methane gas production. U.S. Pat. No. 3,994,780 to Klass et al. discloses the high pressure rupture of cells in an anaerobic digester to render cellular components available to other intact cells in the digester. U.S. Pat. No.3,981,800 to Ort discloses a process for preparing high quality methane (about 98% wt.) with an anaerobic digester operated at 1-5 atm. above atmospheric pressure provided that the sludge is degassed by a recirculator and passed between two digesters connected serially to remove carbon dioxide in the sludge that is then fed back into the digester. Therefore, unlike the presently claimed system, the system or Ort requires that each batch of feedstock under go a two-stage digestion, wherein the feedstock is predigested in a first anaerobic digester and then completely digested in a second anaerobic digester that is connected serially with the first anaerobic digester. U.S. Pat. No. 4,100,023 to McDonald discloses that the internal pressure of the anaerobic digester should be kept at about 1 to 3 inches of water column to ensure proper performance. U.S. Pat. No. 4,568,457 to Sullivan discloses a two-stage anaerobic digester system having an acid forming stage and a methane gas forming stage, wherein the pressure of the gas in the headspace of the two stages can be slightly above atmospheric pressure.
[0007] Methanogenic microbes that create methane from carbon and hydrogen containing feedstocks, such as cellulose, animal waste, food processing waste, and sludge, are well known. These microbes have been used in the waste processing industry and are available in their native forms from natural sources or in genetically altered or manipulated forms, which can produce greater amounts of useful materials per unit weight of waste than can unaltered methanogenic bacteria.
[0008] To date, no equipment containing the required components as described herein has been disclosed. Further, the improved equipment design and layout of the present invention provides a higher yield of methane and other useful materials than other comparable equipment. Still further, the improved process and equipment of the invention can be used in the poultry, swine, dairy or cattle industries to convert cellulose-containing animal waste into methane which is used to operate farm or ranch equipment thereby reducing operating costs and the volume of waste produced.
SUMMARY OF THE INVENTION
[0009] The present invention provides a system for converting cellulose-containing feedstock into useful materials, wherein the system comprises:
[0010] a feedstock slurry feeder;
[0011] a plurality of conduits connecting various components of the system;
[0012] a single pressurizable anaerobic digester comprising agitation means, one or more feed ports, one or more discharge ports, an optional pressure regulator, and a reaction vessel for holding a reaction solution comprising an anaerobic microbe which converts an aqueous slurry of cellulose-containing feedstock into at least methane and an enriched effluent;
[0013] a pressurizer; and
[0014] one or more gas processors directly or indirectly connected to the anaerobic digester;
[0015] wherein the headspace of the anaerobic digester is pressurized to about 10 psi or more to form the enriched effluent and a discharge gas comprising at least methane during anaerobic digestion of the feedstock slurry.
[0016] Depending on the feedstock slurry used, the anaerobic digester will also form a fertilizer, sludge, scum, ammonia, charcoal, carbon black, an organic acid and/or an insecticidal mixture. The anaerobic digester is preferably operated at pressures between 10 to 265 psi, more preferably 10 to 100 psi, and even more preferably 25-75 psi. In preferred embodiments, the system also comprises one or more of the following: one or more gas scrubbers, one or more heaters for heating or preheating the slurry being digested in the anaerobic digester, one or more water storage tanks, one or more feedstock slurry tanks, one or more feedstock grinders, one or more supernatant storage tanks, one or more sludge storage tanks, one or more sludge dryers, one or more scum storage tanks, one or more CO 2 tanks, and/or one or more produced gas storage tanks.
[0017] Other preferred embodiments include those wherein the system does not require a water lagoon, a foam trap, and/or a water vapor trap. Still other preferred embodiments include those wherein: (1) the system is operated in a batch, semi-continuous, or continuous mode; (2) the feedstock slurry comprises from about 1-90% wt. solids, more preferably about 1- 60% wt. solids, or even more preferably about 1-40% wt. solids; (3) the agitation means comprises a gas bubbler, an aerator, a sparger bar, a fluid stream, a mechanical agitator, or a combination thereof; (4) the feedstock slurry is gravity fed or fed under pressure to the anaerobic digester; (5) the pressurizer pressurizes the anaerobic digester with gas or a liquid; (6) the pressurizer is the feedstock slurry feeder, which is preferably a pump, gravity feed system, or a gas compressor; (7) the anaerobic digester does not require aerobic digestion of the feedstock; (8) the anaerobic digester does not require multiple discrete zones of environmentally incompatible waste-digestive microorganisms; (9) the anaerobic microbe is a methanogenic bacterium; (10) the anaerobic microbe is mesophilic or thermophilic; (11) methane produced by the anaerobic digester is used to operate an internal combustion engine, an electrical current generator, an electric engine, a water heater, a furnace, an air conditioning unit, a ventilation fan, a conveyor, a pump, a heat exchanger, fuel cell, or various components of the system itself and/or to recharge power cells; (12) the gas processor comprises a gas scrubber and/or a gas separator; (13) a gas recirculator is used to recirculate gas from the headspace of the reactor to the slurry in the reactor; (14) a gas recirculator adds methane-depleted or carbon dioxide enriched biogas back to the reactor; and/or (15) a fluid recirculator recycles the scum, supernatant, effluent, or sludge of the reactor.
[0018] Another aspect of the invention provides a system for converting cellulose-containing feedstock into useful materials, wherein the system comprises:
[0019] one or more feedstock slurry feeders;
[0020] two or more pressurizable anaerobic digesters connected in parallel, each anaerobic digester comprising agitation means, one or more feed ports, one or more discharge ports, an optional pressure regulator, and a reaction vessel for holding a reaction solution comprising an anaerobic microbe which converts an aqueous slurry of cellulose-containing feedstock into at least methane and an enriched effluent;
[0021] one or more pressurizers;
[0022] one or more gas processors directly or indirectly connected to each anaerobic digester; and
[0023] a plurality of conduits connecting various components of the system;
[0024] wherein the headspace of each anaerobic digester is pressurizable to about 10 psi or more to form the enriched effluent and a discharge gas comprising at least methane during anaerobic digestion of the feedstock slurry.
[0025] Specific embodiments of this aspect of the invention include those wherein: 1) a major portion of the discharge gas is methane; 2) the system comprises a single feedstock slurry feeder connected to each of two or more pressurizable anaerobic digesters connected in parallel; 3) the enriched effluent from a first pressurizable anaerobic digester is not fed into a second pressurizable anaerobic digester; 4) the system further comprises one or more receiving tanks that receive the enriched effluent from each pressurizable anaerobic digester.
[0026] Another aspect of the invention provides an integrated system for converting cellulose-containing feedstock into useful materials, wherein the integrated system comprises:
[0027] a feedstock slurry feeder system that forms an aqueous slurry of cellulose-containing feedstock;
[0028] an anaerobic digester system directly or indirectly connected to the feeder system and comprising two or more pressurizable anaerobic digesters connected in parallel, wherein each anaerobic digester receives the aqueous slurry of cellulose-containing feedstock and converts it into a discharge gas and an enriched effluent; and
[0029] a discharge gas processing system that is directly or indirectly connected to the anaerobic digester system and that at least separates methane from the discharge gas;
[0030] wherein the headspace of each anaerobic digester is pressurizable to about 10 psi or more to form the enriched effluent and a discharge gas comprising at least methane during anaerobic digestion of the feedstock slurry.
[0031] Specific embodiments include those wherein: 1) the integrated system further comprises an enriched effluent processing system; 2) the integrated system further comprises a pressurizer system; 3) the feedstock slurry feeder system comprises one or more mixing vessels and one or more pumps; 4) the discharge gas processing system comprises a dehydrator, separator, and scrubber; 5) each anaerobic digester comprises agitation means, one or more feed ports, one or more discharge ports, an optional pressure regulator, and a reaction vessel for holding a reaction solution comprising an anaerobic microbe that converts the aqueous slurry of cellulose-containing feedstock into at least methane and the enriched effluent; 6) the discharge gas processing system comprises one or more separators for separating CO 2 or ammonia gas from the discharge gas; 7) the integrated system further comprises a gas recirculator to recirculate gas from the headspace of an anaerobic digester to the slurry of the digester; 8) a gas recirculator adds methane-depleted or carbon dioxide enriched discharge gas back to an anaerobic digester; and/or 9) the integrated system further comprises a fluid recirculator system that recycles the scum, supernatant, effluent, or sludge of an anaerobic digester.
[0032] Another aspect of the invention provides an integrated anaerobic digester system comprising:
[0033] a single-stage anaerobic digester system comprising two or more pressurizable anaerobic digesters connected in parallel, wherein each anaerobic digester receives an aqueous slurry of cellulose-containing feedstock and converts it into a discharge gas and an enriched effluent;
[0034] a discharge gas processing system that is directly or indirectly connected to the anaerobic digester system and that at least separates methane from the discharge gas; and
[0035] an enriched effluent processing system that is directly or indirectly connected to the anaerobic digester system;
[0036] wherein the headspace of each anaerobic digester is pressurizable to about 10 psi or more to form the enriched effluent and a discharge gas comprising at least methane during anaerobic digestion of the aqueous slurry of cellulose-containing feedstock.
[0037] Other features, advantages and embodiments of the invention will be apparent to those skilled in the art by the following description, accompanying examples and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] The following drawings are part of the present specification and are included to further demonstrate certain aspects of the invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of the specific embodiments presented herein.
[0039] [0039]FIGS. 1 a and 1 b are process flow schematics of a first preferred embodiment of the anaerobic digester system according to the invention.
[0040] [0040]FIG. 2 is a process flow diagram of a second preferred embodiment of the anaerobic digester system of the invention.
[0041] [0041]FIG. 3 is a chart depicting the temperature, pH, pressure and methane gas volume production of an exemplary digester according to the invention.
[0042] [0042]FIG. 4 depicts a process flow diagram of a third embodiment of the anaerobic digester system, wherein the system comprises two or more pressurizable anaerobic digesters connected in parallel.
DETAILED DESCRIPTION OF THE INVENTION
[0043] The present invention is different than known anaerobic digester system primarily in that it is conducted at elevated pressures of at least about 10 psi up to about 265 psi, more preferably 10 to 100 psi, and even more preferably 25-75 psi, during anaerobic digestion of a feedstock slurry and the system requires only a single stage of anaerobic digestion. The anaerobic digester system also includes an advantageous combination of known and unknown features that unexpectedly provides a very efficient system for converting biomass into methane gas, a nutrient enriched solution, and optionally an insecticidal mixture.
[0044] As used herein, the phrase “single stage of anaerobic digestion” is taken to mean that anaerobic digestion of the aqueous feedstock slurry is accomplished by placing a charge of an aqueous feedstock slurry into a pressurizable anaerobic digester until sufficiently digested and passing the formed gas onto the discharge gas processing system and the remaining fluid (liquid/solids) onto the enriched effluent processing system such that a partially charge of feedstock is not passed from a first anaerobic digester to a second anaerobic digester. Accordingly, a single-stage anaerobic digester system can have one or two or more anaerobic digesters connected in parallel but not in series. A parallel anaerobic digester system is unlike the serial anaerobic digester system of Ort, wherein the charge from a first anaerobic digester is passed onto a second anaerobic digester before it is passed onto the enriched effluent processing system. A serial anaerobic digester system is a two-stage or multi-stage system, whereas the system of the present invention is a single-stage anaerobic digester system.
[0045] As used herein, the term “feedstock” is taken to mean any animal or plant derived material that contains one or more components that can be converted, bioconverted or biodegraded into a useful material by the anaerobic digester of the invention. Animal tissue, biomass, fish tissue or parts, plant parts, fruits, vegetables, plant processing waste, animal processing waste, animal manure or urine, mammalian manure or urine solids isolated from fermentation cultures, and combinations thereof are included in the term feedstock. Particular examples of feedstock include bovine, poultry, equine or porcine manure or urine, wood shavings or chips, slops, mostos, shredded paper, cotton burrs, grain, chaff, seed shells, hay, alfalfa, grass, leaves, sea shells, seed pods, corn shucks, weeds, aquatic plants, algae and fungus and combinations thereof. Combinations of poultry, bovine, equine or porcine urine and/or manure with wood shavings, wood chips, shredded paper, cotton burrs, seed shells, hay, alfalfa, grass, leaves, seed pods, or corn shucks are particularly preferred and are generally referred to as cellulose-containing feedstock.
[0046] A feedstock slurry is prepared by suspending a feedstock in an aqueous solution to form a slurry comprising less than about 90% wt. solids, preferably about 0.1-60% wt. solids, or even more preferably about 1-40% wt. solids. The particle size of the feedstock can be reduced either prior to or during preparation of the feedstock slurry by employing an in-line or immersed abrader, classifier, mill, high shear mixer, grinder, homogenizer or other particle size reducer known to those of ordinary skill in the art. No particular particle size is required for the feedstock; however, smaller particle sizes are preferred as smaller particles are generally bioconverted more quickly than larger particles.
[0047] Grit, such as dirt, sand, soil, stones, pebbles, rocks, feathers, hair and other such materials, is preferably removed prior to addition of the feedstock slurry to the anaerobic digester; however, grit can be removed at any point along the process. Equipment such as classifiers, settling tanks, multiphase tanks, and/or or filters can be used to remove the grit.
[0048] As used herein, the term “useful material” is taken to mean methane gas; hydrogen gas; carbon dioxide; hydrogen sulfide; nitrogen rich fertilizer; protein, amino acid, carbohydrate and/or mineral rich solution or slurry; insecticidal mixture; charcoal; carbon black; insect repellant mixture; combinations thereof and other such materials which can be prepared by anaerobic digesters from a feedstock. Methane, a nitrogen rich fertilizer, charcoal and an insecticidal slurry are particularly preferred useful materials.
[0049] The anaerobic microbe used in the anaerobic digester is any anaerobic bacterium, fungus, mold or alga, or progeny thereof, which is capable of converting the feedstock to a useful material in the anaerobic digester of the invention. Preferred anaerobic microbes are isolated from decaying or composted feedstock, are endogenous to the area in which the feedstock was first obtained, are obtained from bacterial or fungal collections such as those of the American Type Culture Collection (ATCC) or have been genetically altered or engineered to convert a feedstock to a useful material. Particularly preferred anaerobic microbes are those that will convert a cellulose-containing feedstock into methane, a nitrogen rich fertilizer, charcoal, humus and an insecticidal slurry. The anaerobic microbe can be a psychrophile, mesophile or thermophile. Generally, a mesophile will prefer operating temperatures in the range of about 60°-120° F., and a thermophile will prefer operating temperatures in the range of about 120°-160° F.
[0050] Examples of an anaerobic microbe which is useful in the anaerobic digester of the invention include yeast, a methanogenic bacterium, methanobacterium, acetobacterium, acetogenic bacterium, liquefaction bacterium, Clostridium spp. (methane), Bacillus spp., Escherichia spp., Staphylococcus spp., Methanobacter spp., Methanobacter (Mb) omlianskii (methane), Mb. formicicum (methane), Mb. soehngenii (methane), Mb. thermoautrophicum (methane), Mb. ruminatium (methane), Mb. mobile (methane), Mb. methanica (methane), Methanococcus (Mc.) mazei (methane), Mc. vannielii (methane), Ms. mazei (methane), Mb. suboxydans (methane), Mb. propionicum (methane), Methanosarcina (Ms) bovekeri (methane), Ms. methanica (methane), Ms. alcaliphilum (methane), Ms. acetivorans (methane), Ms. thermophilia (methane), Ms. barkeri (methane), Ms. vacuolata (methane), Propionibacterium acidi - propionici (methane), Saccharomyces cerevisae (ethanol), S. ellipsoideus (ethanol), Clostridium propionicum (propanol), Clostridium saccharoacetoper - butylicum (butanol), Clostridium butyricum (hydrogen), wherein the chemical in parentheses indicates a useful material which that microbe produces.
[0051] Other microbes and/or enzymatic catalysts can be added to the anaerobic digester to facilitate breakdown of the feedstock into components which are usable by the anaerobic microbe as either nutrients or starting materials for useful materials made by the anaerobic microbe. Such other microbes and/or enzymes include, for example, amylases, proteases, cellulases, hydrolases, lipid hydrolyzing enzymes, lysozymes, phosphatases, esterases, amidases, and lipases.
[0052] The conditions inside the anaerobic digester will vary according to the useful material being produced, the anaerobic microbe being used, the configuration of the anaerobic digester, the feedstock being converted, the desired productivity of the anaerobic digester, and the form of microbe (immobilized or free-flowing) used. hmobilized microbes can be prepared using any methods known by the artisan of ordinary in the arts. The conditions used to culture the anaerobic microbe and maintain it viable in the anaerobic digester can be varied. Conditions which can be controlled include solids content, reaction solution composition, temperature, gas content, digestion rate, anaerobic microbe content, agitation, feed and effluent rates, gas production rate, carbon/nitrogen ratio of the feedstock, pressure, pH, and retention time in the digester, among other things.
[0053] The amount of solids in the digester will generally range from about 1 to about 60% wt., preferably from about 20 to about 50% wt., or more preferably from about 40 to 50% wt. based upon the total solution weight.
[0054] The particle size of solids in the digester affects the rate of digestion. Generally, the smaller the particle size, the faster the rate of digestion.
[0055] The temperature of the reaction solution is generally in the range of about 60° F. to about 160° F., about 90° F. to about 118° F., about 90° F. to about 115° F., about 90° F. to about 110° F., or about 90°-95° F. The optimum operating temperature will depend upon the anaerobic microbe used, the product being produced, the pressure under which the digestion is conducted, the carbon to nitrogen ratio of the feedstock, and/or the contents of the feedstock. For Clostridium spp., the preferred temperature is in the range of about 70°-100° F., about 70°-95° F., or about 75-95° F. For a mesophilic microbe, the highest level of productivity and highest purity methane is generally attained at a temperature in the range of about 90°-118° F.
[0056] When the digester is operated as described herein, the type of product gas formed will depend upon the operating pressure of the digester and the components of the discharge gas treatment system used to process and purify the gas. The digester system can be made to produce predominantly methane or carbon dioxide. Higher pressure generally promotes the conversion of carbon dioxide to methane and leads to the formation of high purity methane; therefore, lower pressure generally leads to the formation of more carbon dioxide and less methane. Accordingly, when the optimal operating temperature for a particular combination of anaerobic microbe and feedstock slurry components is identified, the composition of the biogas produced can be altered by changing the pressure at which the digestion is conducted.
[0057] The feed rate of the anaerobic digester is expressed in terms of lbs. of feedstock slurry added to the digester per unit time. The feed rate can be varied as desired; however, for a 1000 gal reactor maintained at approximately 80% of capacity, operated at a temperature of about 95°-105° F., and being used to produce methane, about 50 to about 55 lbs. of poultry waste, containing 25% wt. poultry manure and 75% wt. cotton burrs, about {fraction (1/40)} of the total weight per hour can be added to the digester.
[0058] While not absolutely necessary, the feedstock slurry is generally warmed to a temperature approximating the temperature at which the digester is being operated thereby minimizing temperature fluctuations in the digester that might affect the productivity or efficiency of the system.
[0059] The effluent rate, i.e., the rate at which effluent is drawn from the digester, is related to the feed rate of the digester. Generally, the effluent rate will not exceed the feed rate when the digester is operated in a continuous mode. However, the feed rate and effluent rate are generally independent of one another when the digester is operated in a batch or semi-continuous mode. During continuous operation, the slurry level in the digester will preferably remain relatively constant and the feed rate and effluent rate will be kept controlled so as to provide the desired overall residence time in the anaerobic digester. Further, the total amount of feedstock slurry added to the digester will generally exceed the total amount of effluent withdrawn from the digester, since part of the feedstock is converted to a gas that is also drawn from the digester. During continuous operation, feedstock is continuously added to the reactor at approximately the same time that gas, effluent, scum, supernatant and/or sludge are removed from the reactor. During semi-continuous operation, feedstock is added to the reactor incrementally and gas, effluent, scum, supernatant and/or sludge are removed incrementally at the same or different times. It is generally preferred that addition of feedstock slurry and removal of digested slurry occur simultaneously, in an overlapping manner or within a short period of time from one another. During batch operation, larger portions of feedstock are added to the reactor at given time intervals and larger portions of gas, sludge, effluent, supernatant and/or sludge are removed from the reactor at the same or different time intervals. During continuous operation, the operating temperature and rate of gas production will be relatively constant. Generally continuous operation will provide a greater rate of gas production than batch or semi-continuous operation.
[0060] Gas production rate is expressed in terms of volume of fuel gas produced per given time interval of operation, e.g. ft. 3 of fuel gas produced per hour or day of operation, in terms of volume of fuel gas produced per unit weight of feedstock added to the reactor. In the example described herein, the digester produced approximately 5-8 ft. 3 of methane per pound of feedstock.
[0061] The quality of the fuel gas produced is generally expressed in terms of the BTU rating of the gas as it is removed from the reactor. In the example described herein, the methane collected from the digester had an average rating of about 500-800 BTU without a recirculation loop installed. Higher ratings in the range of about 800 to about 1000 BTU can be achieved using one or more of the preferred embodiments described herein. Pure methane, or sweet dry methane, has a rating of 1000 BTU.
[0062] A gas, such as methane, carbon dioxide, hydrogen, ammonia or hydrogen sulfide, which is produced in the anaerobic digester will be present in the reaction solution and headspace above the reaction solution. The content of each gas in the headspace and the reaction solution will vary according to the conditions, feedstock and/or anaerobic microbe present within the anaerobic digester. The content or percentage of each gas can be monitored using a gas chromatograph or other gas sensing or analyzing equipment used to determine the composition or presence of gases or gaseous mixtures. In preferred embodiments for producing methane, the content of the gas in the headspace will be about 60-100% methane, 0-40% carbon dioxide and 0-10% of other gases, such as ammonia, hydrogen or hydrogen sulfide. Since the digester is operated under approximately or strictly anaerobic conditions, the content of oxygen in the digester will generally be less than about 5%, less than about 1% or about 0%. When methane production starts, the content of oxygen in the digester will be about 0%. In order to minimize the introduction of oxygen into the digester, the feedstock slurry may be degassed before or after loading into the digester. Partial degassing can be done by exposing the feedstock slurry to a vacuum or by equilibrating (purging) it with an inert gas. The feedstock slurry will preferably include little to no oxygen, although it can include other gases.
[0063] The methane, carbon dioxide, or hydrogen produced by the anaerobic digester will generally be cleaned or purified by a scrubber to remove moisture, vapor, droplets, suspended solids or other such contaminants. The scrubber can comprise one or more of a filter, desiccant, zeolite, activated carbon, fiber, countercurrent wash solution, mixer, homogenizer, or other such components typically used in association with or comprised within gas scrubbers. Such components are well known to those of ordinary skill in the art of gas processing. In general, hydrogen sulfide is an undesired by-product or off-gas, which is removed from the desired product gas.
[0064] The gases that exit the anaerobic digester or the scrubber are then optionally separated into their individual components using conventional gas separation equipment, which is known to those of ordinary skill in the art for separating gas mixtures. The gases may also be processed with one or more compressor, or dehydration equipment. Alternatively, the gases are stored in pressurized storage vessels or tanks once they have been scrubbed. If the stored gas is purified methane or hydrogen or mixtures of methane or hydrogen with carbon dioxide, it can be used directly to operate the anaerobic digester or one or more of its components or it can be used to operate additional equipment such as that described above. Ammonia may also be found in the above-described gases.
[0065] The agitation means will agitate the reaction solution in the reaction vessel. Exemplary agitation means include one or more sparger bars, one or more mechanical agitators, a fluid recirculator, a gas recirculator and combinations thereof.
[0066] The sparger bar will bubble a gas through the reaction solution. The gas is generally CO 2 , that is produced by the anaerobic digester system, and can also be an inert gas such as nitrogen. The gas source can be the gas in the headspace of the anaerobic digester, gas that is downstream from the anaerobic digester, or a gas cylinder. A preferred sparger bar will recirculate downstream gas, and preferably gas that has had at least some of its methane removed therefrom, back into the reaction vessel. By feeding back into the reaction solution, in particular the sludge layer thereof, a product gas that has had methane removed from it, the reactor will produce more methane per pound of feedstock and the methane will be of higher quality, i.e., it will contain less carbon dioxide and have a higher BTU rating. In a preferred embodiment, a gas recirculator will comprise a sparger bar for adding a methane-stripped or reduced product gas, such as CO 2 , back into the anaerobic digester, an inlet port for receiving gas from the anaerobic digester, and one or more pumps and/or gas separators.
[0067] Another preferred embodiment of the invention provides an anaerobic digester system comprising a gas recirculation system comprising a gas separator for removing methane from the discharge gas received directly or indirectly from the anaerobic digester to form a methane-reduced gas, or carbon dioxide enriched gas, which is subsequently fed directly or indirectly back into the anaerobic digester. In this manner, the thermodynamic equilibrium for the digestion of the feedstock is pushed toward methane production and carbon dioxide consumption.
[0068] Another preferred sparger bar will recirculate gas from the headspace of the reactor back through the reaction solution and preferably the sludge layer to improve conversion of carbon dioxide to methane.
[0069] A fluid recirculator will preferably recirculate reaction solution from a first part of the reaction vessel to a second part of the reaction vessel. Alternatively, the fluid recirculator will recirculate feedstock slurry, scum sludge, supernatant or reaction effluent, or portions thereof through the reaction vessel. For example, the recirculator could recirculate either one or more of the scum, supernatant or sludge phases of the reaction effluent. A recirculator could also recirculate one or more fluids removed from the digester and added to a tank back to the digester. A recirculator could also recycle supernatant into the feedstock feeder to aid in preparing the feedstock slurry. According to another preferred embodiment, a fluid that is recycled back into the reaction vessel will have been stripped of at least some and preferably most or all of its methane gas prior to being added back to the reaction vessel.
[0070] Mechanical agitators which are useful in the anaerobic digester include all known fluid agitators such as a turbine, propeller, impeller, paddle, wheel, helical bar, stirrer, rotating reaction vessel, flexible tube or rod, magnetic agitator, tumbler, paddle wheel, and other mechanical agitators known to those of ordinary skill in the art of fluid mixing. The preferred mechanical agitator is a paddle.
[0071] By operating the anaerobic digester at higher pressures, higher quality, i.e., purer, methane is produced. Generally, the higher the digester pressure, the higher the purity or BTU rating of methane produced by the reaction vessel. The anaerobic digester generally does not require pressurization by external means as gas formation in the digester tends to pressurize the reaction vessel sufficiently. However, the reaction vessel can be pressurized with a pressurizer. The pressurizer can be a compressed gas cylinder, pump, or other such equipment, that forces an inert gas, a produced gas, feedstock slurry, or reaction effluent into the reaction vessel to increase the pressure of the reaction vessel to the desired operating pressure. Accordingly, the feedstock slurry feeder, gas recirculator, fluid recirculator, sparger bar or combinations thereof can serve as the pressurizer. In a preferred embodiment, the anaerobic digester system will comprise one or more pressure relief valves, vents or exhaust valves to reduce pressure within the reaction vessel. The anaerobic digester will also preferably comprise a pressure controller capable of controlling pressure within the reaction vessel and/or a pressure monitor capable of monitoring pressure within the reaction vessel. The anaerobic digester system can also comprise one or more pressure gauges that indicate the pressure within the system.
[0072] The feedstock slurry feeder can be a force-feed or gravity-feed system; however, a force-feed system is preferred. Preferred feeders include pumps of all types or gas pressurized feed tubes or chambers. Pumps are generally more preferred and a progressive cavity pump is most preferred.
[0073] The productivity of the anaerobic digester system, in terms of gas, especially methane, production is related to the pressure within the reaction vessel. The present inventors have found that the anaerobic digester can be operated at pressures exceeding 10 psi up to a pressure that does not exceed the design operating pressure of the gas handling system or prevent methane gas from flashing out of the liquid slurry in the digester. The increased pressure effects an increase in the rate of gas, preferably methane, production and feedstock digestion thereby reducing digestion periods and increasing the overall productivity of the anaerobic digester system in terms of ft. 3 of methane produced per pound of feedstock. Generally, the higher the pressure of the reaction vessel headspace, the higher the BTU rating of the methane gas produced.
[0074] Temperature affects the productivity of the anaerobic digester. Generally, elevating the temperature will increase the productivity, e.g. faster or more efficient gas production, of the digester up to a temperature that is harmful to the microbial flora in the digester, at which temperature productivity will decrease. Different microbes have different optimal temperatures. The temperature of the reaction solution can be controlled with a temperature controller that heats and/or cools the reaction solution. The temperature controller can be a heater, heat exchanger, jacket surrounding the reaction vessel, coil within the reaction vessel or other such equipment used for controlling the temperature of fluids within reactors. The temperature of the reaction vessel will preferably be monitored with a temperature monitor, such as a thermocouple or other equipment known to those of ordinary skill in the art. Alternatively, the temperature of the reaction solution is controlled by adding a temperature controller to the fluid recirculator, the sparger bar, or the feedstock slurry feeder. A heating or cooling jacket surrounding the reaction vessel is alternatively used to control the temperature of the reaction vessel contents.
[0075] Fluid levels in the reaction vessel are monitored with a fluid level detector and controlled with a fluid level controller that either increases or decreases the flow of feedstock slurry into or reaction effluent out of the reaction vessel.
[0076] [0076]FIGS. 1 a and 1 b include a process flow schematic of a first embodiment of the anaerobic digester system according to the invention. In this embodiment, cotton burrs obtained from a cotton gin are converted to methane and a nutrient rich effluent. Cotton burrs are separated from raw cotton in a cotton gin. The processed cotton is baled and the cotton seed is collected. The cotton burrs are collected and sized in a grinder to an acceptable particle size to form a feedstock. The dirt and sand in the feedstock are separated from the cotton burrs in a cleaner. A calculated amount of cotton burrs and a calculated amount of chicken manure, which together provide a feed mixture having an approximately 30:1 carbon:nitrogen ratio, are placed in a slurry mixer and heated fresh water is added to form a feedstock slurry which is fed directly into the digester. An anaerobic microbe is added to the digester to form a reaction solution that is heated. In batch operation, the digestion period is allowed to extend for 1 to 60 days, preferably less than 45 days, and more preferably less than 30 days, while forming a biogas containing predominantly methane and carbon dioxide and possibly other gaseous compounds. The biogas is passed through a scrubber to remove unwanted components to form a raw gas mixture that is then passed through a low-pressure compressor. The raw gas mixture from the low-pressure compressor is collected in a low-pressure storage tank or passed through a gas treater to remove carbon dioxide from the raw gas and form high purity (>90% wt., or >95% wt., or >98% wt.) methane. The high purity methane is then compressed with a high-pressure compressor and dried with a dehydrator to form “sweet-dry” methane. The sludge from the anaerobic digester is sent to a collection tank or a dryer to form dried sludge that can be used as landfill, artificial peat moss, charcoal briquettes, fuel or other similar purpose. The supernatant or effluent from the anaerobic reactor contains ammonia and is sent to an ammonia stripper that removes the ammonia from the supernatant. The treated or ammonia-stripped supernatant is then fed back into the anaerobic digester and used to digest additional feedstock. The ammonia collected from the supernatant can be used to make a plant fertilizer. Alternatively, a diluted form of the ammonia rich supernatant is used as a fertilizer without removing the ammonia therefrom.
[0077] Solid briquettes can be formed from the sludge by a process including the steps of: a) removing the sludge from the digester; b) optionally filtering the sludge in conventional solids filtration equipment to remove the excess fluid from the sludge to form a water-reduced sludge; c) forming the briquettes by pressure molding the water-reduced sludge; and d) optionally drying the briquettes in conventional drying equipment. Alternatively, the sludge can be dried after either step a) or step b) above. The briquettes and/or sludge need not be, but are preferably, completely dried before use as a fuel.
[0078] [0078]FIG. 2 is a process flow diagram of a second preferred embodiment of the anaerobic digester system according to the invention comprising a feedstock source ( 16 ), a feedstock grinder ( 18 ), feedstock slurry tank ( 20 ) and mixer ( 19 ), a fresh water source ( 17 ), a gas-fired water heater ( 6 a ), a solar water heater ( 6 b ), a Jw/Dd-1 hot water heat exchanger ( 6 c ), an engine exhaust water heat exchanger ( 6 e ), a discharge-gas compressor/water heat exchanger ( 6 d ), a feedstock slurry feeder ( 23 ), an inlet port ( 2 ), an anaerobic digester ( 1 ), a reaction solution agitator (comprising a mechanical agitator ( 5 a ) and a sparger bar ( 5 b )), effluent ports ( 3 a -3 c ), a supernatant storage tank ( 8 ), a sludge storage tank ( 9 ), a scum storage tank ( 7 ), a discharge gas scrubber ( 10 ), a discharge gas compressor ( 11 ), a discharge gas treater ( 12 ), a gas treater outlet scrubber ( 13 ), a discharge gas aerial cooler ( 14 ) and a discharge gas storage vessel ( 15 ), a temperature controller coil ( 4 ), an optional low pressure biogas recirculator ( 21 ), and an optional high pressure biogas recirculator ( 22 ). The anaerobic digester ( 1 ) has a temperature controller, e.g. heating coil, ( 4 ) through which water from the heat exchangers or heaters is circulated to control the temperature of the reaction solution. A sparger bar ( 5 b ) in the anaerobic digester in combination with the low pressure gas recirculator ( 21 ) recirculates gas from the headspace through the reaction solution to provide mild agitation of the reaction solution. The mixer ( 5 a ) and the high pressure gas recirculator ( 22 ) provide more strenuous agitation if it is needed to mobilize the solids of the reaction solution.
[0079] Under standard operating conditions, a feedstock is loaded into the grinder ( 18 ) where it is ground to the desired particle size. The ground feedstock and an aqueous solution are then placed in tank ( 20 ) and mixed with the mixer ( 19 ) to form a feedstock slurry. An inoculate of an anaerobic microbe and an aqueous solution is loaded into the anaerobic digester ( 1 ). The feedstock slurry is loaded into the anaerobic digester ( 1 ) with the feeder ( 23 ) through the inlet port ( 2 ) until the desired amount of feedstock slurry is added. The digester contents are thoroughly mixed. The anaerobic digester is operated at an elevated pressure, such as that generated by the digester itself, and at a temperature sufficient to promote the digestion of the feedstock and the formation of the product gas. After a sufficient period of time has passed, the reaction solution is removed from the anaerobic digester as a whole, in portions, or from different parts of the digester. For example, if the reaction solution is permitted to partition in the digester, the reaction solution can be drawn from the scum, supernatant and/or sludge layers and placed in the respective tanks ( 7 , 8 , 9 ). The product gas is removed from the headspace of the digester ( 1 ) and passed through a gas scrubber ( 10 ). Once the product gas is removed from the digester, it is also termed the discharge gas. The discharge gas is then compressed by the gas compressor ( 11 ) and passed through the gas treater ( 12 ) - gas separation system ( 13 ) that removes C0 2 , and H 2 S from the discharge gas. The NH 3 gas can be removed by passing the gas through a contactor and reboiler, regenerator and condenser, and a strong alkaline unit. The gases removed from the discharge gas can be passed through another gas separation system, not shown, that isolates one or more of the gas components. The gas separation system generally comprises a series of compressors, condensers, evaporators, pumps, tanks and optionally heating and/or cooling coils. The isolated component gas, preferably methane for burning or CO 2 for food grade CO 2 production, is then stored in the storage vessel ( 15 ) or released to a pipeline (not shown).
[0080] The supernatant, sludge and scum solutions and slurries, collectively termed the effluent, which are stored in their respective tanks ( 7 , 8 , 9 ), are then used as nitrogen rich fertilizer, insecticidal mixture, landfill, anaerobic digester inoculant, or other useful purpose. In addition, the effluent can be dried using conventional equipment to form valuable solid materials that can also be used as fertilizers, charcoal, carbon black, or other useful materials. The anaerobic digester tends to form ammonia, which can be removed from the product gas by the scrubber ( 10 ), gas treater ( 12 ) or gas separation system ( 13 ). The ammonia can be removed from the effluent by evaporation, condensation, precipitation or reaction with an acid source using methods well known in the art. The effluent can also be filtered, centrifuged or placed in settling tanks to separate the solids from the aqueous solution portion.
[0081] The product gas, if methane, can be used to operate gas-powered machinery such as the hot water heat exchanger ( 6 d ), the water heater ( 6 a ), and other equipment detailed above. Accordingly, the anaerobic digester system of the invention can be used in a ranch or farm setting to form a self-sustaining system. For example, the anaerobic digester system can be operated in conjunction with a chicken (broiler/hens) house to convert waste from the chicken house to methane gas, which is used to operate machinery or equipment associated with the chicken house. A cooperative system as described will in effect permit significant waste reduction thereby reducing the harmful effects that excessive hen house waste has on the environment. According to another example, the anaerobic digester system of the invention is used cooperatively in conjunction with a swine ranch to convert swine waste to methane and a fertilizer solution, wherein the methane is used to operate machinery used in the swine ranch. Other examples include the use of the anaerobic digester system in a cattle feedlot or a dairy cattle operation to convert waste material to methane and an insecticidal solution, wherein the methane is used to operate machinery used in the feedlot or dairy ranch.
[0082] The anaerobic digester can be operated such that the reaction solution is well mixed or stratified into the scum, supernatant and sludge zones or layers. When stratified, the scum layer includes materials that float in the reaction solution or are not well digested by the anaerobic microbe in the digester. The sludge layer includes materials that are denser than water and may or may not be digested by the anaerobic microbe. The sludge can also include feedstock solids that have not yet been digested. The supernatant layer is between the scum and sludge layers and generally comprises the bulk of the reaction solution. The supernatant layer includes water soluble components of the feedstock slurry and water soluble components, such as organic acids and ammonia, produced by the anaerobic microbe or other microbe or enzyme catalyst present in the digester.
[0083] The anaerobic digester system of the invention can be used to digest feedstock comprising any farm plant waste or any farm animal manure mixed with the proper additives to maintain an approximately 30:1 carbon:nitrogen ratio. Exemplary feedstock include cotton burrs; cow manure; cow manure mixed with feed, straw, hay, alfalfa, grass, soil, sand, tumble weeds and/or wood shavings; and chicken manure and urine containing wood shavings or cotton burrs. The useful materials prepared with these feedstock materials include ammonia, methane, charcoal (briquettes), carbon black, carbon dioxide, a nitrogen rich fertilizer, an insecticidal solution, and/or an insect repellant.
[0084] The supernatant solution taken directly from the reactor was tested as an insecticidal solution. The supernatant was applied directly to active fire ant mounds in a lawn. Within 24-48 hours, the ant mounds were inactive. In some cases, no ant activity has been seen in the treated mounds for a period of up to three to five months. The surrounding treated lawn is lush and thriving.
[0085] Methane was prepared in the anaerobic digester system exemplified herein. The product gas was collected from the headspace of the digester and passed through a scrubber containing a mist pad, or a glycol solution. The product gas was then compressed to about 300 psi. The gas was then passed through an amine gas treater to remove CO 2 . The gas was then pressurized above 300 psi and passed through a dehydrator to remove water to form sweet dry methane. Finally, the methane was stored in a pressurized vessel for later use.
[0086] Each of the sludge or supernatant layers prepared with the anaerobic digester served as a nitrogen enriched fertilizer. For example, an effluent solution that had been 80-90% digested was applied to grass at the required rate. The effluent could be diluted with water prior to application. Water containing effluent was applied to a nearby patch of grass. Within about one to four weeks, the treated grass was visibly greener and lusher than nearby untreated grass.
[0087] Carbon dioxide is a common product of anaerobic digestion. The carbon dioxide could be separated from the methane by use of a gas treater. The isolated carbon dioxide can be used to make dry ice, to pressurize the anaerobic digester or to provide an inert atmosphere in the anaerobic digester. Alternatively, the carbon dioxide can be reacted with caustic in the presence of heat or a catalyst to form a bicarbonate salt. The carbon dioxide can also be fed back into the digester to be converted to methane and increase the overall yield of bioconversion to methane.
[0088] Ammonia is also a common product of anaerobic digestion. The ammonia can be separated from the carbon dioxide and methane by using a gas separator. The ammonia can be isolated as liquid, compressed gas, or aqueous solution containing ammonia. For example, when the product gas is treated with water in the scrubber in a countercurrent manner, the water absorbs the ammonia from the product gas thereby generating an aqueous solution containing ammonia. Alternatively, the ammonia can be separated from the other gases by treating the product gas with an acidic agent that reacts with ammonia to form an ammonium salt or by passing the product gas through a bed containing a sequestrant of ammonia to sequester the ammonia. The ammonia can be used to make fertilizer or other nitrogen-based products.
[0089] The sludge and scum layers contain relatively high concentrations of solids. When the solids are dried, they can be used in fertilizer, ground fill, pressed board material, solid fuel, pressed fireplace logs, charcoal briquettes, medium for water filters, or as a “peat moss” equivalent. Alternatively, the sludge and scum layers removed from the reactor can be added back to the reactor. The solids may also be pulverized into a dust and blown into a burner system for a boiler or furnace for use as a fuel. The sludge can be dried by air, sun, and/or heat.
[0090] [0090]FIG. 4 depicts one embodiment of an integrated anaerobic digester system ( 25 ) comprising a feedstock slurry feeder system ( 26 ), a single-stage anaerobic digester system ( 27 ), a discharge gas processing system ( 29 ), an enriched effluent processing system ( 28 ), a gas recirculation system ( 31 ), and an effluent recirculation system ( 30 ). The feeder system prepares the aqueous feedstock slurry in one or more vessels ( 32 - 34 ) and charges the feedstock into the anaerobic digester system ( 27 ). The vessels ( 32 - 34 ) are connected in parallel via the conduits ( 38 ) or each vessel can be connected to a corresponding anaerobic digester ( 35 - 37 , respectively) via the conduits ( 41 - 42 ). The anaerobic digester system ( 27 ) comprises three anaerobic digesters ( 35 - 37 ) connected in parallel, such that the effluent of one digester does not enter another digester by way of the conduits ( 38 ) or ( 39 ). The flow of mass is indicated by the direction of the arrows. Together, the three anaerobic digesters ( 35 - 37 ) represent a single stage of anaerobic digestion, meaning that the feedstock is converted to discharge gas and enriched effluent without having to go from a first anaerobic digester ( 35 ) into a second anaerobic digester ( 36 ). This is unlike the system of Ort, which requires that the feedstock be predigested in a first anaerobic digested and then completely digested in a second anaerobic digester; therefore, the anaerobic digesters of Ort are connected serially as opposed to being in parallel.
[0091] Even though the anaerobic digester system ( 27 ) is depicted with three anaerobic digester vessels ( 35 - 37 ) it can comprise two, four or more such vessels. The vessels can be of the same construction and design or they can be different. In other words, each anaerobic digester vessel within a system can be the same or different than another digester vessel in the same system.
[0092] After digestion has progressed to the desired extent, the effluent is passed onto the effluent processing system ( 28 ) by way of the conduit ( 39 ). There it is processed as described previously herein. The effluent processing system comprises the above-described components. The effluent processing system ( 28 ) can be used as an effluent recirculation system (as indicated by the dash-dot-dot arrow ( 43 )), wherein effluent is returned to the same anaerobic digester from which it is taken. Alternatively, a separate effluent recirculation system ( 30 ) can be used. In either case, effluent is returned to the same anaerobic digester from which it is taken.
[0093] The discharge gas is passed onto the discharge gas processing system ( 29 ) by way of the conduit ( 40 ), where it is processed as described previously herein. The discharge gas processing system comprises the above-described components. The discharge gas processing system can be used as a gas recirculation system (as indicated by the dash-dot-dot arrow ( 44 )). Alternatively, a separate gas recirculation system ( 31 ) can be used.
[0094] The integrated system can also comprise a pressurizer system (not shown in FIG. 4) that pressurizes the anaerobic digester vessels ( 35 - 37 ). The pressurizer system will comprise the above-described components.
[0095] The connection of the various systems ( 26 - 31 ) of the integrated system ( 25 ) permits ease of total system and individual system scaling such that each system and the system as a whole can be scaled as needed. For large scale production, for example, the feeder system could comprise two mixing vessels; the digester system could comprise four digesters; and the entire system could comprise one or more of each an effluent recirculation system, a discharge gas recirculation system, a discharge gas processing system and an enriched effluent processing system. For small scale production, for example, the feeder system would comprise one mixing vessel; the digester system would comprise one digester; and the entire system could comprise one of each an effluent recirculation system, a discharge gas recirculation system, a discharge gas processing system and an enriched effluent processing system.
[0096] The carbon to nitrogen ratio of the non-water components of the feedstock will affect the performance of the digester, i.e., it will affect the productivity of the system, the efficiency of the digestion, the conversion of carbon dioxide to methane, the ability to maintain a stable pH and operating temperature. Generally, the carbon to nitrogen ratio of the feedstock will be about 30:1 for the systems exemplified below; however, feedstock having a carbon to nitrogen ratio in the range of about 25:1 to about 35:1 will still provide suitable results. When the carbon:nitrogen ratio of the feedstock is too high, the digestion will be less efficient and will leave an amount of undigested cellulose material.
[0097] For feedstock material having a low nitrogen content, a suitable feedstock slurry is obtained by adding a high nitrogen content. As detailed in the examples herein, cotton burrs (low nitrogen content feedstock) is mixed with chicken manure (high nitrogen content material) to form a feedstock material having an approximately 31:1 carbon:nitrogen ratio. The ammonia stripped from the digester effluent or discharge gas can be added in salt, liquid or gas form to a low nitrogen containing feedstock in order to raise the nitrogen content of the feedstock before addition to the digester.
[0098] In order to maintain a relatively constant pH for the slurry being digested, it may be necessary to add a buffering agent, alkalizing agent or acidifying agent to the slurry.
[0099] As used herein, the term “buffering agent” is intended to mean a compound used to resist change in pH. Such compounds include, by way of example and without limitation, potassium metaphosphate, potassium phosphate, monobasic sodium acetate and sodium citrate anhydrous and dihydrate and other materials known to one of ordinary skill in the art.
[0100] Generally, an acidifying agent will not be needed as the digestion of the feedstock tends to generate organic acids that drop the pH of digestion medium. As used herein, the term “acidifying agent” is intended to mean a compound used to provide an acidic medium to counteract a rise in pH of the digestion medium. Such compounds include, by way of example and without limitation, inorganic acid, acetic acid, amino acid, citric acid, fumaric acid and other alpha hydroxy acids, such as hydrochloric acid, ascorbic acid, and nitric acid and others known to those of ordinary skill in the art.
[0101] Generally, an alkalizing agent will be required since digestion of the feedstock tends to generate organic acids that drop the pH of digestion medium. As used herein, the term “alkalizing agent” is intended to mean a compound used to provide alkaline medium to counteract a drop in pH of the digestion medium. Such compounds include, by way of example and without limitation, lime, lye, ammonia solution or gas, ammonium carbonate, potassium hydroxide, sodium borate, sodium carbonate, sodium bicarbonate, sodium hydroxide and others known to those of ordinary skill in the art.
[0102] When an anaerobic digester system is constructed according to the invention, loaded with the correct mixture of components in order to form a feedstock having the desired carbon to nitrogen ratio, operated at the desired pressure and temperature and pH, the system will produce high purity methane gas.
[0103] The anaerobic digester system can be used to purify impure methane gas containing carbon dioxide. In this instance, the impure gas is injected into the digester containing a digestion slurry. As the impure gas is added, the methane gas flashes through the digestion slurry while a portion or all of the carbon dioxide is absorbed by the digestion slurry. The absorbed carbon dioxide is then converted to methane such that ultimately higher purity methane gas is produced.
[0104] The following examples should not be considered exhaustive, but merely illustrative of only a few of the many embodiments contemplated by the present invention. The methods described herein can be followed to conduct anaerobic digestion according to the invention.
EXAMPLE 1
Anaerobic Digestion of Cotton Burrs Mixed with Chicken Manure
[0105] This process was conducted in a batch-type manner. Fresh well water (318 gal.) was loaded into a digester equipped with an internal mechanical agitator and a heat controller. The water was heated until it reached a temperature of about 100° F. Then, anaerobic bacterium inoculant (10 gal.) and fresh wet chicken manure (14.5 lbs.) were added to the water with mixing. Finally, clean unground cotton burrs (200 lbs.) were added to the digester with mixing and the digester was sealed. The digester was then purged repeatedly with nitrogen gas to create a substantially anaerobic environment. With this loading, the percent solids of the reaction solution was approximately 4.48%. The digester was run for a period of 45 days with periodic sampling of the headspace. The temperature ranged from about 95° F. to about 120° F. and averaged about 105° F. to about 110° F. The pressure within the digester ranged from about 1 psi to about 45 psi. The total amount of gas produced was about 931.5 ft. 3 . The average rate of gas production was about 0.88 ft. 3 /hr, about 0.004 ft. 3 /hr/lb. of burrs or about 4.66 ft. 3 /lb. of burrs. The individual gas components of the product gas ranged from about 49% wt. to about 65% wt. for methane and from about 51% wt. to about 35% wt. for carbon dioxide. The content of ammonia in the product gas was not measured.
[0106] The following analytical measures were determined for the cotton burrs and chicken manure used in this procedure.
DRIED CHICKEN SOLIDS IN MEASURE BURRS MANURE TOTAL EFFLUENT Carbon (lbs. 16.0789 1.16 17.2389 Nitrogen (lbs.) 0.429 0.1239 0.5529 Carbon/Nitrogen 37.48 9.39 31.18 Energy (BTU/lbs.) 7593 7330 Ash (% wt.) 6.00 10.91 7.22 Volatile Solids (% wt.) 76.30 16.52 69.33 Moisture (% wt.) 17.49 71.5 23.45 Nitrogen (% wt.) 0.21 1.03
[0107] For other 200 lbs. batches using approximately the same amounts of ingredients, the total C/N ratio ranged from about 30 to about 32. In other batches run according to this procedure, the percent solids ranged from 4.5% to 5.0% wt.
EXAMPLE 2
Anaerobic Digestion of Cotton Burrs Mixed with Chicken Manure
[0108] This procedure was substantially the same as that of Example 1. The digester produced product gas containing about 63% methane.
EXAMPLE 3
Anaerobic Digestion of Cow Manure
[0109] This process was conducted in a batch manner. Fresh well water (150 gal.) was loaded into a digester equipped with an internal mechanical agitator and a heat controller. The water was heated until it reached a temperature of about 100° F. Then, a Clostridium spp. inoculant (1 gal.) and cow manure slurry (60 gal.) were mixed in a vessel having a total capacity of 150 gal., added to the digester and the digester was sealed. The digester was then purged repeatedly with nitrogen gas to create a substantially anaerobic environment. With this loading, the percent solids of the reaction solution was approximately 25-50%. The pH of the digester slurry was optionally adjusted to about 6.5-6.8 with lime. The digester was run for a period of 80 days with periodic sampling of the headspace. The temperature ranged from about 70° F. to about 100° F. and averaged about 80° F. to about 85° F. The pressure within the digester ranged from about 5 psi to about 18 psi. The pH of the reaction solution was kept between about 6.5-6.8 by the addition of lime. The methane produced was vented each day and the amount collected ranged from about 20-40 ft. 3 and averaged about 30-40 ft. 3 . The total amount of methane produced was about 2000 ft. 3 . About 10-15 lbs. of feedstock were added on a semi-weekly basis. The total amount of feedstock added was about 300 lbs. The amount of sludge, scum and supernatant removed from the reactor was about equal to the amount of feedstock added. The average rate of gas production was about 6-7 ft. 3 /hr of methane/lb. of feedstock. FIG. 3 depicts a chart of the measurements obtained for reaction solution pH, amount of methane gas produced (ft. 3 ), reaction solution temperature (° F.), and the headspace pressure of the reactor (psi). The BTU rating of the methane produced by the digester operated under these conditions ranged from about 600 to 850.
EXAMPLE 4
Anaerobic Digestion of Partially Composted Chicken Mixed with Cotton Gin Trash
[0110] Compost material, obtained from a plant in Mt. Pleasant, Tex., contained 75% wt. chicken (feathers, blood, bone, organs, flesh, intestines) and 25% wt. gin trash. The compost material had been composted for four days in a rotating composter prior to placement in the anaerobic digester. The anaerobic digester was operated within the acceptable ranges of the operating parameters described herein. The anaerobic digester (55 gal. size drum) included an inoculant obtained from a previous digestion of chicken manure. The particle size of compost material fed into the anaerobic digester was about 1.5 inches initially and was reduced to less than 0.5 inches during the period of digestion. The composted material was slurried with water to a ratio of about 1 part water to 2 parts compost material prior to sealing the digester. Methane production began about four days after the digester was sealed. Methane gas was released from the digester daily. The anaerobic digester was operated for six weeks and produced methane gas at a rate as described herein.
[0111] A process as described herein can be conducted in a meat, in particular chicken, rendering plant.
[0112] The above is a detailed description of particular embodiments of the invention. It is recognized that departures from the disclosed embodiments may be made within the scope of the invention and that obvious modifications will occur to a person skilled in the art. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed herein and still obtain a like or similar result without departing from the spirit and scope of the invention. All of the embodiments disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure.
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A process to recover energy, reduce pollution potential, and add value to organic waste such as animal manure is described. The process involves the anaerobic digestion of feedstocks, such as animal manure, at low to high temperatures in batch, semi-continuous or continuous reactors. The process makes use of existing handling and storage equipment at the farm and requires minimal supervision and skill by the operator. The system is not affected by high concentrations of volatile acids and ammonia or nitrogen. The productivity of the anaerobic digester system, in terms of methane gas production and quality, is exceptionally high. The anaerobic digester employs plural pressurizable anaerobic digesters connected in parallel. Consequently, the process is scaleable, low cost and does not interfere with regular farm operations.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to the following U.S. patent applications, filed concurrently herewith: “HIGH SIGNAL LEVEL COMPLIANT INPUT/OUTPUT CIRCUITS” (Qualcomm reference no. 072123-A); “HIGH SIGNAL LEVEL COMPLIANT INPUT/OUTPUT CIRCUITS” (Qualcomm reference no. 072123-C); “HIGH SIGNAL LEVEL COMPLIANT INPUT/OUTPUT CIRCUITS” (Qualcomm reference no. 072123-D); “HIGH SIGNAL LEVEL COMPLIANT INPUT/OUTPUT CIRCUITS” (Qualcomm reference no. 072123-E); the disclosures of which are expressly incorporated by reference herein in their entireties.
TECHNICAL FIELD
[0002] The present disclosure relates generally to input/output circuits and, more particularly, to input/output circuits compatible with high signal levels.
BACKGROUND
[0003] The use of various electronic devices has become nearly ubiquitous in modern society. For example, desk top and portable electronic devices are typically used daily by office workers and professionals in performing their work. It is not uncommon for such persons to regularly use electronic devices such as personal computer systems, personal digital assistants (PDAs), cellular telephones, pagers, digital sound and/or image recorders, etc. It is not uncommon for such electronic devices to be used in combination with one or more peripherals, such as an external display device, a memory device, a printer, a docking station, a network interface, etc. However, in order to properly interface with a peripheral, not only should the electronic device provide the appropriate physical connection and underlying interfacing protocols, but the electronic device typically must accommodate the signal levels (e.g., voltage levels) native to the peripheral interface.
[0004] It is not uncommon for different peripherals to utilize different signal levels at their associated peripheral interface. For example, a memory device provided by a particular manufacturer and/or operating in accordance with a particular standard may utilize peripheral interface signal levels on the order of 1.8V, whereas a similar memory device provided by a different manufacturer and/or operating in accordance with a different standard may utilize peripheral interface signal levels on the order of 2.6V or 3.0V. Although the foregoing example may not initially appear to be a large difference in signal level, electronic components may experience reliability (the capability of the component to operate without degraded performance over a long period of time) issues if designed for a lower signal level, such as 1.8V, and operated with a higher signal level, such as 2.6V or 3.0V.
[0005] The reliability of individual electronic components, such as transistors, can be compromised in many ways, such as electrical stress caused by prolonged application of electric fields across the terminals of the transistor. As these electric fields become higher, the lifetime of the electronic component is reduced. By way of example, the reliability limits for metal oxide on silicon (MOS) transistors depend on different breakdown phenomena including time dependent dielectric breakdown (TDDB), hot carrier injection (HCI), and negative bias temperature instability (NBTI). The reliability limits associated with each of the foregoing phenomenon for 45 nm MOS (1.8V) electronic components are provided in the table below. From this table, it can readily be appreciated that operation of such electronic components using signal levels of 2.6V or 3.0V are likely to present reliability issues.
[0000]
45 nm (1.8 V thick
Maximum
Phenomenon
oxide device)
Voltage (V)
TDDB
NMOS
2.7
PMOS
2.7
HCI
NMOS
2.0
PMOS
2.2
NBTI
PMOS
2.0
[0006] Various techniques have been employed in attempting to accommodate peripherals having different signal levels associated therewith. FIG. 1 shows exemplary prior art electronic device 100 having a plurality of input/output circuits, each configured to accommodate a particular signal level. Input/output circuit 120 , for example, may comprise electronic components designed to accommodate a first signal level (e.g., 1.8V), whereas input/output circuit 130 may comprise electronic components designed to accommodate a second signal level (e.g., 2.6V). That is, circuitry of output path 121 and circuitry of input path 122 may be adapted to reliably operate with peripherals interfacing using 1.8V signals. Circuitry of output path 131 and circuitry of input path 132 may thus be adapted to reliably operate with peripherals interfacing using 2.6V signals. Host circuitry 101 , such as may provide core operating functions of device 100 , may be adapted to interface with input/output circuits 120 and 130 using respective signal levels.
[0007] The technique for accommodating peripherals having different signal levels shown in FIG. 1 presents issues with respect to size and cost. Specifically, the illustrated embodiment provides for two separate input/output circuits, thus requiring additional physical area to house the circuitry. Moreover, costs associated with added components are incurred in the illustrated technique.
[0008] Another technique for accommodating peripherals having different signal levels is to utilize input/output circuitry, such as input/output circuitry 130 of FIG. 1 , designed to accommodate a higher signal level (e.g., 2.6V) both with peripherals interfaced using the higher signal level and peripherals interfaced using a lower signal level (e.g., 1.8V). Operating electronic devices with an electronic field lower than that the device is designed for will typically not result in the foregoing reliability issues. However, the use of circuitry designed for higher signal levels is generally not energy efficient and also degrades performance. Specifically, utilizing electronic components which are designed to accommodate higher signal levels in processing lower signal levels generally consumes more energy than utilizing appropriately designed electronic components.
[0009] Electronic devices today are becoming smaller and power management is becoming vital. For example, in order to maximize battery life in a portable device, even relatively small savings in power consumption can be important. Thus, utilizing input/output circuitry designed to accommodate higher signal levels when processing lower signal levels, although typically not providing reliability issues, results in undesired power consumption.
BRIEF SUMMARY
[0010] This application discloses a level detector having an input circuit adapted to accept signals of multiple signal levels for detecting a specific level. The signal levels include a first signal level and a larger second signal level. Electronic components of the input circuit have reliability levels less than the second signal level. A latch circuit is coupled to the input circuit for latching a signal consistent with a detected level of an accepted signal.
[0011] This application also discloses a level detector having an input node adapted to accept signals of multiple signal levels for detecting a specific signal level. The signal levels include a first signal level and a larger second signal level. An input transistor stack is coupled to the input node. The transistors have reliability levels less than the second signal level. A latch circuit is coupled to the input circuit for latching a signal consistent with a detected signal level of an accepted signal. The latch circuit's electronic components have reliability levels less than the second signal level. A pass gate is coupled to the output of the transistor stack to an input of the latch circuit. The pass gate prevents a terminal to terminal signal level of electronic components of the latch circuit from exceeding reliability limits.
[0012] This application also discloses a method including providing an input transistor stack adapted to accept signals of multiple signal levels for detecting a specific level. The signal levels include a first signal level and larger second signal level. The transistors have reliability levels less than the second signal level. The stacked configuration of input transistors is adapted to prevent a terminal to terminal signal level at each transistor from exceeding reliability limits. The method also includes providing a latch circuit for latching a signal consistent with a detected level of an accepted signal. The latch circuit has electronics with reliability levels less than the second signal level. The method also couples the input transistor stack to the latch circuit through a pass gate. The pass gate prevents a terminal to terminal signal level of electronic components of the latch circuit from exceeding reliability limits.
[0013] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0015] FIG. 1 shows a prior art electronic device having a plurality of input/output circuits, each configured to accommodate a particular signal level;
[0016] FIG. 2 shows a high level block diagram of an embodiment of high signal level compliant input/output circuitry;
[0017] FIG. 3 shows detail with respect to an embodiment of a predriver as may be used in the high signal level compliant input/output circuitry of FIG. 2 ;
[0018] FIG. 4 shows detail with respect to an embodiment of a level shifter as may be used in the predriver of FIG. 3 ;
[0019] FIG. 5 shows detail with respect to an embodiment of tapered buffers as may be used in the predriver of FIG. 3 ;
[0020] FIG. 6 shows detail with respect to an embodiment of a driver as may be used in the high signal level compliant input/output circuitry of FIG. 2 ;
[0021] FIG. 7 shows detail with respect to an embodiment of a level detector as may be used in the high signal level compliant input/output circuitry of FIG. 2 ;
[0022] FIG. 8 shows detail with respect to an embodiment of a mode controller as may be used in the high signal level compliant input/output circuitry of FIG. 2 ;
[0023] FIG. 9 shows detail with respect to an embodiment of a bias generator as may be used in the mode controller of FIG. 8 ; and
[0024] FIG. 10 shows detail with respect to an embodiment of a level shift controller as may be used in the high signal level compliant input/output circuitry of FIG. 2 .
DETAILED DESCRIPTION
[0025] FIG. 2 shows a high level block diagram of an embodiment of high signal level compliant input/output circuitry according to the concepts herein. Input/output circuit 200 of FIG. 2 is adapted to provide interfacing between host circuitry (not shown) of a host electronic device, such as a personal computer system, personal digital assistant (PDA), cellular telephone, pager, digital sound recorder, digital camera, digital video camera, personal entertainment player, gaming device, etc., and a peripheral, such as a memory device, a display, a printer, an electronic pointer, a transducer, etc. In particular, input/output circuit 200 is adapted to accommodate peripheral interface signals of both high level (e.g., 2.6V and/or 3.0V) and of low level (e.g., 1.8V). In accommodating high signal levels, input/output circuit 200 utilizes electronic components designed for use with respect to the low signal levels. Embodiments thereby provide efficiencies with respect to size and power consumption. As will better be appreciated from the discussion below, in accommodating high signal levels using electronic components designed for low signal levels, input/output circuit 200 is adapted to avoid reliability issues associated with application of relatively large electric fields across the terminals of the electronic components.
[0026] Input/output circuit 200 shown in FIG. 2 comprises output path 210 for interfacing signals from circuitry of a host device to circuitry of a peripheral and input path 220 for interfacing signals from circuitry of the peripheral to circuitry of the host device. Although input/output circuit 200 of the illustrated embodiment comprises both output path 210 and input path 220 , embodiments may implement concepts as described herein in input path circuitry alone or output path circuitry alone. Moreover, concepts described herein are applicable to circuitry in addition to input and output circuitry, and thus embodiments may be provided
[0027] Output path 210 and input path 220 of the illustrated embodiment are each adapted to accommodate both high level (e.g., 2.6V or 3.0V) and low level (e.g., 1.8V) signals. In particular, and as described in detail below, input path 220 includes level shift control 221 comprised of electronic components designed for low signal levels and adapted to reliably operate with respect to both low level and high level signals provided by peripherals coupled thereto. Similarly, and as described in detail below, output path 210 includes predriver 211 coupled to driver 212 , each comprised of electronic components designed for low signal levels and adapted to reliably operate with respect to both low level and high level signals provided to peripherals coupled thereto. Mode control 214 of the illustrated embodiment is coupled to predriver 211 , and in some embodiments to driver 212 , to provide control of circuitry therein for low and high signal level operation.
[0028] In operation according to particular embodiments, input/output circuit 200 is adapted to interact with circuitry of a host device using a predetermined low signal level and to interact with circuitry of peripheral devices using a signal level appropriate to the particular peripheral device currently interfaced. In many configurations, circuitry of the host system will perform power saving operation, such as to shutdown one or more power supply outputs (e.g., the core voltage). In order to accommodate such power saving operation without resulting in an ambiguous state of input/output circuit operation, mode control 214 of embodiments includes internal control signal generation utilized during periods of host circuitry power saving operation. That is, when one or more output of the host circuitry is unavailable due to power saving operation, mode control 214 of embodiments operates to internally generate appropriate control of predriver 211 and/or driver 212 to keep that circuitry latched in a selected low or high signal level state. Thus, when the host circuitry is returned to an operational state from power saving operation, input/output circuit 200 is configured to continue interfacing with the peripheral.
[0029] Input/output circuit 200 illustrated in FIG. 2 is versatile in that it is operable to automatically and autonomously configure itself for operation with respect to an appropriate signal level. That is, input/output circuit 200 of the illustrated embodiment is adapted to automatically select low signal level operation or high signal level operation as appropriate. Accordingly, level detection 213 of output path 210 is coupled to a peripheral for which interfacing is being provided to detect a signal level thereof and provide a mode selection signal to mode control 214 . Mode control 214 may thus provide control with respect to circuitry of predriver 211 and/or driver 212 in accordance with a mode (e.g., low signal level or high signal level) indicated by level detection 213 . Level shift control 221 of input path 220 in the illustrated embodiment is operable to compensate for high signal level operation without a mode control signal.
[0030] Having described operation of input/output circuit 200 of the illustrated embodiment at a high level, the individual functional blocks according to embodiments are described in detail below. It should be appreciated that the particular embodiments described herein are exemplary embodiments and that the concepts described may be implemented in embodiments in addition to or in the alternative to those shown.
[0031] Directing attention to FIG. 3 , detail with respect to an embodiment of predriver 211 is shown. Predriver 211 of the illustrated embodiment accepts input of a data signal from host circuitry directed to an interfaced peripheral, provides level shifting of the data signal from a signal level internal to the host device to a signal level appropriate for the particular peripheral interfaced, and provides outputs to drive driver 212 to provide data output to the peripheral at the appropriate signal level. To provide the foregoing operation, predriver 211 of the illustrated embodiment includes level shifters 311 - 313 and buffers 331 - 335 . Level shifters 311 - 313 operate to provide data signal level shifting from a level provided by host circuitry to a level appropriate for circuitry of an interfaced peripheral, such as in accordance with a mode selection signal provided by mode control 214 . Buffers 331 - 335 operate to provide data signal buffering to result in a data signal suitable for appropriately driving driver 212 . Logic gates 321 and 322 are provided in the illustrated embodiment to facilitate controllable enabling and disabling the output of predriver 211 . Specifically, application of appropriate enable signals to terminals of logic gate 321 (here a NAND gate) and logic gate 322 (here a NOR gate) operates to selectively enable/disable output of predriver 211 .
[0032] In accommodating signal levels higher than those for which electronic components of predriver 211 are designed, predriver 211 utilizes a non-zero signal level (e.g., core voltage of 1.1V) as a bias supply voltage (e.g., provided as virtual ground) when processing higher signal levels (e.g., pad voltages of 2.6V and 3.0V). Accordingly, level shifting of predriver 211 of the illustrated embodiment is provided in multiple stages. Specifically, level shifter 311 operates to level shift a data signal from host circuitry provided at a signal level internal to the host device (e.g., a core voltage such as 1.1V) to the lowest peripheral signal level accommodated (e.g., shown here as the 1.8V pad voltage). Level shifter 312 disposed in the pdata path of predriver 211 operates to level shift (if needed) the data signal as output by level shifter 311 to a level appropriate to the peripheral interfaced (e.g., a pad voltage of 2.6V or 3.0V). Where the interfaced peripheral operates with respect to the lowest peripheral signal level accommodated (shown here as 1.8V), level shifter 312 of the illustrated embodiment does not provide level shifting and effectively operates as a delay device.
[0033] In the 2.6/3.0V mode of operation (as may be selected by the mode signal received from mode control 214 ), the input of level shifter 312 of the illustrated embodiment toggles between 0V and 1.8V while the level-shifted output toggles between 1.1V and 2.6V or 3.0V. During the 1.8V mode of operation (as may be selected by the mode signal received from mode control 214 ), level shifter 312 of the illustrated embodiment does not perform a level translation and the output levels remain the same as the input levels (between 0V and 1.8V). The level shifter thus translates its input signals to levels which are consistent from a reliability point of view for the given mode of operation, as will be better understood from the discussion of an embodiment of level shifter circuitry shown in FIG. 4 below.
[0034] In addition to operating to maintain good reliability levels for the electronic components therein, it is desirable to provide good switching performance with respect to the data path. For example, the signals provided by predriver 211 operate to control electronic components of driver 212 to pull up to a data high level (e.g., 1.8V, 2.6V, or 3.0V using predriver 211 output pdata) and to control electronic components of driver 212 to pull down to a data low level (e.g., 0V using predriver 211 output ndata). Accordingly, embodiments operate to terminate a high or driving signal at one of the predriver outputs (pdata or ndata) before initiating a high or driving signal at the other one of the predriver outputs (ndata or pdata), thereby establishing “break-before-make” switching control of driver 212 . Such switching control avoids ambiguity with respect to the data output as well as avoiding undesired standby current in driver 212 .
[0035] The foregoing switching performance is achieved according to the illustrated embodiment by matching the signal propagation delay associated with the pdata and ndata paths in predriver 211 . For example, although level shifting beyond that provided by level shifter 311 is not needed in the ndata path of predriver 211 , level shifter 313 is provided in the ndata path to provide delay matching between the pdata path and the ndata path of predriver 211 . That is, the illustrated embodiment of level shifter 313 operates to both accept and output signal levels at the lowest peripheral signal level accommodated (here the 1.8V pad voltage) without level shifting the signal, but provides a propagation delay useful for matching the total delays of the pdata and ndata paths. The use of additional elements, such as an additional inverter in the output chain of the ndata path (e.g., inverters 333 - 335 in the ndata path as compared to inverters 331 and 332 in the pdata path) may additionally or alternatively be used for the foregoing delay matching. Delay matching ensures a good duty cycle for the final output signal. The delay can be programmed in each component of the ndata path based upon a mode signal received from mode control 214 . From the above is should be appreciated that low signal levels (e.g., 1.8V) are sufficient to provide switching off with respect to driver 212 , and thus the ndata path of the illustrated embodiment does not operate at the higher signal level (e.g., 2.6V or 3.0V) regardless of the particular mode output path 210 is operating in.
[0036] A virtual ground signal provided to the pdata path of predriver 211 is controlled by mode control 214 , i.e., based upon whether the system is in the 1.8V, 2.6V, or 3.0V mode of operation according to embodiments. In one embodiment, a 0V ground is provided when the system is connected to a 1.8V peripheral and a 1.1V ground is provided when the system is operating with 2.6V or 3.0V peripherals.
[0037] Directing attention to FIG. 4 , details with respect to an embodiment of a level shifter as may be utilized in providing the level shifter 312 are shown. Level shifter 410 shown in FIG. 4 provides a timing based level shifter configuration to accommodate signal levels higher than electronic components thereof are designed to reliably operate with. The configuration does not compromise the reliability of the electronic components of level shifter 410 .
[0038] In operation, a digital level shifter such as level shifter 410 converts a full-swing digital input between ground and a power supply level to a full-swing digital output that swings between ground and a different power supply level. Ideally, the level shifter circuit retains the phase information from the input signal to the output signal. Voltage level shifters utilized by input/output circuits typically shift signals from a core voltage (e.g., 1.1V) to a single pad voltage (e.g., either 1.8 V, 2.6V, or 3.0 V). Accordingly, in the case of a core voltage of 1.1V and a pad voltage of 2.6V or 3.0V, the voltage level shifting provided is from 1.1V to 2.6V or 3.0V, respectively. However, for purposes of meeting reliability limits of electronic components designed to operate with respect to 1.8V (e.g., 45 nm 1.8V transistors), terminals of these electronic components (e.g., the gate of a transistor) should not be allowed to toggle between 0 and 2.6V or 3.0V. Accordingly, in operation according to the illustrated embodiment, the two stage level shifting configuration of FIG. 3 results in level shifters 311 and 313 operating to toggle their output between 0V and 1.8V and level shifter 312 operating to toggle its output between 0V and 1.8V (in 1.8V mode) and 1.1V and 2.6V or 3.0V (in 2.6V or 3.0V mode). In the 2.6V mode, for example, level shifter 410 level shifts signals from 1.8V (shown as vdd_ 18 ) to 2.6V (shown as vddp) and from 0V (shown as vssx) to 1.1V (shown as vddc).
[0039] The mode in which level shifter 410 of this illustrated embodiment operates is controlled using the virtual ground signal provided by mode control 214 . In 2.6V mode, for example, virtual ground is set to 1.1V, whereas in 1.8V mode virtual ground is set to 0V. It should be appreciated that the high level voltage (shown as vddp) used by components of level shifter 312 , as well as other components of input/output circuit 200 , changes in each mode (e.g., 1.8V in 1.8V mode or 2.6V in 2.6V mode) as a result of that pad voltage being used by the interfaced peripheral. For example, where the interfaced peripheral provides the pad voltage, this voltage changes as a result of the peripheral having been interfaced. Where the host circuitry provides the pad voltage, this voltage changes as a result of the host circuitry being configured to interface with the peripheral. For example, versatile circuitry, such as level detection 213 , may be utilized in combination with the host circuitry to automatically and autonomously provide selection of an appropriate pad voltage by the host circuitry. Alternatively, the host circuitry may be manually switched to provide a pad voltage appropriate to a particular interfaced peripheral.
[0040] In 2.6V mode, when the input to level shifter 410 is 1.8V, transistors M 2 and M 1 (shown here as field effect transistors (FETs), more specifically, NFETS) are turned ON and transistors M 4 and M 3 (also shown as NFETs) are turned OFF. In operation, the gate voltage to transistor M 1 is HIGH (1.8v input to level shifter 410 ) for a certain time “d” and then goes low turning the transistor OFF. The delay “d” is provided by programmable delay logic 411 providing a selected delay that is long enough to pull down the voltage at node output_n. below vddc (core voltage of 1.1V), but that is short enough to avoid pulling the voltage at node output_n all the way down (0V). Thus, the voltage at node output goes to 2.6V (pad voltage vddp) and the voltage at node output_n goes to 1.8V.
[0041] Conversely to the foregoing operation, when the input to level shifter 410 is 0V, transistors M 4 and M 3 are turned ON (note inverter 430 disposed between the input to level shifter 410 and transistors M 3 and M 4 ) and transistors M 2 and M 1 are turned OFF. The gate voltage to transistor M 3 is HIGH (0v input to level shifter 410 ) for time ‘d’ and then goes low turning the transistor OFF. The delay ‘d’ is provided by programmable delay logic 421 , such as circuitry corresponding to that of programmable delay logic 411 , providing a selected delay that is long enough to pull down the voltage at node output below vddc (core voltage of 1.1V), but that is short enough to avoid pulling the voltage at node output all the way down (0V). Thus, the voltage at node output_n goes to 2.6V (pad voltage vddp) and the voltage at node output goes to 1.8V.
[0042] Relative sizing of the components of the pull down stacks and inverters controls to what levels the voltage nodes output and output_n are pulled down. For example, the voltage to which nodes output and output_n are pulled down to may be controlled by appropriately sizing electronic components of inverters 412 and 422 and the transistors of the corresponding pull down stack (transistors M 1 and M 2 for inverter 412 and transistors M 3 and M 4 for inverter 422 ). The main function of transistors M 1 and M 2 are to pull down sufficiently to write into the latch 412 , 422 . Similarly, transistors M 3 and M 4 have the same function.
[0043] The foregoing timing based operation of level shifter 410 avoids exposing terminals of M 1 and inverter 412 (e.g., a gate of a P-type FET (PFET) to the full pad voltage (e.g., vddp=2.6V) as would happen if output_n was pulled to 0V. This timing based operation avoids reliability issues because the full pad voltage, which is larger than what the electronic components can reliably withstand, is never present across the terminals of the electronic components.
[0044] In the 1.8 V mode, level shifter 410 of the illustrated embodiment does not perform level shifting of voltage levels but instead acts like a buffer. In this mode, where virtual ground is 0V, the delay logic of programmable delay logic 411 and 421 does not generate a time-shifted pulse but instead follows the input. Therefore, when the input to level shifter 410 is 1.8V, transistors M 1 and M 2 are both turned ON (transistors M 3 and M 4 are both turned OFF) and remain ON as long as the input is HIGH. Similarly, when the input to level shifter 410 is 0V, transistors M 3 and M 4 are both turned ON (transistors M 1 and M 2 are both turned OFF) and remain ON as long as the input is LOW. This continuous operation is permitted because there are no reliability restrictions as both the inputs and outputs toggle between 1.8V and 0V only.
[0045] Having described operation of level shifters as may be utilized in embodiments of predriver 211 , attention is again directed toward FIG. 3 . As previously mentioned, predriver 211 of the illustrated embodiment includes buffers 331 - 335 to provide data signal buffering in order to result in a data signal suitable for appropriately driving driver 212 . Buffering according to embodiments is performed by tapered buffers which toggle between a virtual ground (e.g., core voltage vddc of 1.1V) and the pad voltage (e.g., vddp of 2.6V) as shown in FIG. 5 . During 1.8V mode, the tapered buffers toggle between 0V and 1.8 V. Each buffer in a chain (e.g., buffers 331 - 332 and buffers 333 - 335 ) provides sufficient buffering (e.g., is comprised of larger transistors) to thereby step up the drive of the level shifted signal in order to sufficiently drive electronic components of the much larger driver 212 .
[0046] Referring again to FIG. 2 , it can be seen that the output of predriver 211 is coupled to the input of driver 212 according to the illustrated embodiment. As discussed above, the buffered, level shifted signals output by predriver 211 are provided to driver 212 for driving a signal to an interfaced peripheral at an appropriate signal level.
[0047] FIG. 6 shows detail with respect to an embodiment of driver 212 . The illustrated embodiment of driver 212 employs a stacked device driver strategy. Such a stacked driver configuration facilitates use of electronic components designed for a lower signal level being operated with a higher signal level without presenting reliability issues, such as to avoid the HCI breakdown phenomena as discussed below. Moreover, the stacked driver configuration facilitates electrostatic discharge (ESD) protection, such as by preventing snapback in driver FETs.
[0048] The stacked driver structure shown in FIG. 6 provides the pdata signal from predriver 211 to transistor M 17 (here a PFET), whose source is tied to Vddp, whereas transistor M 18 (here also a PFET) whose drain is closer to the output is controlled by a bias voltage pbias. During pull up, there is a small duration of time during which transistor M 17 is not fully turned ON and thus transistor M 18 would experience a higher voltage across its drain and source terminals, potentially causing a transient HCI issue. However, in avoiding the forgoing HCI issue, the drain of transistor M 18 is coupled to the output node through resistor Rp. The use of resistor Rp reduces the transient Vds overshoot of transistor M 18 , thereby keeping the voltages across its terminals within reliability limits.
[0049] Although the upper half of the exemplary circuitry of driver 212 , used for providing the data high portion of signal output, has been described above, it should be appreciated that the lower half of driver 212 , used for providing the data low portion of signal output, works similarly. Specifically, the ndata signal from predriver 211 is provided to transistor M 20 (here an NFET), whose source is tied to ground, whereas transistor M 19 (here also an NFET) whose drain is closer to the output is controlled by a bias voltage nbias. During pull down, there is a small duration of time during which transistor M 20 is not fully turned ON and thus transistor M 19 would experience a higher voltage across its drain and source terminals. Similar to the stacked configuration of the upper half of driver 212 , the drain of transistor M 19 is coupled to the output node through resistor Rn. The use of resistor Rn reduces the transient Vds overshoot of transistor M 19 , thereby keeping the voltages across its terminals within reliability limits. In one embodiment, the resistors are roughly 100 Ohms. The resistor type chosen should have high current carrying capacity.
[0050] As discussed above, predriver 211 and driver 212 provide level shifting and output of data signals provided from host circuitry to interfaced peripheral circuitry. As shown in FIG. 2 , mode control 214 and level detection 213 of the illustrated embodiment are utilized in output path 210 operation to facilitate operation of predriver 211 and driver 212 as described herein. Detail with respect to an embodiment of level detection 213 is shown in FIG. 7 and detail with respect to an embodiment of mode control 214 is shown in FIG. 8 .
[0051] Directing attention to FIG. 7 , detail with respect to an embodiment of level detection 213 is shown. Level detection 213 provides versatile operation with respect to input/output circuit 200 in that input/output circuit 200 is operable to automatically and autonomously configure itself for operation with respect to an appropriate signal level using level detection 213 . As shown in FIG. 7 , level detection 213 is coupled to a peripheral for which interfacing is being provided to detect a signal level thereof and provide a signal or signals for controlling a mode of operation (e.g., 1.8V mode, 2.6V mode, or 3.0V mode) of input/output circuit 200 . For example, level detection 213 of embodiments automatically detects the power supply voltage of the interfaced peripheral and causes circuitry of input/output circuit 200 to bias pad voltages accordingly. Accordingly, level detection 213 is able to automatically detect the voltage of an interfaced peripheral's power supply. Using such level detection circuitry, the use of external input or control for mode selection or, in the absence of mode selection, the use of separate input/output circuitry accommodating different signal levels can be avoided.
[0052] [In facilitating automatic detection of signal levels, circuitry of level detection 213 is high signal level compliant (e.g., high voltage compliant). However, as discussed in further detail below, such high signal level compliance is provided using electronic devices which themselves are designed for use with lower signal levels according to the illustrated embodiment. Accordingly, although potentially having voltage levels ranging from 1.8V to 3.0V applied thereto, embodiments of transistors M 5 -M 7 (shown here as FETs) comprise 1.8V transistors.
[0053] In operation, level detection 213 of the illustrated embodiment provides a digital signal level (mode) to various parts of input/output circuit 200 indicating the appropriate mode, thereby facilitating input/output circuit 200 functioning seamlessly irrespective of the signal level used by the particular peripheral interfaced thereto.
[0054] To better understand the operation of level detection 213 of the illustrated embodiment, assume that the voltage level the interfaced peripheral is operating at is 2.6V. Thus, vddp provided to transistor M 5 is 2.6V. Assuming vdd_ 18 is 1.8V, transistor M 5 is biased with a gate voltage of 1.8V which ensures that the gate to source voltage (Vgs) of this device is under reliable voltage levels, even where transistor M 5 is designed to operate at 1.8V, because Vgs minus the threshold voltage (Vth) of transistor M 5 is greater than Vth. This ensures that no two terminals of transistor M 5 exceed the maximum voltage level acceptable for reliability. In the foregoing example (vddp is 2.6V) transistor M 5 is turned ON and charges node 1 to vddp (2.6V). Transistor M 5 is sized so that it is large enough so that when M 5 is ON and M 6 and M 7 are also ON, the voltage at node 1 is vddp. In the case when the voltage level of the interfaced peripheral is 1.8V (or a voltage compatible with the host circuit), M 5 is OFF because vddp is 1.8 and the bias voltage to M 5 is 1.8. Thus, node 1 is pulled down to 0 by M 6 and M 6 . In either case, a latch 710 latches a value (node 3 ) related to the value at node 1 , as described below.
[0055] In the example when vddp is 2.6, transistor M 6 sees a drain voltage of vddp (2.6V) at node 1 . However, like transistor M 5 , the gate of transistor M 6 is biased suitably (here biased with vdd_ 18 ) to ensure reliable voltages across its terminals. Whether transistor M 7 is ON or OFF (depending upon the reset state discussed below), transistor M 6 is ensured an acceptable voltage at node 2 because the transistor M 6 is always ON and its gate is biased at 1.8V. Accordingly, the input stack of level detection 213 of the illustrated embodiment ensures that none of the transistors thereof experience voltages across their terminals which result in reliability issues.
[0056] As can be seen in FIG. 7 , transistor M 8 also has the drain thereof coupled to node 1 , which is charged to 2.6V in the foregoing example. Because transistor M 8 of the illustrated embodiment is an NFET, transistor M 8 does not let node 3 charge to more than Vdd_ 18 (1.8V) minus the threshold voltage (Vth) of M 8 . This ensures acceptable voltages across the terminals of transistor M 8 . Moreover, as a result of the voltage drop at node 3 associated with transistor M 8 , none of the other electronic components of level detection 213 see a voltage greater than Vdd_ 18 (1.8V). From the above, it can be appreciated that the circuitry of level detection 213 of the illustrated embodiment is made high voltage tolerant by the component layout and by biasing the components appropriately.
[0057] High/low stack 710 provides latching of mode levels in accordance with the source voltage of transistor M 8 . For example, a high voltage (1.8V in the illustrated embodiment) is latched when vddp is detected to be 2.6V or 3.0V and a low voltage (0V in the illustrated embodiment) is latched when vddp is detected to be 1.8V. These values occur because transistor M 8 controls node 3 to be Vdd_ 18 (1.8V) minus the threshold voltage (Vth). Buffers 721 - 723 of the illustrated embodiment operate to provide mode signal buffering to result in a mode control signal suitable for appropriately driving various components of input/output circuit 200 .
[0058] Level shifter 731 , inverter delay 732 and NOR gate 733 of the illustrated embodiment provide mode reset control according to an embodiment of level detection 213 . Level shifter 731 may be comprised of level shifter circuitry such as that described above with respect to level shifters 311 - 313 . Inverter delay 732 may be comprised of delay logic such as that described above with respect to programmable delay logic 411 and 421 .
[0059] In operation according to embodiments, the reset signal provided by the host circuitry is level converted by level shifter 731 to the signal voltage used by input/output circuit 200 (in the foregoing example, vdd_ 1 p 8 (1.8V)) for use by circuitry of level detection 213 . The configuration shown in FIG. 7 accommodates a reset
[0060] Directing attention to FIG. 8 , detail with respect to an embodiment of mode control 214 is shown. According to embodiments, mode control 214 provides the correct value of “ground” to circuitry of input/output circuit 200 (e.g., buffers 331 - 335 , level shifters 312 and 313 , inverters 412 and 422 , etc.) in order to facilitate voltages across electronic device terminals of input/output circuit 200 which are within reliability limits for those electronic devices to meet reliability limits.
[0061] During 1.8V mode (as indicated by the mode control signal provided by level detection 213 ), the value of virtual ground is switched to 0V (here vss) by switching circuitry 810 of the illustrated embodiment since the signal voltages are sufficiently low that reliability is not a concern. However, during 2.6V or 3.0V mode (again as indicated by the mode control signal), virtual ground of the illustrated embodiment is switched to the core voltage (here 1.1V) by switching circuitry 810 since the core voltage is sufficiently high to avoid voltages across terminals of the electronic components which exceed reliability limits.
[0062] Switching circuitry 810 of embodiments may be provided in various configurations. For example, solid state switching devices, such as FETs or the like may be used. Additionally or alternatively, mechanical switching mechanism may be utilized, if desired.
[0063] Mode control 214 of the illustrated embodiment is not only adapted to provide signal output consistent with a selected mode of operation, but is also adapted to maintain selection of a particular mode through a host circuitry power saving mode (e.g., sleep or freeze I/O mode), wherein one or more outputs of the host circuitry (e.g., power supply voltages) are unavailable to input/output circuit 200 . In order to accommodate such power saving operation without resulting in an ambiguous state of input/output circuit operation, mode control 214 of the illustrated embodiment includes bias generation 820 . Bias generation 820 of embodiments operates to generate a appropriate “virtual ground” level during periods of host circuitry power saving operation. That is, when one or more output of the host circuitry is unavailable due to power saving operation, bias generation 820 operates to internally generate appropriate control of predriver 211 and/or driver 212 to keep that circuitry latched in a selected low or high signal level state. Thus, when the host circuitry is returned to an operational state from power saving operation, input/output circuit 200 is configured to continue interfacing with the peripheral.
[0064] Directing attention to FIG. 9 , detail with respect to an embodiment of bias generation 820 is shown. In operation, power supply voltages provided by the host circuitry, such as the core voltage, collapse during power saving mode (as indicated by the freezio mode signal). Inverters 911 and 912 and NOR gate 921 cooperate to control circuitry of bias generation 820 to provide a bias during freeze I/O mode.
[0065] Bias generation according to the illustrated embodiment is provided by voltage divider 930 comprising OFF devices (shown here as transistors M 9 -M 12 latched in an OFF state) operable to pull the voltages at nodes vir_grnd_nfet_gate and vir_gnd_pfet_gate to vddp (e.g., 2.6V) and vdd_ 18 (e.g., 1.8V). Transistors M 13 and M 14 are switched on by the output of inverters 911 and 912 and NOR gate 921 , to thereby provide output at virtual ground which is the difference between the voltages of nodes_vir_gnd_nfet_gate and vir_gnd_pfet_gate. According to embodiments, the virtual ground node is a relatively high impedance node and thus is not intended to function as a charge sink. Accordingly, all nodes that are to be held at a certain state during freeze I/O mode are expected to settle to their steady state values before the virtual ground bias of bias generation 820 is provided to them.
[0066] The bias provided by voltage divider 930 during high signal level mode (e.g., 2.6V or 3.0V mode), wherein the freeze I/O signal provided by the host circuitry in the illustrated embodiment is 1.1V, is approximately the core voltage (e.g., 1.1.V). According to the illustrated embodiment, transistors M 9 and M 10 are PFETs disposed in a stacked configuration. Similarly, transistors M 11 and M 12 are PFETs disposed in a stacked configuration. The voltage provided to each of the foregoing stacks is, however, different. Specifically vddp (e.g., 2.6V) is provided to the gate of transistor M 9 whereas vdd_ 18 (e.g., 1.8V) is provided to the gate of transistor M 11 . Using these transistors in the illustrated configuration (and the leakage associated with their OFF state), the difference in voltage at the gates of transistors M 15 and M 16 settles down to a voltage that is very close to 1.1V. If there is a noise event that draws current from or to the virtual ground node, then one of the FETs turns on once the voltage of the virtual ground node goes outside a certain range from the steady state condition. At this point the bias becomes a low-impedance bias and makes sure the node returns to steady state condition. This voltage is thus used, as provided at the virtual ground output to bias other circuits of input/output circuit 200 during host circuitry freeze I/O mode when input/output circuit 200 is operating in a high signal level mode.
[0067] In operation according to embodiments of mode control 214 , bias generation is activated only when input/output circuit 200 is in a high signal level mode (e.g., 2.6V or 3.0V). Where input/output circuit 200 is in a low signal level mode (e.g., 1.8V), such as may be indicated by the mode control signal level from level detection 213 , mode control 214 of embodiments operates to couple virtual ground to vss (here 0V), whether the host circuitry is in a freeze I/O mode or in an operating mode.
[0068] Although embodiments of level detection 213 and mode control 214 are described above to provide versatile operation of output path 210 wherein operation thereof is automatically and autonomously adjusted for high or low signal level processing, embodiments of input/output circuit 200 may utilize manual selection of modes. For example, switching circuitry 810 of embodiments may be manually controlled in accordance with a signal level of an interfaced peripheral, if desired.
[0069] Having described detail with respect to functional blocks of output path 210 of embodiments, attention is directed to FIG. 10 wherein detail with respect to an embodiment of input path 221 is shown. In order to provide signal levels which are appropriate for the host circuitry, input path 220 of the illustrated embodiment includes level shift control 221 . Similar to operation of level detection 213 , level shift control preferably operates to accommodate input of both high and low level signals without resulting in voltages across terminals of the electronic components thereof exceeding reliability limits. In particular, although high signal levels (e.g., 2.6V and/or 3.0V) and low level signals (e.g., 1.8V) may be provided at the data input node of level shift control 221 labeled “padloc,” level shift control 221 is configured to automatically accommodate such signals and provide a desired signal level (e.g., 1.8V) at the data output node labeled “schm_out.”
[0070] In the high voltage compliant configuration of FIG. 10 , always on NFET transistor M 21 , disposed in a pass gate configuration, ensures that the electronic components of level shift control 221 do not see high voltage levels. More specifically, transistor M 21 operates to bring the node labeled lvl_dn_int down to 1.8-Vt. The first stage receiver, e.g., Schmitt trigger 1020 receives the 1.8-Vt signal and determines whether a 0 or 1 has been transmitted by the peripheral. Because the first stage receiver 1020 may be referenced to a different voltage than the input signal, it is important to have correct trip points. Pull up keeper circuitry 1011 , comprised of transistors M 22 and M 23 (shown here as PFETs) in a stacked configuration, and pull down keeper circuitry 1012 , comprised of transistors M 24 and M 25 (shown here as NFETs) in a stacked configuration, ensure that the input trip points (Vih, Vil) is met and that the signal level is referenced to the input path supply. The weak PFET keeper configuration of pull up keeper circuitry 1011 of the illustrated embodiment ensures the input to Schmitt trigger 1020 rises all the way to vdd_ 18 (1.8V) and shuts off any leakage. This ensures that this node rises quickly despite being driven by the NFET pass gate of transistor M 21 . NFET pull down keeper circuitry 1012 voltage divides the rising edge and provides better trip points (Vil) on the rising edge of the signal. Such a configuration is particularly useful in achieving a good trip point in high signal level modes (e.g., 2.6V and/or 3.0V) because the input to level shift control 221 is at a higher voltage and the first stage of level shift control 221 is referenced to a lower voltage (e.g., 1.8V). Accordingly, the foregoing embodiment of level shift control 221 maintains desired trip points whether operating at high signal levels or low signal levels. In one embodiment, a core_ie_h signal is provided, along with an enable signal to enable the NFET keeper when receiving a high voltage signal. The enable signal is also provided to enable the PFET keeper when receiving a high voltage signal (e.g., 2.6V or 3.0V).
[0071] Transistor M 26 of the illustrated embodiment is provided to facilitate disabling the peripheral input path. Specifically, providing an appropriate signal level to the node labeled “core_ie_h” (e.g., 1.8V) may be used to disable the output of level shift control 221 , and thus disable input path 220 .
[0072] Although various functional blocks have been described herein with reference to described embodiments, it should be appreciated that various circuitry an addition to or in the alternative to that described may be used in keeping with the concepts described herein. For example, ESD may be provided with respect to input/output circuit 200 , such as to provide human body model (HBM) ESD protection at the data output of output path 210 and to provide charged device model (CDM) ESD protection at the data input of input path 220 .
[0073] Moreover, circuit configurations different than those of the illustrated embodiments may be used in accordance with the concepts herein. For example, although various illustrated embodiments show a particular number of electronic components (e.g., FETs) disposed in a stacked configuration in order to accommodate the illustrative voltage levels described, different numbers of such electronic components may be used in such stacked configurations. For example, the stacked driver structure shown in FIG. 6 may utilize a stack of three FETs in the pdata (pull up) and/or ndata (pull down) driver stacks, such as where a higher signal level that discussed above is accommodated (e.g., 4.0V).
[0074] From the foregoing, it can be appreciated that input/output circuit 200 facilitates the use of electronic components designed for a lower signal level, such as 1.8V, and operated with a higher signal level, such as 2.6V or 3.0V. Accordingly, not only may a single input/output interface be used with respect to peripherals using different signal levels, but the input/output interface may use physically smaller and faster switching electronic components (e.g., 45 nm MOS, 1.8V electronic components). Moreover, embodiments described herein accommodate such different signal levels using a versatile operable to automatically and autonomously configure itself for operation with respect to an appropriate signal level.
[0075] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.
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A level detector has an input circuit adapted to accept signals of multiple signal levels for detecting a specific level. The signal levels include a first signal level and a larger second signal level. Electronic components of the input circuit have reliability levels less than the second signal level. A latch circuit is coupled to the input circuit for latching a signal consistent with a detected level of an accepted signal.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to a U.S. patent application Ser. No. (not yet assigned, but Attorney Docket Number EH-10586) filed on Feb. 12, 2002, herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates to brush seals. Specifically, the invention relates to brush seals that have reduced clearances.
[0003] A brush seal includes a side plate, a back plate and bristles between the plates. Gas turbine engines commonly use brush seals to prevent secondary flow from escaping through a gap between a stationary part (e.g. a diffuser case) and a rotating part (e.g. a turbine shaft). In this arrangement, the bristles of the brush seal impede the ability of the secondary flow to pass between the stationary and rotating parts. The bristles impede the secondary flow by extending from the stationary part, into the gap, and into contact with the rotating part.
[0004] The back plate of the brush seal remains a distance away from the rotating part. The size of the clearance between the back plate and the rotating part directly affects the efficiency of the brush seal. A brush seal with a larger back plate clearance allows a greater amount of secondary flow to pass through the bristles. A brush seal with a smaller back plate clearance allows a lesser amount of secondary flow to pass through the bristles.
[0005] Conventional brush seals tend to have larger clearances. While less efficient, these larger clearances help the brush seal to avoid contact between the back plate and the rotating component during operation of the engine. Contact between the metallic back plate of a conventional brush seal and the metallic rotating component can damage the brush seal. For example, such contact between the brush seal and the rotating component can wear away the back plate. Wearing away the back plate increases the clearance between the brush seal and the rotating component.
[0006] Such contact between the metallic back plate and rotating component can also form burrs on the back plate. Any burrs present on the back plate could nick or cut the adjacently located bristles. Depending on the severity of damage to the bristles, the entire bristle pack could fail.
[0007] One solution to this problem has been to allow the brush seal to float between the stationary component and the rotating component. The use of a floating brush seal, however, increases the complexity and part count of the brush seal assembly.
BRIEF SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to provide a new and improved brush seal.
[0009] It is a further object of the present invention to provide a more efficient brush seal.
[0010] It is a further object of the present invention to provide a brush seal that can be placed at a reduced clearance with the rotating component.
[0011] It is a further object of the present invention to provide a brush seal that exhibits less wear after contact with the rotating component.
[0012] It is a further object of the present invention to provide a brush seal that exhibits less damage after contact with the rotating component.
[0013] It is a further object of the present invention to provide a brush seal that is not complex.
[0014] It is a further object of the present invention to provide a brush seal that does not have a high part count.
[0015] These and other objects of the present invention are achieved in one aspect by a brush seal, comprising: a side plate; a back plate; and a bristle arrangement between the side plate and back plate. At least a portion of the back plate is made from a material that tends not to burr when contacting a rotating component.
[0016] These and other objects of the present invention are achieved in another aspect by a brush seal, comprising: a side plate; a back plate; and a bristle arrangement between the side plate and back plate. The bristle arrangement includes a plurality of bristles secured together by a joint. At least the back plate is made from a low coefficient of friction or low wear rate material.
[0017] These and other objects of the present invention are achieved in another aspect by a brush seal, comprising: a side plate; a back plate; and a plurality of bristles between the plates. The bristles are metallic and at least one of the plates is plastic.
[0018] These and other objects of the present invention are achieved in another aspect by a method of reducing a clearance between a brush seal and a component. The method comprises the steps of: providing a brush seal having a back plate and bristles; forming at least a portion of the back plate from a material that resists burring when contacting a rotating component; and spacing the portion from said component at a reduced distance. The reduced distance is less than a distance if the portion was not made from the low coefficient of friction or low wear rate material.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Other uses and advantages of the present invention will become apparent to those skilled in the art upon reference to the specification and the drawings, in which:
[0020] [0020]FIG. 1 is a cross-sectional perspective view of a conventional brush seal engaging a rotor;
[0021] [0021]FIG. 2 is a cross-sectional perspective view of a brush seal of the present invention;
[0022] [0022]FIG. 3 a is a detailed view of a section of the brush seal in FIG. 2;
[0023] [0023]FIG. 3 b is a detailed view of an alternative arrangement of the section in FIG. 3 a;
[0024] [0024]FIG. 4 is a cross-sectional perspective view of another alternative embodiment of a brush seal of the present invention;
[0025] [0025]FIG. 5 is a cross-sectional perspective view of another alternative embodiment of a brush seal of the present invention; and
[0026] [0026]FIG. 6 is a side-by-side comparison of the conventional brush seal in FIG. 1 and the brush seal of the present invention in FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
[0027] [0027]FIG. 1 displays a conventional brush seal arrangement 100 . The arrangement 100 includes a brush seal 101 rigidly secured to a first component 103 (typically a stationary component of the engine). The brush seal 101 extends from the first component 103 to engage a second component 105 (typically a rotating component of the engine).
[0028] The brush seal 101 includes a side plate 107 , a back plate 109 and a bristle pack 111 between the plates 107 , 109 . The plates 107 , 109 are made from suitable alloys, such as Inconel® or 400-series stainless steel. The side plate 107 can include a windage cover 113 . Typically, the plates 107 , 109 and the bristle pack 111 are welded together.
[0029] As seen in FIG. 6, the back plate 109 of the brush seal 101 remains a distance d 1 , from the second component 105 . The distance d 1 , is sufficient to ensure that the metallic back plate 109 tends to avoid contact with the metallic second component 105 . As described above, avoiding contact between the back plate 109 and the second component 105 helps prevent damage to the brush seal 101 .
[0030] [0030]FIG. 2 displays one embodiment of a brush seal arrangement 200 of the present invention. The arrangement likewise includes a brush seal 201 rigidly secured to a first component 203 . The brush seal 201 extends from the first component 203 to engage a second component 205 .
[0031] Similar to the conventional brush seal 101 , the brush seal 201 includes a side plate 207 , a back plate 209 and a bristle pack 211 between the plates 207 , 209 . The side plate 207 can include a windage cover 213 . The plates 107 , 109 and the bristle pack 111 can be secured together using suitable techniques such as welding.
[0032] [0032]FIG. 3 a displays a detailed view of the distal end of the brush seal 201 . In the arrangement shown in the figures, the distal end of the brush seal 201 is the inner diameter of the annular brush seal 201 . The inner face of the back plate 209 has a coating 215 placed thereon using known techniques. Preferably, application of the coating 215 on the back plate occurs before assembly of the brush seal 201 .
[0033] The coating 215 should be a material that tends not to produce burrs during contact with the rotating component. The coating 215 should also have capability to withstand the elevated temperatures encountered in the secondary flow of the engine. A suitable coating 215 could have a low coefficient of friction and/or a low wear rate. For example, the coating 215 could be a fluoropolymer such as PTFE. Alternatively, the coating 215 could be an abradable metal.
[0034] [0034]FIG. 3 b displays a detailed view of an alternate embodiment of the distal end of the brush seal 201 . Rather than the coating 215 of FIG. 3 a , the back plate 209 has an insert 217 secured thereto using known techniques. Depending upon the insert material, such techniques could include epoxy bonding or brazing. The back plate 209 could include a shoulder 219 to receive a correspondingly shaped extension 221 from the insert 217 . Preferably, bonding the insert 217 to the back plate occurs before assembly of the brush seal 201 .
[0035] The insert 217 should likewise be a material that resists burrs during contact between the back plate 209 and the rotating component. The insert 217 should also have capability to withstand the elevated temperatures encountered in the secondary flow of the engine. As discussed above, a fluoropolymer like PTFE could be used. In addition, the insert 217 could also be made from carbon, graphite or sintered impregnated metal matrix materials.
[0036] The alternative embodiments described above are preferably used with brush seals having the typical bristle arrangement shown in FIG. 2. The alternative embodiments described below are preferably used with brush seals having the bristle arrangement described in U.S. patent application Ser. No. (not yet assigned, but Attorney Docket Number EH-10586) filed on Feb. 12, 2002.
[0037] [0037]FIG. 4 shows another alternative embodiment of a brush seal 301 of the present invention. The brush seal 301 rigidly secures to a first component (not shown) and engages a second component (not shown).
[0038] The brush seal 301 includes a side plate 307 , a back plate 309 and a bristle pack 311 between the plates 307 , 309 . The annular bristle pack 311 (also referred to as a bristle ring) includes a plurality of bristles 323 secured together by a joint 325 . The joint 325 forms while welding the alloy bristles 323 (such as cobalt) together during an earlier assembly step.
[0039] The plates 307 , 309 each include a groove 327 , 329 to receive the joint 325 . The grooves 327 , 329 preferably prevent radial movement of the bristle pack 311 during engine operation without creating an interference fit. Differently than the earlier embodiments, the back plate 309 is made entirely from the aforementioned materials. For example, the back plate 309 could be made entirely from a suitable low coefficient of friction or low wear rate material. The back plate 309 could be made from these materials using known techniques such as injection molding, machining or extruding.
[0040] The plates 307 , 309 secure together using suitable techniques such as epoxy or braze bonding or using rivets (not shown) or threaded fasteners (not shown). The metallic side plate 307 helps provide rigidity to the brush seal 301 . If rigidity is not a concern, then the side plate 307 could also be made from the aforementioned materials. For example, the side plate 307 could also be made from a low coefficient of friction or low wear rate material. Preferably, the side plate 307 would be made from the same material as the back plate 309 .
[0041] [0041]FIG. 5 shows another alternative embodiment of a brush seal 401 of the present invention. The brush seal 401 has a one-piece body 431 rather than the discrete side plates and back plates of the earlier embodiments. The brush seal 401 also includes an annular bristle pack 411 with bristles 423 secured together by a joint 425 . The body 431 retains the joint 425 and a section of the bristles 423 .
[0042] The body 431 is preferably made from the aforementioned materials. For example, the side plate 307 could be made from a low coefficient of friction or low wear rate material. Preferably, the body 431 is plastic and is overmolded about the bristle pack 411 using known techniques. Other methods of forming the brush seal 401 could be used.
[0043] [0043]FIG. 6 displays the benefits of the present invention. Using suitable materials, the brush seal 201 of the present invention can position the back plate at a distance d 2 from the second component 105 . The distance d 2 of the present invention is less than the distance d 1 , of conventional brush seals with all-metallic back plates. The distance d 2 could be approximately 10-25% less than the distance d 1 , of conventional brush seals.
[0044] The reduced clearance exhibited by the brush seal of the present invention helps increase efficiency. The efficiency of the brush seal increases as the gap between the brush seal and the rotating component decreases. A smaller gap impedes the ability of the secondary flow to pass between the stationary and rotating parts.
[0045] The reduced clearance of the present invention also helps prevent bristle blowover. Blowover occurs when the secondary flow begins to urge the bristles in the flow direction. The bristles tend to wrap under the back plate. Such bending of the bristles introduces stresses to the bristles.
[0046] Since the present invention has a reduced clearance, shorter lengths of the bristles extend in cantilever fashion from the back plate. In other words, the back plate of the present invention supports a greater length of the bristles. This support helps the bristles withstand the urging of the secondary flow. As a result, the bristles tend to exhibit less stress.
[0047] Even with this reduced clearance, the present invention does not exhibit the damage encountered by conventional brush seals during contact with the rotating component. The aforementioned materials, such as a low coefficient of friction or low wear rate material, does not form burrs during such contact. Lacking burrs, the back plate does not nick or cut the bristles. With intact bristles, the efficiency of the brush seal tends not to degrade after contact between the back plate and the rotating component.
[0048] The present invention has been described in connection with the preferred embodiments of the various figures. It is to be understood that other similar embodiments may be used or modifications and additions may be made to the described embodiment for performing the same function of the present invention without deviating therefrom. Therefore, the present invention should not be limited to any single embodiment, but rather construed in breadth and scope in accordance with the recitation of the appended claims.
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A brush seal, comprising: a side plate; a back plate; and a bristle arrangement between the side plate and back plate. At least a portion of the back plate is made from a material that tends not to burr when contacting a rotating component. The bristle arrangement could include a plurality of bristles secured together by a joint. The entire back plate could be made from the low coefficient of friction or low wear rate material. In addition, the side plate could also be made from the low coefficient of friction or low wear rate material. The material allows a reduced clearance between the brush seal and the component engaged by the brush seal.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Provisional Application No. 61/607,022 filed on Mar. 6, 2012 and U.S. Provisional Application No. 61/609,447 filed on Mar. 12, 2012, herein incorporated by reference.
FIELD
[0002] The present telephone handset includes a housing with the appearance of an old-style handset that includes internal electronics, a simplified interface, and a multifunction interface.
BACKGROUND
[0003] Conventional cellular telephones are increasingly taking a variety of shapes not traditionally associated with telephone devices. This can cause confusion for individuals, particularly those suffering from age related loss of faculties, who previously used and were familiar with telephone handsets of an earlier design.
[0004] There exist a general shape that is largely universally recognized as representing a telephone type device. One example of such a device is the Western Electric Model 500 telephone handset that was manufactured for over 30 years. Millions of these devices were sold and many remain in use today. The pervasiveness of this and similarly shaped devices have caused the shape and silhouette of such telephones to represent a particular function to the general population. For example, pay phone stalls typically have imagery that shows the silhouette of a telephone handset that resembles the Western Electric Model 500 telephone handset. Many software packages that allow individuals to communicate with others use similar icons. Smartphone devices like the Apple iPhone also include a similar icon to represent the activation of the telephone functionality of the device. Thus, a device with a similar shape and silhouette will cause individuals to immediately understand that the device is usable as a telephone type device.
[0005] Additionally, individuals with limited physical and mental capabilities may have difficulty and even be unable to operate a conventional telephone device. These individuals nonetheless have a desire and/or need to communicate with others, and in particular with loved ones and caregivers. Family members, loved ones, and caregivers also have a desire to be able to communicate with these individuals and ensure their wellbeing. As the population ages, the number of these individuals will tend to increase.
[0006] Furthermore, a limited number of phone numbers are called with any frequency by individuals with limited physical and mental capabilities, or are of sufficient importance that they should always be easily accessible to these individuals.
[0007] Accordingly, it would be desirable to have a telephone handset that addresses these and other needs, particularly for individuals with limited physical and mental capabilities.
SUMMARY
[0008] It would be advantageous to include a way to associate keys of a simplified interface with desired phone numbers so that the dialing process can be simplified. The use of imagery may help simplify an interface even further. Both regular and impeded individuals can benefit from the simplified interface and easily operate the simplified interface and dial desired phone numbers.
[0009] The telephone handset for the infirm includes a housing, wherein the housing has the appearance of an old-style telephone handset, internal electronics including a microphone, a speaker, wireless communication circuitry, and signal processing circuitry for processing signals received by the wireless communications circuitry to drive the speaker and for processing signals received from the microphone to transmit a signal representative of the received microphone signal wireless to one or more remote audio communication devices. The telephone handset also includes a simplified user interface which includes a predetermined number of keys less than ten, where the keys are programmed to cause the internal electronics to initiate contact with at least one specific remote audio communication device upon actuation. The telephone handset also has a multifunction user interface with at least a full numeric keypad and other keys sufficient to program the keys of the simplified user interface.
[0010] The telephone handset for the infirm may be included in a telephone system. The telephone system includes the telephone handset with a housing, internal electronics, a simplified user interface, and a multifunction user interface. The telephone system also includes a base station that includes a multifunction user interface, a speaker, a microphone, and a camera, where the multifunction user interface has at least a full numeric keypad and other keys sufficient to program the keys of the simplified user interface of the telephone handset.
[0011] The details of one or more embodiments of the disclosure are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and drawings, and from the claims.
BRIEF DESCRIPTION OF DRAWINGS
[0012] The telephone handset and system will now be described by way of exemplary embodiments to which it is not limited by reference to the accompanying drawings, in which:
[0013] FIG. 1 illustrates one embodiment of the telephone handset with a simplified interface.
[0014] FIG. 2 illustrates another view of the embodiment of the telephone handset shown in FIG. 1 .
[0015] FIG. 3 illustrates the internal electronics of an embodiment of the telephone handset.
[0016] FIG. 4 illustrates a rear view of the embodiment of the telephone handset shown in FIG. 1 .
[0017] FIG. 5 illustrates one embodiment of the telephone handset and the base station.
DETAILED DESCRIPTION
[0018] FIG. 1 illustrates one exemplary embodiment of a telephone handset 1 with a housing 10 styled with the appearance of an old-style telephone handset. The handset 1 as shown in FIG. 2 has an oblong central section 11 that has a curved axis. The oblong central section 11 is sufficiently long to permit an average person to easily grasp. The oblong central section 11 connects two substantially similar disc-shaped end sections 12 . The disc-shaped end sections 12 resemble the ends of an old-style telephone handset and may include a plurality of apertures that allow for the passage of sound with minimal distortion. Each of the disc-shaped end sections 12 may include differing numbers of apertures or detents that visually simulate apertures, and at least one of the disc-shaped end sections 12 may include no apertures, but generally resemble apertures that had been needed for old-style audio transducers (speaker and microphone). The housing 10 in FIG. 1 may include apertures at a location other than the disc-shaped end sections 12 that also allow for the passage of sound with minimal distortion. For example, the ear-piece side of the housing 10 can have apertures for micro-electrical-mechanical (MEMs) based transducers around the periphery of one of the discs of the end sections 12 such that the sound is omnidirectional and acts as a speakerphone, so that if the user holds the telephone away from their ear, or even upside-down, the user can still hear the speaker on the other side of the line.
[0019] The housing 10 may include a base portion 13 at one end of the handset that helps allow the handset to sit on a surface in a manner that allows for hands-free operation of the device. In one embodiment, as shown in FIG. 2 , the base portion causes the curved axis of the oblong central section 11 to be more vertical than horizontal. The housing 10 may also include an attachment portion adapted for a lanyard or other device to ensure the telephone handset is easily accessible for the user. The attachment portion of the housing 10 may be structurally reinforced so that any additional stresses on the housing due to the use of a lanyard or other device do not compromise the housing 10 of the telephone device 1 .
[0020] The housing 10 of the telephone handset 1 encloses internal electronics 100 that perform the various functions of the phone. The internal electronics 100 include a central processing unit 104 that is connected to a microphone 101 , a speaker 102 , and a wireless communication module 103 (enabled to communicate using one or more of cellular, WiFi, BlueTooth, ZigBee, etc. protocols), among other features. The internal electronics 100 shown in FIG. 3 are powered by a battery 130 . The battery 130 may be recharged when the telephone handset 1 is connected to a power source through a wired connection such as power line, a Universal Serial Bus (USB) connection, or a wireless connection like an inductive charger. In an alternate embodiment, the internal electronics 100 may also include an on/off switch. The on/off switch deactivates the phone and helps reduce the possibility of unintentional activation of the phone in situations where the privacy of the individuals speaking near the handset is paramount. For example, when the user is speaking with his or her doctor, the user, or in some circumstances, the doctor may actuate the on/off switch so that the phone is deactivated and the privacy of the user can be ensured.
[0021] The central processing unit 104 executes programs stored in memory 116 , which can be flash memory or any suitable non-volatile memory. The central processing unit 104 receives inputs from the keypad 126 , the microphone 101 , the accelerometer 122 , the ambient light sensor 120 , the ringer mode switch 110 , the volume control switch 108 , and a USB interface, among others. The central processing unit 104 provides output by using the LCD 124 , the lighting of the keypad 126 , and the speaker 102 , among others. The central processing unit 104 also enables a remote device to monitor the inputs or readings from the different components of the telephone handset 1 and to execute various functions with the components of the internal electronics 100 of the telephone handset 1 . In an alternate embodiment, a camera that is optionally configured to capture panoramic images is included in the internal electronics 100 and may be remotely activated by a smartphone or other communication device to view the surrounding area of the telephone handset 1 .
[0022] A telephone handset 1 of the embodiment shown in FIG. 1 includes a simplified interface 20 . The simplified interface 20 has fewer keys than a conventional numeric keypad that has at least ten keys, such as six or four physical buttons 21 with imagery associated with the respective keys. The four keys 21 are associated with pre-programmed numbers so that when pressed, the associated number is automatically dialed.
[0023] The simplified interface 20 is illustrated as positioned on the oblong central section 11 of the housing 10 . The simplified interface 20 may be arranged on any portion of the handset 1 that is appropriate and is not limited to the positioning depicted in the included figures.
[0024] As stated above, each of the buttons 21 of the simplified interface 20 is programmed to activate a particular function. One such function is to dial the telephone number of a family member. Another function is to dial the telephone number of a caregiver or other service provider. A further function is to initiate contact with a remote audio communication device using a particular communications network. The functions programmed for each button 21 may include multiple aspects. One example is for the button to activate a function that plays prerecorded audio before dialing the telephone number of a particular family member. This helps improve the usability of the telephone handset by providing the user an audio message that corresponds to the actuated button 21 and confirms to the user the correct function is being executed. In fact, if the initiated communication path is not completed, an automated message may be played. For example, activation of a key might result in “Mom, thanks for calling me” and if the connection is not completed, “I can't pick up the telephone right now, but please leave me a message at the beep and I will call back as soon as I can” or the like. The functions activated by each of the buttons 21 of the simplified interface 20 may also perform aspects that are not associated with connecting to a remote audio communication device. For example, one of the buttons 21 of the simplified interface 20 may cause the telephone handset 1 to play prerecorded audio that indicates who the main user of the telephone handset 1 is. This function is particularly useful in situations where a plurality of telephone handsets 1 may exist in the same area, leading to confusion as to whom each telephone handset 1 belongs.
[0025] The imagery of the physical buttons 21 corresponds to the function of the particular button. The imagery may be affixed to the button 21 or may be an integral part of the physical button 21 . The imagery helps a user to easily and intuitively understand the function associated with the button even when the user has reduced or limited mental abilities. A further embodiment may use physical buttons that each include screens that are easily reprogrammable to display the desired imagery. A still further embodiment may use a touch screen with areas that when activated execute a particular function. The touch screen may display imagery in the areas that when activated execute a particular function so that the function associated with the area can be easily and intuitively understood by the user.
[0026] A multifunction user interface 30 may be included on the telephone handset 1 . In an embodiment depicted in FIG. 4 , the multifunction user interface 30 is located on the rear surface of the oblong central portion 11 of the housing 10 . The multifunction user interface 30 may be positioned on any portion of the handset 1 that is appropriate and is not limited to the positioning illustrated in the included Figures. The multifunction user interface 30 has a full numeric keypad and other multifunction keys 31 . The multifunction user interface 30 programs the keys 21 of the simplified interface 20 and assigns the particular functions that are executed when the keys 21 of the simplified interface 20 are activated. The multifunction user interface 30 may include a display for facilitating the programming of the keys 21 of the simplified interface 20 . The multifunction user interface 30 causes the internal electronics 100 to change the functions that are executed when the buttons 21 of the simplified interface 20 are activated by the user. In an alternate embodiment, the multifunction user interface 30 also assigns the imagery displayed on each of the buttons 21 of the simplified interface 20 .
[0027] The multifunction user interface 30 may be covered by an access cover 40 . The access cover 40 may be secured and require the use of a separate unsecuring device (such as a paperclip) to allow access to the multifunction user interface 30 . In one embodiment, a paper clip is used to unsecure the access door 40 . In an alternate embodiment, a small coin or other unsecuring device may be used to unsecure the access door. The access cover 40 may be transparent, translucent, or opaque so as to obscure the components underneath.
[0028] In an alternate embodiment, the simplified interface 20 may be programmed by a separate control device. The separate control device may be connected to the telephone handset 1 by a wired or a wireless connection. The separate control device may use a USB, Thunderbolt, FireWire, Ethernet, or another common wired interface. The separate control device may use a Bluetooth, WiFi (IEEE 802.11), Zigbee, inductive, or other common wireless interface. The separate device may include a multifunction user interface that can assign the particular functions that are executed when the keys 21 of the simplified interface 20 are activated. The multifunction user interface of the separate control device may also assign the imagery displayed on each of the buttons 21 of the simplified interface. The separate control device may also control other aspects of the telephone handset 1 including the ringer mode and the volume.
[0029] The separate control device may also monitor the inputs or readings from the different components of the telephone handset 1 and execute various functions with the components of the internal electronics 100 of the telephone handset 1 . In one embodiment, the separate control device may be used to monitor the ambient light sensor 120 to determine if the user of the telephone handset 1 has turned on a light in the room. In another embodiment, the separate control device may be used to monitor the accelerometer 122 to determine if the handset 1 has abruptly changed from a substantially vertical orientation to a substantially horizontal orientation. In response, the separate control device may remotely activate the microphone 101 and the speaker 102 so that communication may be established with the user of the telephone handset 1 so that the condition of the user may be ascertained. In a further embodiment, the separate control device may remotely activate the camera so that the condition of the user may be ascertained.
[0030] The telephone handset 1 may be programmed to respond in a predetermined manner depending on which remote audio communication device is attempting to page the user of the telephone handset 1 . One example of a predetermined response is automatically answering the page from the remote audio communication device after a set number of rings. This predetermined response allows the user of the telephone handset 1 to easily and automatically respond to pages from a particular remote audio communication device without user intervention. Another example of a predetermined response is to play prerecorded audio that corresponds to the remote audio communication device that is paging the telephone handset. The prerecorded audio may announce to the user of the telephone handset 1 who is attempting to contact the user. This predetermined response allows the user of the telephone handset 1 to determine who is attempting to contact the user without requiring any intervention by the user. The predetermined response may also include a visual indication of who is attempting to contact the user. For example, if the person attempting to contact the user of the telephone handset 1 is associated with one of the keys 21 of the simplified interface 20 , the key 21 may be illuminated in a distinctive fashion so that the user can immediately understand who is attempting to contact the user. A further example of a predetermined response is to require user intervention to respond to pages from remote audio communication devices. One example of such a predetermined response requires that the user press one of the simplified interface keys 21 to respond to the page from the remote audio communication device. Another example of such a predetermined response requires the user to press a particular sequence of keys 21 of the simplified interface 20 to respond to the page from the remote audio communication device. The predetermined responses may be programmed by the multifunction interface 30 or may be programmed by a separate control device connected by a wired or wireless connection. Other predetermined responses may be configured to improve the usability of the telephone handset 1 .
[0031] The telephone handset 1 may also be programmed to respond in a predetermined manner when the remote audio communication device that corresponds to the actuated key does not respond to the request to initiate contact. In one embodiment, after the remote audio communication device has not responded to the request to initiate contact for a predetermined period of time, the telephone handset 1 plays prerecorded audio that corresponds to the remote audio communication device that did not respond. One example of such prerecorded audio may indicate to the user that the person to whom the remote audio communication device is associated with is currently not available but will return the call as soon as the person returns to the remote audio communication device. This improves the usability of the telephone handset 1 by providing information to the user when the person associated with the remote audio communication device does not respond.
[0032] The telephone handset 1 may be operated as a speaker phone where the handset 1 may be placed on a surface that is not adjacent to the user's head. The telephone handset 1 may also be operated like conventional telephone device that is placed adjacent to the user's head. The speaker 102 of the telephone handset 1 may be configured so that the volume will not damage the user's hearing or cause discomfort when the telephone handset 1 is operated adjacent to the user's head.
[0033] The telephone handset 1 may also be part of a telephone system. The telephone system includes the telephone handset 1 and also a base station 50 . One embodiment of the base station 50 is illustrated in FIG. 5 . The base station 50 accepts at least one telephone handset and secures the handset in an upright manner so that the plane defined by the two substantially similar disc-shaped end sections 12 is substantially perpendicular to the horizontal surface on which the base station 50 rests. In an alternative embodiment, the base station 50 accepts two or more telephone handsets 1 and secures the handsets 1 in an upright manner so that the planes defined by the two substantially similar disc-shaped end sections 12 are substantially perpendicular to the horizontal surface on which the base station 50 rests.
[0034] The base station 50 is adapted to both secure the handsets in an upright manner and also to recharge the telephone handsets 1 . The base station 50 may recharge the telephone handsets 1 through inductive charging or through a standard electrical connection. The base station 50 also includes a multifunction interface 60 for each of the telephone handsets 1 Like the multifunction user interface 30 of the telephone handset 1 , the multifunction interface 60 may be used to program the corresponding telephone handset 1 and assign the particular functions that are executed when the keys 21 of the simplified interface 20 are activated.
[0035] The base station 50 may also include a speaker and a microphone. The speaker and the microphone of the base station 50 allows the base station 50 transmit and receive audio to and from the remote audio communication device even if the speaker 102 and the microphone 101 of the telephone handset 1 are partially or completely obstructed by the base station 50 when the telephone handset 1 is secured to the base station 50 . The base station 50 may also include a camera optionally configured to capture panoramic images and a display device 70 for displaying imagery. The multifunction interface 60 of the base station 50 may be used to assign the imagery displayed on the display device 70 of the base station 50 . The base station 50 also includes internal electronics that allow the inputs or the readings from the different components of the base station 50 to be monitored remotely and that also allow the components of the internal electronics of the base station 50 to execute various functions. The base station 50 may be controlled by a separate control device connected by a wired or wireless connection.
[0036] The telephone system may include a separate central control device. The separate central control device is similar to the separate control device but is also configured to control multiple telephone handsets 1 and multiple base stations 50 . The separate central control device connects to multiple telephone handsets 1 and multiple base stations 50 by way of a wired or a wireless interface. The separate central control device may monitor the inputs or readings from the different components of the multiple telephone handsets 1 and execute various functions with the components of the internal electronics 100 of the multiple telephone handsets 1 . The separate central control device may also monitor the inputs or readings from the different components of multiple base stations 50 and execute various functions with the components of the internal electronics of the multiple base stations. In an alternate embodiment, the separate central control device may assign the imagery displayed on the display device 70 of the base station 50 .
[0037] In one embodiment, the separate central control device may be used to monitor the accelerometers 122 of multiple telephone handsets 1 . For example, when the accelerometer 122 of a particular telephone handset 1 indicates that the handset 1 has abruptly changed from a substantially vertical orientation to a substantially horizontal orientation, the separate central control device may remotely activate the microphone 101 and the speaker 102 of the telephone handset 1 so that communication may be established with the user of the telephone handset so that the user's condition may be ascertained. The separate central control device may also remotely activate the microphone and the speaker of the base station 50 to ascertain the user's condition also. The separate central control device may also act as a remote audio communication device so that the user of the telephone handset 1 and the base station 50 may communicate with an individual operating the separate central control device.
[0038] It will be understood that the foregoing description is of the preferred embodiments, and is, therefore, merely representative of the article. It can be appreciated that many variations and modifications of the different embodiments in light of the above teachings will be readily apparent to those skilled in the art. Accordingly, the exemplary embodiments, as well as alternative embodiments, may be made without departing from the spirit and scope of the articles and methods as set forth in the attached claims.
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The telephone handset for the infirm includes a housing, wherein the housing has the appearance of an old-style telephone handset, internal electronics including a microphone, a speaker, wireless communication circuitry, and signal processing circuitry for processing signals received by the wireless communications circuitry to drive the speaker and for processing signals received from the microphone to transmit a signal representative of the received microphone signal wireless to one or more remote audio communication devices. The telephone handset also includes a simplified user interface which includes a predetermined number of keys less than ten, where the keys are programmed to cause the internal electronics to initiate contact with at least one specific remote audio communication device upon actuation. The telephone handset also has a multifunction user interface with at least a full numeric keypad and other keys sufficient to program the keys of the simplified user interface.
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TECHNICAL FIELD
This invention relates generally to circuits for providing analog information to a load, and more specifically, for providing a low power and low noise circuit for providing audio input to a load.
BACKGROUND
Various circuits are known for providing information from a digital source to an analog output such as a speaker. For example, common consumer applications such as portable music or communication devices provide digital data for conversion to an analog output such as a speaker or headphones. A goal for such devices is to reduce the amount of power used in driving its playback circuit such that there can be an increase in the playback time for the device. For certain audio playback devices, the audio quality relies on the dynamic range at negative 60 decibels power output. Various elements of the playback circuits, however, can create noise that necessitates consuming more power to overcome the noise introduced by those circuit elements.
FIG. 1 depicts one such known architecture for a circuit that provides an audio signal to a headphone for playback for a listener. In this architecture, an over-sampled sigma delta modulator 105 receives an audio signal from an UP-sampler circuit 110 . The output of the over-sampled sigma delta modulator 105 is provided to a current steering digital to analog converter 115 . The digital to analog converter 115 provides two outputs that are received by a current to voltage converter 120 . The current to voltage converter includes multiple elements such as two resistors R 1 and R 2 and an amplifier A 1 . The output of this circuit is provided to a headphone amplifier 125 . The headphone amplifier 125 includes multiple resistors R 3 , R 4 , R 5 , and R 6 and a further amplifier. The output of the headphone amplifier 125 is provided to the headphone speakers that, in turn, produce the audible signal for the listener. In this circuit, the noise for the audio signal is created primarily by the current steering digital to analog converter 115 , the current to voltage converter 120 , and the headphone amplifier 125 . The noise provided by the circuit elements results in a minimum power needed to drive the audio signal to have a sufficient audio quality above the background noise created by the circuit elements. Moreover, the noise created by the circuit elements negatively affects the dynamic range of the audio signal thereby reducing the audio quality experienced by the listener.
SUMMARY
Generally speaking and pursuant to these various embodiments, a circuit for providing audio signals to a load such as a speaker is provided that uses the speaker or headphone amplifier structure as a current to voltage converter, thereby eliminating a separate current to voltage converter from the circuit. Such a design removes one of the elements that creates noise in the circuit architecture and improves the dynamic range for the audio signal.
In one such example, the output of a digital to analog converter of the audio signal may be a single ended output provided to the speaker or headphone amplifier. An example of such a digital to analog converter can include a series of current sources that are summed up to provide the single ended output to the speaker or headphone amplifier. In the case where the current sources have positive and negative current source mismatch, a feedback mechanism can be employed to correct for the mismatch and reduce introduction of harmonic noise into the signal through the digital to analog converter. So configured, noise introduced by a current to voltage converter in previous known circuits is eliminated. Implementation of new circuits such as those described herein improve the dynamic range of the audio signal and reduces noise, thereby improving audio quality and extending the battery life of devices implementing such a design. These and other benefits may become clear upon making a thorough review and study of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The above needs are at least partially met through the provision of the low noise and low power arrangement for playing audio signals described in the following detailed description, particularly when studied in conjunction with the following drawings wherein:
FIG. 1 comprises an example prior art circuit scheme as configured in accordance with various previously known circuit designs;
FIG. 2 comprises an example circuit scheme as configured in accordance with various embodiments of the invention;
FIG. 3 comprises a circuit diagram of an example digital to analog converter with an amplifier and feedback circuit as configured in accordance with various embodiments of the invention;
FIG. 4 comprises an example feedback circuit as configured in accordance with various embodiments of the invention;
FIG. 5 comprises a circuit diagram showing one cell of an example digital to analog converter connected to an amplifier into one representation of a feedback circuit as configured in accordance with various embodiments of the invention;
FIG. 6 comprises a representation of an example of cycling of current sources being connected to the feedback circuit with respect to the clock cycle of the circuit as configured in accordance with various embodiments of the invention; and
FIG. 7 comprises a flow diagram of an example method of operation of a circuit as configured in accordance with various embodiments of the invention.
Skilled artisans will appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions and/or relative positioning of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of various embodiments of the present invention. Also, common but well-understood elements that are useful or necessary in a commercially feasible embodiment are often not depicted in order to facilitate a less obstructed view of these various embodiments. It will further be appreciated that certain actions and/or steps may be described or depicted in a particular order of occurrence while those skilled in the art will understand that such specificity with respect to sequence is not actually required. It will also be understood that the terms and expressions used herein have the ordinary technical meaning as is accorded to such terms and expressions by persons skilled in the technical field as set forth above except where different specific meanings have otherwise been set forth herein.
DETAILED DESCRIPTION
Referring now to the drawings, and in particular, to FIG. 2 , an illustrative circuit architecture that is compatible with many of these teachings will now be presented. The example apparatus 200 of FIG. 2 includes a modulator 205 configured to receive an input signal and to output a digital signal that is a modulated form of the input signal. A digital to analog converter 215 is configured to receive the digital signal, by one example audio data, and provide a single ended analog output, representing in this example audio signaling, at output 217 . Other types of digital data can be so processed. The described digital to analog converter 215 in one example comprises a Class B style single ended output digital to analog converter. The apparatus 200 further includes a current to voltage converter 220 , which may be a speaker or headphone amplifier, including a resistor 225 and an amplifier 230 . The amplifier 230 in this example includes at least a first input 233 configured to receive the single ended analog output from output 217 and a second input 237 connected to a common mode voltage (Vcm). The resistor 225 is connected between the first input 233 of the amplifier 230 and an output 239 of the amplifier 230 . The output 239 is configured to connect to a load, for example, a speaker or headphone. So configured, the apparatus 200 can provide an audio signal through a modulator and digital to analog converter to a load such as the headphone speaker without including a separate current to voltage converter, instead using the headphone amplifier as the current to voltage converter.
With reference to FIG. 3 , an example approach to the digital to analog converter 215 will be described. In this example, the digital to analog converter 215 includes a plurality of positive current sources 320 and a plurality of negative current sources 330 . The individual current sources 320 and 330 of this example feed into one of three paths through switches 340 . The three paths include the single ended analog output 217 , the common mode voltage (Vcm), and a path 350 to a feedback circuit 360 . In this example, the digital to analog converter 215 is a “2N−1” level digital to analog converter implemented using current sources in sync. In this example, the modulator 205 is a delta sigma modulator that also provides a “2N−1” level output. In other words, the outputs from the modulator 205 are N−1, N−2, . . . , 1, 0, −1, −2, . . . , −N+2, and −N+1. The output of the digital to analog converter 215 is single ended so that it can be fed directly to the headphone amplifier 220 . More specifically, in the example of FIG. 3 , the digital to analog converter has N positive current sources (Ip 1 through Ipn) and N negative current sources (Im 1 through Imn). The current sources are individually connected to the amplifier 230 depending on the output of the modulator 205 . Table 1 below summarizes the connection of the current sources 320 and 330 to the amplifier 230 in the example of FIG. 3 .
TABLE 1
Number of Positive
Number of Negative
Current Sources
Current Sources
Serial
Modulator
Connected to
Connected to
No.
Output
the Amplifier A2
the Amplifier A2
1
N − 1
N − 1
0
2
N − 2
N − 2
0
. . .
. . .
. . .
. . .
N − 1
1
1
0
N
0
0
0
N + 1
−1
0
1
. . .
. . .
. . .
. . .
2N − 2
−N + 2
0
N − 2
2N − 1
−N + 1
0
N − 1
The table shows the number of and type of current sources connecting to the amplifier 230 as decided by the modulator output. In other words, the digital to analog converter 215 is configured to connect the individual current sources 320 and 330 to the amplifier 230 based upon the single ended digital output from the modulator 205 . Per Table 1 above, zero current sources connect to the amplifier when the modulator 205 output is 0, and the number of sources connected to the amplifier 230 increases when signal strength increases. The type of current source connected to the amplifier 230 , positive or negative, is determined in response to the signal polarity. Such an arrangement is common with Class B type digital to analog converters. In one approach, the digital to analog converter 215 comprises an analog finite impulse response (FIR) filter including a plurality of cells 370 . Individual cells 370 each have a plurality of positive current sources 320 and a plurality of negative current sources 330 . Individual ones of current sources 320 and 330 feed into one of three paths through the switches 340 as described above. In the example of FIG. 3 , an individual cell 370 is illustrated where multiple individual cells are contemplated to be included in the circuit structure with their combined output being provided to the single ended output 217 to the amplifier 230 . When not connected to the amplifier 230 , individual current sources 320 or 330 are connected to either the common mode voltage Vcm or to the feedback circuit 360 .
An example feedback circuit 360 will be described with reference to FIG. 4 and FIG. 5 . The feedback circuit 360 includes an integrator circuit 410 including a summing amplifier 413 and an integrating capacitor 417 connected together receive an error signal. The error signal includes current from individual ones of the positive current sources 320 and negative current sources 330 connected to the path 350 to the feedback circuit 360 . The feedback circuit 360 of this example further includes switches 420 with gates 430 connected to a node 440 electrically connecting an output 415 of the summing amplifier 413 and a compensation capacitor 450 . The compensation capacitor 450 is connected between the output 415 of the summing amplifier 413 and a node 460 between the integrating capacitor 417 and a resistor 470 . The switches 420 of the feedback circuit 360 individually correspond to the individual cells 370 of the digital to analog converter 215 , and the switches 420 are individually configured to route current to the individual cells 370 to control positive and negative currents to effect current value matching for the individual cells 370 .
In the example where the digital to analog converter 215 implements an analog FIR filter by having multiple cells 370 , each of which having multiple positive current sources 320 and negative current sources 330 . This implementation of the filter allows the digital to analog converter 215 to reduce out of band noise for the analog output signal. The positive current sources 320 and negative current sources 330 , however, can have the mismatch between them. The current mismatch can cause harmonics to appear in the output of the digital analog converter thereby degrading the audio quality of the ultimate output of the circuit. For example, positive current sources 320 may be implemented using PMOS transistors whereas negative current sources 330 can be implemented using the NMOS transistors. Thus, because the positive current sources 320 and negative current sources 330 are using different types of devices, a mismatch in the individual current output of the individual sources can occur.
Implementation of the example feedback circuit of FIG. 4 , however, can correct this current mismatch. In one approach, the positive and negative current sources that are connected to the feedback circuit 360 are rotated over time. The feedback structure integrates this mismatch signal that is manifested in an error signal provided on the path 350 . In response, the switches 420 provide a control circuit signal in the form of a current that is routed back to individual cells 370 of the digital to analog converter 215 . An example of such a structure is shown in FIG. 5 .
In FIG. 5 , the output from an individual switch 420 of the feedback circuit 360 is connected via an electronic path 575 back to the individual cell 370 of the digital to analog converter 215 . This path 575 provides the feedback signal to the controls for the individual current sources 320 and 330 , thereby effecting a correction of the mismatch between the positive current sources 320 and the negative current sources 330 . A control for matching the positive and negative sources can be done in one of three ways. First, the control can be done such that there is a control of all the positive current sources 320 provided together to a given cell 370 , which is known in the art as gang control of the current sources 320 . Second, control of all the negative sources 330 of a given cell 370 can be ganged together. Third, there can be individual control of both types of current sources, the positive current sources 320 and the negative current sources 330 . The example of FIG. 5 illustrates gang control of the positive current sources 320 through connection of the feedback path 575 to a link 580 to the controls for the positive current sources 320 of cell 370 . The current provided from the feedback circuit 360 , therefore, is used to control the positive current sources 320 to help correct the current mismatch with the negative current sources 330 . Implementation of control of the negative current sources 330 or of simultaneous feedback control of both types of current sources can be implemented by one of skill in the art using similar approaches.
An example approach to connecting positive and negative current sources from the digital to analog converter 215 to the feedback circuit 360 will be discussed with respect to FIG. 6 . In this approach, individual cells 370 are configured to rotate connection of individual positive current sources 320 together with individual negative current sources 330 to the path 350 to the feedback circuit 360 . For example, current sources Ip(n−1) and Im(n−1) are connected to the path 350 to the feedback circuit 360 for one clock cycle 610 of the circuit. This connection is effected through the switches 340 , which are controlled by a separate controller (not shown) controlling the operation of the circuit. The effect of the connection is to have a positive current source's signals and its corresponding negative current source's signals add together on the path 350 to the integrator circuit 410 , such that the mismatching current between the individual positive current source and the corresponding individual negative current source is detected for this single clock cycle 610 . On the next clock cycle 620 , a second pair of a positive current source Ipn and a corresponding negative current source Imn is connected to feed into the path 350 to the feedback circuit 360 . Again, this connection of a pair of current sources, one positive current source Ipn and one negative current source Imn, is connected to the path 350 to the feedback circuit 360 for one clock cycle 620 . At the start of the next clock cycle 630 , another different pair of current sources, one positive Ip 1 and one negative Im 1 , is connected to the path 350 to the feedback circuit 360 . Although the integrating of the error signals is described as happening over a single clock cycle for the circuit, other time periods or methods can used for sensing the error signal and providing the feedback control to the individual cells.
So configured, the chosen positive and negative current sources are rotated every cycle such that the integrator circuit sees the average error over time. Based on this average error, a feedback correction current is provided from the individual switch 420 that corresponds to the cell 370 corresponding to the sensed current sources along the feedback path 575 as described above. So configured, the digital to analog converter 215 can be controlled to manage errors introduced by mismatches of the positive current sources 320 and the negative current sources 330 and still provide a low noise and low power single ended output through output 217 to the amplifier 230 .
With reference to FIG. 7 , an example method of operation of the circuit such as that described above will be described. The method includes receiving 710 the modulator output signal at a digital to analog converter. In one example, the receiving includes receiving the modulator output signal at a current steering digital to analog converter. The method further includes controlling 720 a single ended output from the digital to analog converter based on the modulator output signal. The controlling 720 includes controlling connection of current sources of the digital to analog converter to the single ended output based on the modulator output signal received at the digital to analog converter. In one example, this controlling includes connecting an increasing number of current sources to the single ended output in response to receiving increasing signal strength of the modulator output signal. The type of current source connected to the single ended output is determined in response to the polarity of the modulator output signal. Such an approach can be effected through the use of a Class B digital to analog converter. In yet another example, the method may further include implementing an analog finite impulse response filter in the digital to analog converter.
Referring again to FIG. 7 , the illustrated method includes matching 730 positive and negative current values for the digital to analog converter through a feedback circuit electrically connected to the digital to analog converter. The method further includes at 740 sending an output signal from the single ended output to a headphone amplifier connected to receive the output signal and a common mode voltage. The matching positive and negative current values through the feedback circuit may in one approach include integrating current sources from the digital to analog converter and providing a current control signal to individual cells of the digital to analog converter. So configured, a circuit implementing this method can provide a single ended output to an amplifier to eliminate the noise introduced by a separate current voltage converter that is typically implemented in audio circuits of this kind. Accordingly, noise is reduced, and an improved dynamic range can be realized in the audio output through the method executed by such a circuit.
A more specific example of a circuit embodying the teachings as described herein will be described with reference to FIGS. 2 and 5 . In this example, a sigma delta modulator 205 is configured to receive an UP-sampled audio signal from an UP-sampler circuit 210 and to output a modulated digital signal. A current steering digital to analog converter 215 is configured to receive the modulated digital signal from the sigma delta modulator 205 and provide a single-ended analog output 217 . The current steering digital to analog converter 215 includes at least a plurality of cells 370 configured to allow the current steering digital to analog converter 215 to operate as an analog finite impulse response filter. Individual cells 370 of the plurality of cells 370 include at least a series of positive current sources 320 and a series of negative current sources 330 . The current steering digital to analog converter 215 also includes switches 340 configured to connect the positive current sources 320 and the negative current sources 330 individually to one of the group including single-ended analog output 217 , a common mode voltage (Vcm), and a path 350 to a feedback circuit 360 . The switches 340 are configured to connect a positive current source 320 and a corresponding negative current source 330 for a given cell 370 to the path 350 to the feedback circuit 360 for a clock cycle for the apparatus 200 and to connect a different positive current source and a corresponding negative current source for the given cell 370 to the path 350 to the feedback circuit 360 for a next cycle for the apparatus 200 . The connection of current sources to the path to the feedback circuit for a single cycle is further illustrated in the example of FIG. 6 and described above.
The feedback circuit 360 of this example includes at least an integrator circuit 410 including a summing amplifier 430 and an integrating capacitor 417 connected to together to receive an error signal including current from individual ones of the positive current sources 320 and the negative current sources 330 connected to the path 350 to the feedback 360 . The feedback circuit 360 further includes feedback switches 420 with gates 430 connected to a node 440 connecting an output 415 of the summing amplifier 413 and a compensation capacitor 450 . The compensation capacitor 450 is connected between the output 415 of the summing amplifier 413 and a node 460 between the integrating capacitor 417 and a resistor 470 . In one example, the resistor 470 has a value of 100 kilo ohms, the integrating capacitor 417 has a capacitance of 10 pico farads, and the compensation capacitor has a capacitance of 1 pico farad, although other values of course may be used in other applications. The switches 420 individually correspond to the individual cells 370 and are individually configured to route current to the individual cells 370 to control positive and negative currents to effect current value matching for the individual cells 370 .
The single-ended analog output 217 is configured to feed to a headphone amplifier 220 , which is configured to receive the single-ended analog output 217 and the common mode voltage (Vcm). In this example, the headphone amplifier includes the resistor 225 and an amplifier 230 . The amplifier 230 includes at least a first input 233 configured to receive a single-ended amplifier output 217 and a second input 237 connected to the common mode voltage (Vcm). The resistor 225 is connected between the first input 233 of the amplifier 230 and an output 239 of the amplifier 230 , which is configured to connect to a load. The load typically is a speaker or a headphone speaker. In this example, the headphone amplifier 220 is configured to act as a current voltage converter between the current steering digital to analog converter 215 and the load.
So configured, the digital to analog converter is designed to reduce noise in the audio signal provided to a speaker. Moreover, in various examples, a differential signal chain implemented in the digital to analog converter provides an output directly to the headphone amplifier, which itself acts as a current to voltage converter. Accordingly, a separate current to voltage converter circuit is not needed, thereby eliminating a potential source of noise in the system. The dynamic range of such an arrangement increases the volume in the digital and reduces the gain in the analog for lower input signals. This is done dynamically but does not provide any dynamic change to the signal and therefore introduces limited audio artifacts for the listener. Accordingly, the circuit arrangement described above can provide a low power, high dynamic range digital to analog conversion, for example, in a headphone application, which is common for portable consumer music devices such as MP3 players and the like.
Those skilled in the art will recognize that a wide variety of modifications, alterations and combinations can be made with respect to the above described embodiments without departing from the scope of the invention. Such modifications, alterations and combinations to be viewed as being within the ambient concept.
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A circuit for providing audio signals to a load such as a speaker is provided that uses the speaker or headphone amplifier structure as a current to voltage converter, thereby eliminating a separate current to voltage converter from the circuit. Such a design removes one of the elements that creates noise in the circuit architecture and improves the dynamic range for the audio signal. For example, the output of a digital to analog converter is a single ended output provided to the speaker or headphone amplifier. The digital to analog converter can include a series of current sources that are summed up to provide the single ended output. Where the current sources have positive and negative current source mismatch, a feedback mechanism is employed to correct for the mismatch and reduce introduction of harmonic noise into the signal through the digital to analog converter.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2013-213144 filed on Oct. 10, 2013, the entire contents of which are incorporated herein by reference.
FIELD
The embodiments discussed herein are related to a level shifter, a DC (direct current)-DC converter, and a level shift method.
BACKGROUND
A DC-DC converter has two switch elements which are cascode-coupled between a power supply and the ground and performs DC-DC conversion by turning the two switch elements on and off in a complementary manner. As these two switch elements, N-channel metal-oxide semiconductor field effect transistors (MOSFETs) are used. An N-channel MOSFET has a lower on-resistance and a smaller parasitic capacitance (a smaller amount of capacitance charging and discharging) than a p-channel MOSFET.
Related techniques are disclosed in Japanese Laid-open Patent Publication No. 2010-4198 and a non-patent document: V. Pinon et al. (STMicroelectronics), “A Single-Chip WCDMA Envelope Reconstruction LDMOS PA with 130 MHz Switched-Mode Power Supply”, ISSCC Dig. Tech. Papers, pp. 564-565, February 2008.
SUMMARY
According to an aspect of the embodiment, a level shifter includes: a first cascode portion, including a first transistor of a first conductivity type and a second transistor of a second conductivity type which are cascode-coupled to each other, configured to transmit a first input signal; a second cascode portion, including a third transistor of the first conductivity type and a fourth transistor of the second conductivity type which are cascode-coupled to each other, configured to transmit a second input signal which is in a complementary relation with the first input signal; a latch portion configured to retain a first output signal and a second output signal obtained by changing, based on a first voltage obtained by boosting a power supply voltage, potential levels of the first input signal and the second input signal; and a potential-difference suppression circuit, coupled in parallel to the first cascode portion, configured to control a potential difference between a source and a drain of each of the first transistor and the second transistor.
The object and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the claims.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 illustrates an example of a DC-DC converter;
FIG. 2 illustrates an example of a DC-DC converter;
FIG. 3 illustrates an example of an operation of a level shifter;
FIG. 4 illustrates an example of a DC-DC converter;
FIG. 5 illustrates an example of an operation of a level shifter;
FIG. 6 illustrates an example of a method for determining a capacitance of a capacitive element;
FIG. 7 illustrates an example of a method for determining a capacitance of a capacitive element;
FIG. 8 illustrates an example of a DC-DC converter;
FIG. 9 illustrates an example of result of breakdown-voltage validation for transistors;
FIG. 10 illustrates an example of result of breakdown-voltage validation for transistors; and
FIG. 11 illustrates an example of result of breakdown-voltage validation for transistors.
DESCRIPTION OF EMBODIMENTS
A potential at a source of one of two switch elements which is coupled to the power supply side (called a high-side switch hereinbelow) changes from 0 V to a power supply voltage. In order to drive the high-side switch, a level shifter and a booster circuit, for example, a bootstrap circuit, are used to change a control signal (gate signal) to a voltage larger than the power-supply voltage.
For example, the voltage exceeding the power-supply voltage and applied to a transistor included in the level shifter may exceed a breakdown voltage of the transistor. Therefore, if a transistor with a high withstanding voltage is used, manufacture costs might increase.
FIG. 1 illustrates an example of a DC-DC converter. A DC-DC converter 1 may be a buck circuit, and includes a level shifter 2 , a booster circuit 3 , inverters 4 and 5 , a buffer 6 , a pulse signal generator 7 , a high-side switch HSW, a low-side switch LSW, a coil Lx, and a capacitive element Cx.
The high-side switch HSW and the low-side switch LSW may be n-channel MOSFETs, and are cascode-coupled between a power supply and the ground. Via the coil Lx, an output terminal OUT and one terminal of the capacitive element Cx are coupled to a midpoint between the high-side switch HSW and the low-side switch LSW. The other terminal of the capacitive element Cx is coupled to ground.
An output signal VoutP of the level shifter 2 is input as a control signal to a gate of the high-side switch HSW via the inverter 4 . A pulse signal generated by the pulse signal generator 7 is input as a control signal to a gate of the low-side switch LSW via the buffer 6 . The inverter 4 may operate at a voltage obtained by boosting Vdd (power-supply voltage) in the booster circuit 3 . The buffer 6 may operate at Vdd.
The level shifter 2 changes the potential level of the control signal to the high-side switch HSW by receiving the voltage obtained by the booster circuit 3 by boosting Vdd and changing the potential level of the pulse signal generated by the pulse signal generator 7 .
The level shifter 2 receives an input signal VinP which is the pulse signal generated by the pulse signal generator 7 and an input signal VinN obtained by inverting, in the inverter 5 , the logic level of the pulse signal generated by the pulse signal generator 7 . For example, the input signal VinP and the input signal VinN may be in a complementarity relation with each other. The inverter 5 may operate at Vdd.
In FIG. 1 , the booster circuit 3 may be a bootstrap circuit. The booster circuit 3 includes: a diode 3 - 2 whose anode is coupled to the power supply and whose cathode is coupled to the level shifter 2 ; and a capacitive element 3 - 1 whose one terminal is coupled to the cathode of the diode 3 - 2 and the other terminal is coupled to the midpoint between the high-side switch HSW and the low-side switch LSW. The booster circuit 3 boosts Vdd when the high-side switch HSW is on.
The level shifter 2 includes input inverters 2 - 1 and 2 - 2 , cascode portions 2 - 3 and 2 - 4 , a latch portion 2 - 5 , a transistor pair 2 - 6 , and a potential-difference suppression circuit 2 - 7 .
The input inverter 2 - 1 inverts the logic level of the input signal VinP, and the input inverter 2 - 2 inverts the logic level of the input signal VinN. The input inverters 2 - 1 and 2 - 2 may operate at Vdd.
The cascode portion 2 - 3 includes a transistor Tr 1 which is a p-channel MOSFET and a transistor Tr 2 which is an n-channel MOSFET, the transistors Tr 1 and Tr 2 being cascode-coupled to each other. The cascode portion 2 - 3 transmits an input signal VA which is a signal obtained by inverting the logic level of the input signal VinP in the input inverter 2 - 1 .
A source of the transistor Tr 1 is coupled to the latch portion 2 - 5 , and a drain of the transistor Tr 1 is coupled to a drain of the transistor Tr 2 . A gate of the transistor Tr 1 is coupled to the transistor pair 2 - 6 and the midpoint between the high-side switch HSW and the low-side switch LSW.
A source of the transistor Tr 2 is coupled to an output terminal of the input inverter 2 - 1 , and Vdd is applied to a gate of the transistor Tr 2 . The cascode portion 2 - 4 includes a transistor Tr 3 which is a p-channel MOSFET and a transistor Tr 4 which is an n-channel MOSFET, the transistors Tr 3 and Tr 4 being cascode-coupled to each other. The cascode portion 2 - 4 transmits an input signal VC which is a signal obtained by inverting the logic level of the input signal VinN in the input inverter 2 - 2 .
A source of the transistor Tr 3 is coupled to the latch portion 2 - 5 , and a drain of the transistor Tr 3 is coupled to a drain of the transistor Tr 4 . A gate of the transistor Tr 3 is coupled to the midpoint between the high-side switch HSW and the low-side switch LSW.
A source of the transistor Tr 4 is coupled to an output terminal of the input inverter 2 - 2 , and Vdd is applied to a gate of the transistor Tr 4 . The latch portion 2 - 5 includes transistors Tr 5 and Tr 6 which are p-channel MOSFETs. The latch portion 2 - 5 outputs, as a control signals to the high-side switch HSW, output signals VoutP and VoutN obtained by changing, based on a voltage obtained by boosting Vdd, the potential of the input signal VA or VC transmitted from the cascode portion 2 - 3 or 2 - 4 , and also retains the output signals VoutP and VoutN. In FIG. 1 , the output signal VoutP may be used as the control signal.
Sources of the transistors Tr 5 and Tr 6 are coupled to the booster circuit 3 , and a voltage Vbst is applied to the sources of the transistors Tr 5 and Tr 6 . The voltage Vbst may be a voltage obtained by boosting Vdd, for example, 2Vdd, when the booster circuit 3 performs boosting operation. A drain of the transistor Tr 5 is coupled to a gate of the transistor Tr 6 and the source of the transistor Tr 1 of the cascode portion 2 - 3 . A drain of the transistor Tr 6 is coupled to a gate of the transistor Tr 5 and the source of the transistor Tr 3 of the cascode portion 2 - 4 .
The transistor pair 2 - 6 has transistors Tr 7 and Tr 8 which are n-channel MOSFETs. A drain of the transistor Tr 7 is coupled to the drain of the transistor Tr 5 and the gate of the transistor Tr 6 of the latch portion 2 - 5 . A drain of the transistor Tr 8 is coupled to the drain of the transistor Tr 6 and the gate of the transistor Tr 5 of the latch portion 2 - 5 .
The potential-difference suppression circuit 2 - 7 is coupled in parallel to the cascode portion 2 - 3 , and may suppress a potential difference between the source and the drain of each of the transistors Tr 1 and Tr 2 . In the cascode portion 2 - 3 , the output signal VoutN has a voltage obtained by boosting Vdd, at a falling timing of the input signal VA. If the rate of fall of the output signal VoutN is slower than that of a potential VB at a midpoint between the transistors Tr 1 and Tr 2 , the potential difference between the source and the drain of the transistor Tr 1 might increase, resulting in that a drain-source voltage exceeds its breakdown voltage (see FIG. 3 ). If the rate of fall of the potential VB is slower than that of the input signal VA, the potential difference between the source and the drain of the transistor Tr 2 might increase, resulting in that a drain-source voltage exceeds its breakdown voltage (see FIG. 3 ). Therefore, the potential-difference suppression circuit 2 - 7 may have a function to reduce increase in the drain-source potential difference (see FIG. 5 ).
In the potential-difference suppression circuit 2 - 7 , the above function may be implemented by two breakdown-voltage protection elements 2 - 7 a and 2 - 7 b . The breakdown-voltage protection elements 2 - 7 a and 2 - 7 b may, for example, each be a capacitive element or multiple diodes coupled in series.
When capacitive elements are used as the breakdown-voltage protection elements 2 - 7 a and 2 - 7 b (see FIG. 4 ), the capacitive elements adjust the rate of fall of the potential of the output signal VoutN and the potential VB. Thus, the drain-source voltage of each of the transistor Tr 1 and Tr 2 might not exceed the breakdown voltage.
When diodes are used as the breakdown-voltage protection elements 2 - 7 a and 2 - 7 b (see FIG. 8 ), the diodes are coupled in series, the number of the diodes being determined based on the breakdown voltage of the transistor Tr 1 and/or the transistor Tr 2 . Thus, the diodes are turned on before the drain-source voltage of each of the transistors Tr 1 and Tr 2 reaches the breakdown voltage, and the diodes thus perform clipping.
Such provision of the potential-difference suppression circuit 2 - 7 may decrease occurrence of a case where a voltage exceeding a breakdown voltage is applied to the transistors Tr 1 and Tr 2 . For this reason, transistors with a high breakdown voltage do not have to be used as the transistors Tr 1 and Tr 2 , which may decrease the costs for manufacturing the level shifter 2 and the DC-DC converter 1 .
In the cascode portion 2 - 4 , the output signal VoutP is Vdd at a falling timing of the input signal VC (see FIG. 3 ). Thus, a potential difference exceeding Vdd might not be applied to the transistors Tr 3 and Tr 4 . For this reason, the potential-difference suppression circuit 2 - 7 provided to the cascode portion 2 - 3 does not have to be provided to the cascode portion 2 - 4 .
The provision of the transistor pair 2 - 6 in which the transistors Tr 7 and Tr 8 are coupled in the coupled state illustrated in FIG. 1 may decrease occurrence of a case where a voltage exceeding a breakdown voltage is applied to the transistors Tr 5 and Tr 6 of the latch portion 2 - 5 .
FIG. 2 illustrates an example of a DC-DC converter.
Elements of a DC-DC converter 1 a illustrated in FIG. 2 which are substantially the same as or similar to elements of the DC-DC converter 1 illustrated in FIG. 1 are denoted by the same reference numerals, and the description thereof will be omitted or reduces. A level shifter 2 a of the DC-DC converter is illustrated in FIG. 2 is not provided with the potential-difference suppression circuit 2 - 7 illustrated in FIG. 1 . A transistor pair 2 - 6 a has a different configuration from the transistor pair 2 - 6 of the level shifter 2 illustrated in FIG. 1 .
One I/O terminal (source or drain) of the transistor Tr 7 of the transistor pair 2 - 6 a is coupled between the transistor Tr 1 of the cascode portion 2 - 3 and the transistor Tr 5 of the latch portion 2 - 5 . One I/O terminal of the transistor Tr 8 is coupled between the transistor Tr 3 of the cascode portion 2 - 4 and the transistor Tr 6 of the latch portion 2 - 5 .
Vdd is applied to the other I/O terminals of the transistors Tr 7 and Tr 8 . The gates of the transistors Tr 7 and Tr 8 are coupled to the midpoint between the high-side switch HSW and the low-side switch LSW (and the coil Lx). The transistor pair 2 - 6 a has a function to reduce increase in the potential difference between the output signal VoutN or VoutP and the boosted voltage Vbst when the output signal VoutN or VoutP transitions.
Other configurations illustrated in FIG. 2 may be substantially the same as or similar to the configuration of the DC-DC converter 1 illustrated in FIG. 1 . FIG. 3 illustrates an example of an operation of a level shifter. FIG. 3 illustrates the input signals VinN and VinP, the input signal VA to the cascode portion 2 - 3 , the potential VB at the midpoint between the transistors Tr 1 and Tr 2 , the input signal VC to the cascode portion 2 - 4 , the potential VD at the midpoint between the transistors Tr 3 and Tr 4 , and the output signals VoutN and VoutP, as well as the voltage Vbst supplied to the latch portion 2 - 5 . For example, the booster circuit 3 may boost Vdd to, but not limited to, 2Vdd.
At an initial stage of “State 1”, the high-side switch HSW is on so that the voltage Vbst obtained by the booster circuit 3 is 2Vdd. At a falling timing of the input signal VA, the transistors Tr 5 and Tr 6 are on and off, respectively, and the output signal VoutN and the potential VB are about 2Vdd, while the output signal VoutP is at a potential lower than Vdd.
When the input signal VinP rises from 0 V to Vdd and the input signal VinN falls from Vdd to 0 V, the input signal VA of the cascode portion 2 - 3 falls from Vdd to 0 V. Thereby, the potential VB starts falling to 0 V with a delay equivalent to a delay by the transistor Tr 2 . The potential of the output signal VoutN also starts falling, but since the Transistor Tr 5 is on, the rate of fall is slower than that of the potential VB.
The input signal VC to the cascode portion 2 - 4 rises from 0 V to Vdd by the fall of the potential of the input signal VinN, and the potential VD starts rising with a delay equivalent to a delay by the transistor Tr 4 . As the potential of the output signal VoutN decreases, the transistor Tr 6 starts being turned on. Thus, the potential of the output signal VoutP and the potential VD increase up to about 2Vdd.
In “State 2”, once the output signal VoutP increases up to about 2Vdd, the transistor Tr 5 is turned off. Thus, the output signal VoutN falls at a higher rate down to 0 V. Output of the inverter 4 becomes Low level, and the voltage Vbst falls to Vdd by turning-off of the high-side switch HSW. Thereby, the output signal VoutP also falls to about Vdd.
In “State 3”, when the input signal VinP falls from Vdd to 0 V and the input signal VinN rises from 0 V to Vdd, the input signal VA of the cascode portion 2 - 3 rises from 0 V to Vdd. Subsequently, the potential VB and the potential of the output signal VoutN also start rising.
By the rise of the potential of the input signal VinN, the input signal VC to the cascode portion 2 - 4 falls from Vdd to 0 V. The potential VD subsequently falls, as well. By the fall of the potential VD, the output signal VoutP also starts falling, but since the transistor Tr 6 is on, the rate of the fall is slower that of the potential VD. As the potential of the output signal VoutP decreases, the transistor Tr 5 starts being turned on.
In “State 4”, when the output signal VoutP reaches about 0 V, output of the inverter 4 becomes High level, turning on the high-side switch HSW so that the booster circuit 3 performs boosting operation. Consequently, the voltage Vbst becomes twice as large as Vdd, and the output signal VoutN and the potential VB also increase to about 2Vdd.
Once the high-side switch HSW is turned on, Vdd is applied to the source of the high-side switch HSW. Thus, Vdd is applied to the gates of the transistors Tr 1 , Tr 3 , Tr 7 , and Tr 8 . For example, when the output signal VoutP is about 0 V and the output signal VoutN is about Vdd, the transistor Tr 3 is off, and the transistors Tr 8 and Tr 7 of the transistor pair 2 - 6 a are on and off, respectively. Thus, the potential of the output signal VoutP rises via the transistor Tr 8 up until it reaches a voltage lower than Vdd by a threshold voltage Vth of the transistor Tr 8 .
In the operation of the level shifter 2 a described above, in “State 1”, the falling timing of the potential VB is later than the falling timing of the input signal VA. Hence, a voltage equal to or larger than Vdd may be applied to between the drain and source of the transistor Tr 2 . The rate of fall of the potential of the output signal VoutN is slower than that of the potential VB. Hence, a voltage equal to or larger than Vdd may be applied to between the drain and source of the transistor Tr 1 . In this way, in “State 1”, a voltage exceeding the breakdown voltage of the transistor Tr 1 or Tr 2 might be applied.
In “State 4”, when the voltage Vbst is 2Vdd, the output signal VoutP is a voltage lower than Vdd by the threshold voltage Vth of the transistor Tr 8 . Thus, a voltage equal to or larger than Vdd may be applied to between the drain and source of the transistor Tr 6 of the latch portion 2 - 5 , and a voltage equal to or larger than Vdd may be applied to between the drain and source of the transistor Tr 5 of the latch portion 2 - 5 . In this way, in “State 4”, a voltage exceeding the breakdown voltage of the transistor Tr 5 or Tr 6 of the latch portion 2 - 5 might be applied.
FIG. 4 illustrates an example of a DC-DC converter. The DC-DC converter illustrated in FIG. 4 has a level shifter using capacitive elements as breakdown voltage protection elements.
In a DC-DC converter 1 b , a potential-difference suppression circuit 2 b - 7 of a level shifter 2 b has capacitive elements C 1 and C 2 . The capacitive element C 1 is coupled between the output terminal of the input inverter 2 - 1 and the midpoint between the transistors Tr 1 and Tr 2 of the cascode portion 2 - 3 . The capacitive element C 2 is coupled between the drain of the transistor Tr 1 and the midpoint between the transistors Tr 1 and Tr 2 of the cascode portion 2 - 3 .
FIG. 5 illustrates an example of an operation of a level shifter. FIG. 5 illustrates the input signals VinN and VinP, the input signal VA to the cascode portion 2 - 3 , the potential VB at the midpoint between the transistors Tr 1 and Tr 2 , the input signal VC to the cascode portion 2 - 4 , the potential VD at the midpoint between the transistors Tr 3 and Tr 4 , and the output signals VoutN and VoutP, as well as the voltage Vbst supplied to the latch portion 2 - 5 .
In the level shifter 2 b illustrated in FIG. 4 , “State 1” may be divided into Steps S 1 and S 2 below:
(Step S 1 ) The potential VB falls from 2Vdd to Vdd almost at the same time that the input signal VA falls, due to feedforward from the capacitive element C 1 . The capacitance of the capacitive element C 1 is set to a certain value, for example, Cmin or larger. Thus, when the potential of the input signal VA is 0 V, the potential VB may be about Vdd. For this reason, occurrence of a case where a drain-source voltage to the transistor Tr 2 exceeds Vdd may be suppressed. Hence, a transistor with a high breakdown voltage might not have to be used as the transistor Tr 2 . In Step S 1 , the potential of the output signal VoutN largely falls at almost the same time that the potential VB falls, due to feedforward from the capacitive element C 2 .
(Step S 2 ) Due to a voltage retaining function of the capacitive element C 1 , when the voltage VB falls from Vdd to 0 V at a lower rate, the rate of fall of the potential VB decreases. The potential of the output signal VoutN further decreases due to a current source effect of the transistor Tr 1 and the capacitive element C 2 . For this reason, occurrence of a case where a drain-source voltage to the transistor Tr 1 exceeds Vdd may be suppressed. Hence, a transistor with a high breakdown voltage might not have to be used as the transistor Tr 1 .
FIG. 6 illustrates an example of a method for setting the capacitance of a capacitive element. The capacitance of the capacitive element C 1 may be set in FIG. 6 . FIG. 6 illustrates an equivalent circuit of part of the level shifter 2 having a signal source 10 and two capacitive elements C 1 and Cpb. The signal source 10 may be an equivalently-illustrated part configured to supply the input signal VA. The capacitive element Cpb is a gate-drain parasitic capacitance of the transistors Tr 1 and Tr 2 .
When Vmax is the breakdown voltage of the transistor Tr 2 , the condition for the potential VB may be VB Vmax. Assume that, when the potential of the input signal VA falls down to 0 V, ΔC 1 is the amount of change in voltage across the capacitive element C 1 , and ΔC pb is the amount of voltage change in voltage across the capacitive element Cpb. Then, under an assumption that the total amount of charge does not change, Formula (1) below is obtained:
C 1 ·ΔC 1 =C pb ·ΔC pb (1)
where C 1 indicates the capacitance of the capacitive element C 1 , and C pb indicates the capacitance of the capacitive element Cpb. Formula (2) below is obtained by rearranging Formula (1):
C 1 =C pb ·ΔC pb /ΔC 1 =C pb ·(2 Vdd−VB )/( VB−Vdd ). (2)
To satisfy the relation VB Vmax, the capacitance C 1 only has to satisfy the relation of Formula (3) below:
C 1 ≧C pb ·(2 Vdd−V max)/( V max− Vdd ). (3)
“C pb ·(2Vdd−Vmax)/(Vmax−Vdd)” in the above formula may correspond to Cmin.
FIG. 7 illustrates an example of a method for setting a capacitance of a capacitive element. The capacitance of the capacitive element C 2 may be set in FIG. 7 . FIG. 7 illustrates an equivalent circuit of part of the level shifter 2 having a signal source 11 and two capacitive elements C 2 and CpboutN. The signal source 11 may be an equivalently-illustrated part configured to generate the potential VB. The capacitive element CpboutN is the parasitic capacitance of the transistors Tr 1 , Tr 5 , Tr 6 , Tr 7 , and Tr 8 which are coupled to a node N 1 in FIG. 4 .
When the capacitive element C 2 is added, the output signal VoutN falls at the same time that the potential VB falls, decreasing the potential difference between the potential VB and the output signal VoutN. Consequently, the transistor Tr 1 may be protected so that a drain-source voltage will not exceed the breakdown voltage of the transistor Tr 1 . The larger the capacitance of the capacitive element C 2 , the more effective that may be.
However, too large capacitance of the capacitive element C 2 makes the falling width of the output signal VoutN large, which may possibly cause the drain-source voltage to the transistor Tr 5 or the gate-source voltage to the transistor Tr 6 of the latch portion 2 - 5 to exceed the breakdown voltage. For this reason, when the potential VB falls down to 0 V, the voltage of the output signal VoutN (simply referred to as VoutN hereinbelow) may satisfy the relation of Formula (4) below:
V out N≧Vbst−V max=2 Vdd−V max. (4)
Since the total amount of charge does not change, a capacitance C 2 of the capacitive element C 2 is expressed as Formula (5) below:
C 2 =C pboutN ·(2 Vdd−V out N )/ V out N. (5)
To satisfy the relation in Formula (4), the capacitance C 2 only has to satisfy the relation in Formula (6) below:
C 2 ≦C pboutN ·V max/(2 Vdd−V max). (6)
If the capacitance C 2 of the capacitive element C 2 is increased, the rate of fall of the potential of the output signal VoutN becomes high, which may possibly protect the transistor Tr 1 . For example, providing an upper limit to the capacitance C 2 as indicated in Formula (6) may decrease occurrence of a case where a drain-source voltage exceeding the breakdown voltage of the transistor Tr 5 of the latch portion 2 - 5 is applied to the transistor Tr 5 .
The potential-difference suppression circuit 2 b - 7 includes the capacitive elements C 1 and C 2 . The potential-difference suppression circuit 2 b - 7 may suppress occurrence of direct current and decrease power consumption. Between “State 3” and “State 4” depicted in FIG. 5 , the voltage Vbst and the output signal VoutN are about Vdd, and the output signal VoutP is about 0 V. Thus, the transistors Tr 5 and Tr 6 are on and off, respectively, and the transistors Tr 7 and Tr 8 of the transistor pair 2 - 6 are off and on, respectively. The transistor Tr 8 is coupled to the coil Lx. When the output signal VoutP is about 0 V, the high-side switch HSW is turned on, and therefore the voltage at the source of the high-side switch HSW becomes about Vdd. Thus, the output signal VoutP rises to about Vdd. In the transistor pair 2 - 6 of the level shifter 2 b , the gate of the transistor Tr 8 is not coupled to the coil Lx, but is coupled so that the output signal VoutN may be input thereto. For this reason, when the transistor Tr 8 is on, the output signal VoutP might not fall short of Vdd by the amount of Vth, and therefore the output signal VoutP may be maintained at about Vdd. In “State 4”, the potential difference between the voltage Vbst and the output signal VoutP is about Vdd. Hence, occurrence of a case may be suppressed where a voltage exceeding the breakdown voltage is applied to the transistor Tr 5 or Tr 6 of the latch portion 2 - 5 .
FIG. 8 illustrates an example of a DC-DC converter. The DC-DC converter illustrated in FIG. 8 has a level shifter using diodes as breakdown voltage protection elements.
A potential-difference suppression circuit 2 c - 7 of a level shifter 2 c of a DC-DC converter is includes diodes Da 1 to Dan and Db 1 to Dbn. The diodes Da 1 to Dan are coupled in series between the output terminal of the input inverter 2 - 1 and the midpoint between the transistors Tr 1 and Tr 2 . The cathode is coupled to the output terminal of the input inverter 2 - 1 , and the anode is coupled to the midpoint between the transistors Tr 1 and Tr 2 .
The diodes Db 1 to Dbn are coupled in series between the midpoint between the transistors Tr 1 and Tr 2 and the drain of the transistor Tr 1 . The cathode is coupled to the midpoint between the transistors Tr 1 and Tr 2 , and the anode is coupled to the drain of the transistor Tr 1 .
The number of the diodes Da 1 to Dan and Db 1 to Dbn may be set according to the breakdown voltage of the transistors Tr 1 and Tr 2 . The number of the diodes Da 1 to Dan and that of the diodes Db 1 to Dbn may be set to satisfy Formula (7) below:
Vds max> n·Vf (7)
where Vdsmax is the drain-source breakdown voltage of the transistors Tr 1 and Tr 2 , and Vf is a forward voltage of the diodes Da 1 to Dan and Db 1 to Dbn.
For example, when Vdsmax=5.5 V and Vf=0.6 V, n may be 9. Before a drain-source voltage exceeding the breakdown voltage Vdsmax is applied to the transistor Tr 1 or Tr 2 , the diodes Da 1 to Dan and Db 1 to Dbn are turned on to possibly protect the transistors Tr 1 and Tr 2 .
Since the potential-difference suppression circuit 2 c - 7 includes the diodes Da 1 to Dan and Db 1 to Dbn, the circuit area may be reduced compared to a case using capacitive elements.
FIG. 9 illustrates an example of result of breakdown-voltage validation for transistors. FIG. 9 illustrates a result of withstanding-voltage validation by simulation for the transistors Tr 1 , Tr 2 , Tr 5 , or Tr 6 of the level shifter 2 a illustrated in FIG. 2 . The horizontal axis represents time (ns), and the vertical axis represents voltage (V). FIG. 9 illustrates drain-source voltages Vdstr 1 , Vdstr 2 , and Vdstr 6 of the transistors Tr 1 , Tr 2 , and Tr 6 and a gate-source voltage Vgstr 5 of the transistor Tr 5 . Vmax and −Vmax indicate the breakdown voltage of the transistor Tr 1 , Tr 2 , Tr 5 , or Tr 6 .
As depicted in FIG. 9 , in the level shifter 2 a , the drain-source voltage Vdstr 2 of the transistor Tr 2 exceeds the breakdown voltage Vmax. The drain-source voltage Vdstr 1 and Vdstr 6 of the transistors Tr 1 and Tr 6 exceed the breakdown voltage −Vmax. The gate-source voltage Vgstr 5 of the transistor Tr 5 also exceeds the breakdown voltage −Vmax.
Since a voltage exceeding the breakdown voltage Vmax or −Vmax is applied to the transistors Tr 1 , Tr 2 , Tr 5 , and Tr 6 of the level shifter 2 a , the transistors Tr 1 , Tr 2 , Tr 5 , and Tr 6 may break.
FIG. 10 illustrates an example of result of breakdown-voltage validation for transistors. FIG. 10 illustrates a result of breakdown-voltage validation by simulation for the transistors of the level shifter 2 b having the potential-difference suppression circuit using capacitive elements. The horizontal axis represents time (ns), and the vertical axis represents voltage (V). Like FIG. 9 , FIG. 10 illustrates drain-source voltages Vdstr 1 , Vdstr 2 , and Vdstr 6 of the transistors Tr 1 , Tr 2 , and Tr 6 and a gate-source voltage Vgstr 5 of the transistor Tr 5 .
As depicted in FIG. 10 , in the level shifter 2 b having the potential-difference suppression circuit 2 b - 7 using the capacitive elements C 1 and C 2 , a voltage exceeding the breakdown voltage Vmax or −Vmax is not applied to the transistors Tr 1 , Tr 2 , Tr 5 , and Tr 6 . Hence, transistors with a high breakdown voltage might not have to be used.
FIG. 11 illustrates an example of result of breakdown-voltage validation for transistors. FIG. 11 illustrates a result of breakdown-voltage validation by simulation for the transistors of the level shifter 2 c having the potential-difference suppression circuit using diodes. The horizontal axis represents time (ns), and the vertical axis represents voltage (V). Like FIG. 9 , FIG. 11 illustrates drain-source voltages Vdstr 1 , Vdstr 2 , and Vdstr 6 of the transistors Tr 1 , Tr 2 , and Tr 6 and a gate-source voltage Vgstr 5 of the transistor Tr 5 .
As depicted in FIG. 11 , in the level shifter 2 c having the potential-difference suppression circuit 2 c - 7 using the diodes Da 1 to Dan and Db 1 to Dbn, a voltage exceeding the breakdown voltage Vmax or −Vmax is not applied to the transistors Tr 1 , Tr 2 , Tr 5 , and Tr 6 . Hence, transistors with a high breakdown voltage might not have to be used.
All examples and conditional language recited herein are intended for pedagogical purposes to aid the reader in understanding the invention and the concepts contributed by the inventor to furthering the art, and are to be construed as being without limitation to such specifically recited examples and conditions, nor does the organization of such examples in the specification relate to a showing of the superiority and inferiority of the invention. Although the embodiments of the present invention have been described in detail, it should be understood that the various changes, substitutions, and alterations could be made hereto without departing from the spirit and scope of the invention.
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A level shifter includes: a first cascode portion, including a first transistor of a first conductivity type and a second transistor of a second conductivity type which are cascode-coupled to each other, configured to transmit a first input signal; a second cascode portion, including a third transistor of the first conductivity type and a fourth transistor of the second conductivity type which are cascode-coupled to each other, configured to transmit a second input signal; a latch portion configured to retain a first output signal and a second output signal obtained by changing, based on a first voltage obtained by boosting a power supply voltage, potential levels of the first input signal and the second input signal; and a potential-difference suppression circuit, coupled in parallel to the first cascode portion, configured to control a potential difference between source and drain of each of the first transistor and the second transistor.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to a shadow mask for a color cathode ray tube, and more particularly to a shadow mask for a color cathode ray tube having a modified shape and arrangement of slits, and embossments of a skirt portion of the shadow mask.
[0003] 2. Description of the Related Art
[0004] As a main element for realizing pictures in a picture display apparatus such as a television receiver or a computer monitor, a color cathode ray tube (CRT) is a device for realizing color pictures by emitting light from fluorescent substance in a fluorescent screen including R, G and B fluorescent substance patterned in an inner side of a panel, which is a front body of the CRT, by means of electron beam controlled by picture signals.
[0005] [0005]FIG. 1 is a partial sectional view showing a structure of a general color CRT.
[0006] Referring to FIG. 1, the color CRT generally comprises a panel 1 having a roughly rectangular shape and arranged in the front of the color CRT and a funnel 2 having a roughly conical shape and arranged in the rear of the panel 1 .
[0007] In addition, in an inner space formed by the panel 1 and the funnel 2 , the color CRT further includes a fluorescent screen 4 for emitting light, an electron gun 12 provided within a neck 13 of the funnel 2 for projecting electron beam 6 for emitting light from the fluorescent screen 4 , a shadow mask 3 for selecting color so that light is emitted from the fluorescent screen 4 , a frame assembly 7 for supporting the shadow mask 3 by applying tension to it, a spring 8 for coupling the frame assembly 7 to the panel 1 , an inner shield 9 welded and fixed to the frame assembly 7 for shielding an external earth magnetic field, and a reinforcement band 11 for provided at a circumference of a side portion of the panel 1 for preventing an external impact.
[0008] In addition, outside the neck 13 of the funnel 2 is provided a deflection yoke 5 for deflecting the electron beam 6 projected from the electron gun 12 in various directions, i.e., up, down, left and right and 2, 4 and 6-pole magnets for correcting a traveling locus of the projected electron beam 6 so that the projected electron beam 6 is precisely hit on prescribed fluorescent substance for the purpose of preventing the badness of color purity.
[0009] Now, as a main element in connection with the present invention, the shadow mask 3 will be in detail explained.
[0010] [0010]FIG. 2 is a front sectional view of the shadow mask 3 .
[0011] Referring to FIG. 2, the shadow mask 3 made of thin metal film having a thickness of about 0.1 to 0.12 mm is a portion positioned opposite the fluorescent screen 4 . The shadow mask 3 is completed by punching a circle plate with a plurality of electron beam through holes 110 formed by an etching process into a prescribed shape, pressing the punched plate into a curve shape such that it has same curve as a screen of the panel 1 , and forming a skirt portion 130 to be welded to the frame assembly 7 by bending four sides of the curve shape by 90 degree.
[0012] Herein, the steps of pressing and bending are continuously performed in a single process.
[0013] Therefore, the shadow mask 3 includes a porous portion 100 having a curved shape, a nonporous portion 120 connected adjacent to the porous portion 100 and having a curved shape, and the skirt portion 130 bent backward from a periphery of the nonporous portion 120 .
[0014] In the shadow mask 3 formed as above, the so-called “spring back” due to a property of material is generated in the skirt portion 130 . Accordingly, the skirt portion is bent in a spaced direction from an outside direction. That is, when a specific time elapses after pressing the skirt portion 130 by use of a presser, the skirt portion 130 becomes wider at an initial position with a specific interval. Under such a condition, when the skirt portion 130 is fixed to the frame assembly 7 , a deformation due to the bend of the skirt portion 130 is generated in a part of the porous portion having the curved shape (hereinafter referred to as “a curved portion”) of the shadow mask 3 . In this way, as the skirt portion 130 becomes more widened, a support force for supporting the curved portion become more weakened, which results in decrease of a strength of the curved portion of the shadow mask 3 . In addition, due to a close pressing to the shadow mask 3 by an amount of the widened of the skirt portion, a repulsive force is applied to the curved portion, which results in a variation of a curvature of the curved portion.
[0015] As a solution for the above problems, Korean patent application No. 10-1998-0008030 (published on Nov. 25, 1998, with publication No. 1998-0080110) is disclosed, which will be explained below.
[0016] [0016]FIG. 3 is a side sectional view of long and short sides of a shadow mask in the published patent application.
[0017] Referring to FIG. 3, a skirt portion ( 130 in FIG. 2) of the shadow mask has a plurality of pairs of embossments 200 and 300 and slit 210 and 310 having a prescribed shape and formed alternately in parallel, with one of the plurality of pairs of embossments positioned at both sides on the basis of central lines of the long and short sides.
[0018] By absorbing surplus material remaining after performing the steps of pressing and bending the shadow mask, the slits 210 and 310 and the embossments 200 and 300 formed in the skirt portion 130 are intended to substantially reduce a tendency of returning to an initial shape of the skirt portion 130 , reduce a curl generated in the skirt portion 130 , and minimize the occurrence of curl into a comparatively small region over the whole periphery of the skirt portion.
[0019] As shown in FIG. 3, however, the slits 210 and 310 and the embossments 200 and 300 in the skirt portion 130 of the conventional shadow mask 3 are configured to be positioned erectly and alternately in parallel with a specific interval. Thus, since the erected slits 210 and 310 and the embossments 200 and 300 undertake all amount of curl of the skirt portion 130 generated in a crossing direction upon forming the shadow mask 3 , they do not have a strength sufficient to absorb a compression force applied upon forming the shadow mask, which results in excessive creases in the slits 210 and 310 and the embossments 200 and 300 and a deformation of contour of the curved shape of the shadow mask 3 .
[0020] Typically, after a CRT is manufactured using a conventional shadow mask 3 as shown in FIG. 1, the CRT is subject to various kinds of reliability tests including, particularly, a falling test as a strength test. The falling test is a test for checking whether the shadow mask is deformed when the CRT is fallen from a specific height.
[0021] If an impact on the fallen CRT is weak in the falling test, the shadow mask 3 returns immediately to its original state though it is slightly deformed. In contrast, if the impact is strong, the shadow mask 3 cannot return to the original state due to a deformation such as a distortion of a portion of its surface caused while it is largely vibrated up and down.
[0022] The above problem involves with various causes, particularly, a structure of the shadow mask 3 . In other words, the slits 210 and 310 and the embossments 200 and 300 in the skirt portion 130 of the shadow mask 3 cannot endure the impact in the falling test due to failure of a proper dispersion of load, which results in a serious deformation of the shadow mask.
[0023] When such a plastic deformation is generated in the shadow mask, the electron beam 6 emitted from the electron gun 12 can collide with the shadow mask since it cannot properly pass through the electron beam through holes of the shadow mask 3 , which results in a deterioration of the shadow mask. In addition, the electron beam 6 cannot properly hit the fluorescent substance on the fluorescent screen 4 of the panel 1 , which results in a badness of the picture on the screen and hence a deterioration of productivity.
[0024] In addition, for an acoustic impact test, vibration of the shadow mask cannot be sufficiently absorbed, which results in a serious vibration of the picture on the screen and a deterioration of a strength of the shadow mask.
[0025] In summary, conventionally, the slits 210 and 310 and the embossments 200 and 300 each having a prescribed shape are placed in a parallel and alternate manner in order to minimize the amount of curl being an amount of spring-back of the skirt portion 130 of the shadow mask 3 . However, such a conventional structure for shadow mask has a limitation on reduction of the spring-back and is insufficient to prevent a deterioration of the strength of the shadow mask.
[0026] Accordingly, there is a need for a new shadow mask having a higher strength.
SUMMARY OF THE INVENTION
[0027] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a shadow mask for a color CRT whose strength is increased and whose curve distortion is reduced by inclining angles of a plurality of slits formed in a skirt portion of a shadow mask.
[0028] Another object of the present invention is to provide a shadow mask for a color CRT in which an amount of curl in a skirt portion of the shadow mask is minimized and a curve distortion of the shadow mask is prevented by an increase of a strength of the shadow mask by forming prescribed bridges in a plurality of slits provided in the skirt portion of the shadow mask including the plurality of slits and a plurality of embossments or inclining angles of the plurality of slits in which the bridges are formed.
[0029] Through the above objects, the present invention has an eventual object of improving a quality of picture and a productivity of the CRT.
[0030] In order to accomplish the above objects, the present invention provides a color cathode ray tube including a generally rectangular shadow mask having a curved apertured portion having a multiplicity of electron-transmissive apertures, a curved imperforate portion surrounding and integral with said apertured portion and a skirt portion being bent back from a periphery of said curved imperforate portion; said skirt portion being provided with a plurality of tilted slits and a plurality of embossments.
[0031] In addition, the present invention provides a color cathode ray tube including a generally rectangular shadow mask having a curved apertured portion having a multiplicity of electron-transmissive apertures, a curved imperforate portion surrounding and integral with said apertured portion and a skirt portion being bent back from a periphery of said curved imperforate portion; said skirt portion being provided with a plurality of tilted slits with bridge and a plurality of embossments.
[0032] In addition, the present invention provides a color cathode ray tube including a generally rectangular shadow mask having a curved apertured portion having a multiplicity of electron-transmissive apertures, a curved imperforate portion surrounding and integral with said apertured portion and a skirt portion being bent back from a periphery of said curved imperforate portion; said skirt portion being provided with a plurality of tilted slits with bridges are tilted from the vertical position toward a direction of the end portion of the skirt portion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[0034] [0034]FIG. 1 is a sectional view of a general CRT on which a conventional shadow mask is mounted;
[0035] [0035]FIG. 2 is a front sectional view of a conventional shadow mask;
[0036] [0036]FIG. 3 is a side sectional view of long and short sides of a conventional shadow mask;
[0037] [0037]FIG. 4 is a side sectional view of long and short sides of a shadow mask according to a preferred embodiment of the present invention;
[0038] [0038]FIG. 5 is a graph showing a result of improvement of a howling characteristic according to a preferred embodiment of the present invention, compared with a conventional result;
[0039] [0039]FIG. 6 is a side sectional view of long and short sides of a shadow mask according to another preferred embodiment of the present invention;
[0040] [0040]FIG. 7 is a graph showing an enhancement of strength of mask slits in the embodiment of FIG. 6;
[0041] [0041]FIG. 8 is a view showing a first example of slits provided in a skirt portion of the shadow mask in the embodiment of FIG. 6;
[0042] [0042]FIG. 9 is a view showing a second example of slits provided in a skirt portion of the shadow mask in the embodiment of FIG. 6;
[0043] [0043]FIG. 10 is a side sectional view of long and short sides of a shadow mask according to still another preferred embodiment of the present invention;
[0044] [0044]FIG. 11 is a graph showing an enhancement of strength of mask slits in the embodiment of FIG. 10;
[0045] [0045]FIG. 12 is a view showing a first example of slits provided in a skirt portion of the shadow mask in the embodiment of FIG. 10; and
[0046] [0046]FIG. 13 is a view showing a second example of slits provided in a skirt portion of the shadow mask in the embodiment of FIG. 10.
DETAILED DESCRIPTION OF THE INVENTION
[0047] Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
[0048] In the preferred embodiments of the present invention, since only slits in a skirt portion 130 are modified, a front sectional view of a shadow mask of the present invention is similar to FIG. 2 showing the front sectional view of the conventional shadow mask.
[0049] [0049]FIG. 4 is a side sectional view of long and short sides of a shadow mask according to a preferred embodiment of the present invention.
[0050] Referring to FIG. 4, the shadow mask according to a preferred embodiment of the present invention will be described.
[0051] In the side sectional view of FIG. 4, a long portion having a prescribed thickness and forming a slightly curved surface represents a shape of a curve surface of the shadow mask. One of a plurality of embossments 410 indented, with an arched shape, into a central internal portion in the skirt portion ( 130 in FIG. 2) of the shadow mask is arranged in a center of each of long and short sides of the skirt portion. A pair of slits of a plurality of slits are arranged in a center of each of long and short sides of the skirt portion with a prescribed interval in both sides of one embossments 410 . Then, the plurality of slits 400 are inclined toward the embossments 410 being a central axis of each of the long and short sides with a prescribed angle with respect to a direction of an end portion of the skirt from a direction of height of the skirt of the shadow mask. The plurality of slits 400 inclined at the prescribed angle and the remaining of the plurality of embossments 410 are arranged in an alternate and parallel manner.
[0052] More particularly, if the prescribed angle θ of the plurality of slits 400 lies between 60° and 90° in the direction of an end portion of the skirt from the direction of height of the skirt of the shadow mask, when the skirt portion 130 of the shadow mask is bent, many creases occur in the slits and a remarkable improvement effect for the spring-back and the strength of the shadow mask cannot be achieved. However, if the angle θ of the slits 400 continues to be modified to lie between 30° and 60° in the direction of an end portion of the skirt from the direction of height of the skirt of the shadow mask, the shadow mask having a high strength, a reduced deformation and a reduced curl can be obtained when the shadow mask is formed.
[0053] At this time, in order to prevent folding of a diagonal corner of the shadow mask when the shadow mask is formed, slits 420 at both ends of the long and short sides of the skirt portion are arranged without any inclination.
[0054] In practicing the present invention, preferably, the plurality of slits 400 are formed by 20%-60% of entire height of the skirt portion from the end portion of the skirt portion and the plurality of embossments 410 are formed over the entire height of the skirt portion.
[0055] The reason of such a formation is that if the slits 400 are formed at a too low location, a curl prevention effect in the skirt portion of the shadow mask is low and a strength improvement of the shadow mask cannot be achieved up a desired level, in contrast, if the slits 400 are formed at a too high location above 60% of the entire height of the skirt portion, a stress generated in the skirt portion when the shadow mask is fitted into the frame assembly ( 7 in FIG. 1) cannot be properly dispersed and hence is transmitted up to the porous portion having a curved shape, which results in a deformation of the porous portion of the shadow mask to be used in future.
[0056] [0056]FIG. 5 is a graph showing a result of improvement of a howling characteristic according to a preferred embodiment of the present invention, compared with a conventional result.
[0057] Herein, a horizontal axis indicates a frequency Hz and a vertical axis indicates a grade of a howling characteristic.
[0058] Grade 1 indicates that the howling characteristic is fine, grade 2 indicates that ¼ of a picture is shivered, and grade 3 indicates that the howling characteristic is wrongest. Namely, a higher grade means a wronger howling characteristic.
[0059] Referring to FIG. 5, it can be seen that a proportion of grade 2 in the present invention is certainly decreased compared to the prior art.
[0060] Therefore, it can be seen that the preferred embodiment of the present invention considerably improves a picture shivering phenomenon compared to the prior art.
[0061] In addition, a Doming characteristic is conventionally 7-11 μm in three and nine o'clock directions, but is 6-8 μm in three and nine o'clock directions and 4 μm in a two o'clock direction in the present invention. This shows that the Doming characteristic improves by a comparative decrease of its value.
[0062] On the other hand, although one of the plurality of embossments is located at the center axis of the long and short sides of the skirt portion of the shadow mask in the preferred embodiment of the present invention, it is possible to locate a pair of slits at both sides of the center axis without an embossments, arrange the plurality of embossments and the remaining slits in the alternate and parallel manner, and then arrange the plurality of slits symmetrical with respect to the center axis to be inclined toward a center point.
[0063] In addition, although the present invention illustrates, as an example, the shadow mask including the skirt portion having a structure in which the slits forming six bridges are arranged in the long side of the skirt portion and the slits forming four bridges are arranged in the short side of the skirt portion in the alternate and parallel manner, such a structure can be varied depending on a size of a screen, and therefore, the principle of the present invention is applicable to a shadow mask for a color CRT having different number of the slits and/or embossments.
[0064] In addition, it is preferred that the panel has a substantially flat outer surface and a curved inner surface.
[0065] <Another Preferred Embodiment>
[0066] Another preferred embodiment of the present invention provides a shadow mask 3 comprising a porous portion 100 with a curved shape including a plurality of beam through holes 110 , a nonporous portion 120 with a curved shape connected adjacent to the porous portion 100 , and a skirt portion 130 bent backward from a periphery of the porous portion 100 and including a plurality of slits 500 , 600 and 700 forming bridges as strength enhancing means and a plurality of embossments 520 , 620 and 720 .
[0067] [0067]FIG. 6 is a side sectional view of long and short sides of a shadow mask according to another preferred embodiment of the present invention.
[0068] As a more particular embodiment of the present invention, the side sectional view of the long and short sides of the shadow mask in FIG. 6 show bridges added, as strength enhancing means, to the slits 500 in the skirt portion 130 of the shadow mask.
[0069] As can be seen from a more particular observation of the side sectional view of FIG. 6, a long portion having a prescribed thickness in the upper of the skirt portion and forming a slightly curved surface represents a shape of a curve surface of the shadow mask. In the skirt portion below the long portion, a pair of slits of a plurality of slits 500 are arranged at both sides of the center point of each of long and short sides of the skirt portion with a prescribed interval and the remaining of the plurality of slits 500 are arranged together the plurality of embossments 520 in an alternate and parallel manner, as shown in FIG. 6.
[0070] The plurality of slits 500 are separated into upper slits 530 and lower slits 540 to form bridges 510 having a prescribed shape. The plurality of slits 500 extend up to 30 to 70% of the entire height of the skirt portion from the end of the skirt portion. The plurality of embossments 520 extend over the entire height of the skirt portion from the end of the skirt portion and have an arch-shaped section and a shape indented into an inside from the skirt portion.
[0071] On the other hand, in order to prevent folding of a diagonal corner of the shadow mask when the shadow mask is formed, slits 550 at both ends of the long and short sides of the skirt portion are arranged without any bridge.
[0072] [0072]FIG. 7 is a graph showing an enhancement of strength of mask slits in the embodiment of FIG. 6.
[0073] As can be seen from the graph of FIG. 7, while a conventional limit of maximal falling height at which mask slits are broken is 160 mm, a limit of maximal falling height at which mask slits are broken according to the present invention is 180 mm. That is, the limit of maximal falling height of slits of the present invention is higher 20 mm than that of the prior art in a characteristic estimation (impact test). This shows that the slits modified according to the present invention have high strength over the slits in the prior art.
[0074] On the other hand, several embodiments of a shape of slit in the present invention will be explained with reference to FIGS. 8 and 10.
[0075] [0075]FIG. 8 is a view showing circular slits provided in a skirt portion of the shadow mask in the embodiment of FIG. 6.
[0076] As can be seen from FIG. 8, the slits in the long and short sides of the skirt portion of the shadow mask are separated by bridges 610 into upper slits 630 having a circular shape and lower slits 640 .
[0077] [0077]FIG. 9 is a view showing triangular slits provided in a skirt portion of the shadow mask in the embodiment of FIG. 6.
[0078] As can be seen from FIG. 9, the slits in the long and short sides of the skirt portion of the shadow mask are separated by bridges 710 into upper slits 730 having a triangular shape and lower slits 740 .
[0079] As described above, although the preferred embodiment of the present invention shown in FIG. 6 is for rectangular slits, the shape of the slits is not limited to that, but can be diversely formed as circular 630 or triangular 730 , as shown in FIG. 8 or 9 .
[0080] In addition, although the preferred embodiment of the present invention shown in FIG. 6 illustrates, as an example, the shadow mask including the skirt portion having a structure in which the slits forming six bridges are arranged in the long side of the skirt portion and the slits forming four bridges are arranged in the short side of the skirt portion in the alternate and parallel manner, such a structure can be varied depending on a size of a screen, and therefore, the principle of the present invention is applicable to a shadow mask for a color CRT having different number of the slits and/or embossments.
[0081] In addition, although not shown in the drawings, preferably, as another example, one embossments is located on the center axis of the long and short sides of the skirt portion.
[0082] In other words, it is possible to locate one of the plurality of embossments on the center axis in the long and short sides of the skirt portion of the shadow mask, arrange slits forming a pair of bridges at both sides of the center axis with a specific interval, and arrange the slits and the remaining embossments in the alternate and parallel manner.
[0083] In addition, it is preferred that the panel has a substantially flat outer surface and a curved inner surface.
[0084] <Still Another Preferred Embodiment>
[0085] [0085]FIG. 10 is a side sectional view of long and short sides of a shadow mask according to still another preferred embodiment of the present invention.
[0086] As shown in FIG. 10, still another preferred embodiment is characterized in that a plurality of slits 800 including the bridges 810 in the skirt portion 810 of the shadow mask 130 are inclined by a prescribed angle.
[0087] Herein, when the plurality of slits 800 are inclined, a pair of slits 800 are arranged to be inclined toward the center axis with respect to a direction of height of the skirt portion at both sides of the center axis of the long and short sides of the skirt portion with a specific interval. Also, a structure composed of one embossments 820 and a pair of slits 800 inclined toward the embossments 820 with respect to the direction of height of the skirt portion at both sides of the embossments 820 is arranged in parallel at both sides of the center axis with a prescribed interval.
[0088] In the other hand, in order to prevent folding of a diagonal corner of the shadow mask when the shadow mask is formed, slits 850 at both ends of the long and short sides of the skirt portion are arranged without any inclination and bridge.
[0089] In addition, the plurality of slits 800 are separated into upper slits 830 and lower slits 840 to form bridges 810 having a prescribed shape. The plurality of slits 800 extend up to 30 to 70% of the entire height of the skirt portion from the end of the skirt portion. The plurality of embossments 820 extend over the entire height of the skirt portion from the end of the skirt portion and have an arch-shaped section and a shape indented into an inside from the skirt portion.
[0090] In addition, if the prescribed angle θ of the plurality of slits 800 forming the bridges lies between 60° and 90° in the direction of an end portion of the skirt from the direction of height of the skirt of the shadow mask, when the skirt portion 130 of the shadow mask is bent, many creases occur in the slits and a remarkable improvement effect for the spring-back and the strength of the shadow mask cannot be achieved. However, if the angle θ of the slits 800 continues to be modified to lie between 0° and 60° in the direction of an end portion of the skirt from the direction of height of the skirt of the shadow mask, the shadow mask having a high strength, a reduced deformation and a reduced curl can be obtained when the shadow mask is formed. Such a structure has same strength as the structure in which the slits not inclined in the preferred embodiment of FIG. 6 are separated into the upper and lower slits to form the bridges.
[0091] Namely, when the slits forming the bridges are inclined with a prescribed angle to be selected from a range of 0° to 90° in the direction of an end portion of the skirt from the direction of height of the skirt of the shadow mask, the spring-back is reduced, the strength of the shadow mask is increased, and the curl of the skirt portion is reduced.
[0092] [0092]FIG. 11 is a graph showing an enhancement of strength of mask slits in the embodiment of FIG. 10.
[0093] As can be seen from the graph of FIG. 11, while a conventional limit of maximal falling height at which mask slits are broken is 160 mm, a limit of maximal falling height at which mask slits are broken according to the present invention is 180 mm. That is, the limit of maximal falling height of slits of the present invention is higher 20 mm than that of the prior art in a characteristic estimation (impact test). This shows that the slits modified according to the present invention have high strength over the slits in the prior art.
[0094] On the other hand, several embodiments of a shape of slit in the present invention will be explained with reference to FIGS. 12 and 13.
[0095] As can be seen from FIG. 12, the slits in the long and short sides of the skirt portion of the shadow mask are separated by bridges 910 into upper slits 930 having a circular shape and lower slits 940 .
[0096] In addition, as can be seen from FIG. 13, the slits in the long and short sides of the skirt portion of the shadow mask are separated by bridges 1010 into upper slits 1030 having a triangular shape and lower slits 1040 .
[0097] As described above, although the preferred embodiment of the present invention shown in FIG. 10 is for rectangular slits, the shape of the slits is not limited to that, but can be diversely formed as circular 930 or triangular 1030 , as shown in FIG. 11 or 12 .
[0098] Although the preferred embodiment of the present invention shown in FIG. 10 illustrates, as an example, the shadow mask including the skirt portion having a structure in which the slits forming six bridges are arranged in the long side of the skirt portion and the slits forming four bridges are arranged in the short side of the skirt portion in the alternate and parallel manner, such a structure can be varied depending on a size of a screen, and therefore, the principle of the present invention is applicable to a shadow mask for a color CRT having different number of the slits and/or embossments.
[0099] In addition, although not shown in the drawings, preferably, as another example, one embossments is located on the center axis of the long and short sides of the skirt portion.
[0100] In other words, it is possible to locate one of the plurality of embossments on the center axis in the long and short sides of the skirt portion of the shadow mask, arrange slits forming a pair of bridges at both sides of the center axis with a specific interval, and arrange the slits and the remaining embossments in the alternate and parallel manner. In addition, it is possible to incline the slits forming the bridges located at both sides of the embossments on the center axis toward the embossments on the center axis with a prescribed angle between 0° and 60° in the direction of an end portion of the skirt from the direction of height of the skirt of the shadow mask and incline pairs of slits of the remaining slits toward adjacent embossments with a prescribed angle selected from the range of 0° to 60°, with the embossments centered, in the alternate and parallel manner.
[0101] In addition, it is preferred that the panel has a substantially flat outer surface and a curved inner surface.
[0102] As described above, by locating one of the plurality of embossments having a prescribed shape on the center axis of the long and short sides of the skirt portion of the shadow mask for the color CRT and arranging a pair of slits at both sides of the center axis to be symmetrically inclined toward the embossments on the center axis with a prescribed angle, the spring-back in the skirt portion can be reduced when the shadow mask is formed.
[0103] Accordingly, since the amount of curt generated in the curved portion of the skirt portion can be minimized so that a stress applied to the skirt portion when the skirt portion is fitted into the frame assembly does not propagate up to the porous portion or the nonporous portion, it is possible to prevent a distortion from being generated in the curved shape of the porous portion of the shadow mask.
[0104] In addition, by adding bridges to a plurality of slits and inclining the plurality of slits above an angle of 30° with one embossments centered, the amount of curl generated in forming the skirt portion by press can be reduced so that the skirt portion can be easily fixed to the mask frame. In addition, since a stress of the skirt portion fitted into the frame assembly is small, a distortion of contour of the curved shape of the porous portion can be prevented. As a result, a deterioration generated by hitting the electron beam on the shadow mask can be prevented, and accordingly, a selectivity for color become better and the strength of the shadow mask is further enhanced.
[0105] In addition, since a falling impact is dispersedly and sufficiently absorbed by the slits having a strengthened structure in the present invention, it is possible to reduce a deformation of the shadow mask generated since erected slits in the skirt portion of the shadow mask cannot properly disperse a load by an impact in the falling test as the reliability test in the conventional CRT. As a result, the problems in the prior art can be solved by increasing the strength of the shadow mask and sufficiently absorbing the shivering of the shadow mask in the acoustic impact test and hence reducing the shivering of the picture in the CRT.
[0106] Accordingly, color purity characteristic of the shadow mask becomes better and the strength of the shadow mask becomes enhanced, which results in improvement of productivity and reliability of products employing the shadow mask.
[0107] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
[0108] For example, a shape of the slits and the embossments or an angle of the slits can be variously modified and practiced by those skilled in the art.
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Disclosed herein is a shadow mask for a color cathode ray tube, and more particularly to a shadow mask for a color cathode ray tube having a modified shape and arrangement of slit and embossments of a skirt portion of the shadow mask.
The present invention provides a color cathode ray tube including a generally rectangular shadow mask having a curved apertured portion having a multiplicity of electron-transmissive apertures, a curved imperforate portion surrounding and integral with said apertured portion and a skirt portion being bent back from a periphery of said curved imperforate portion; said skirt portion being provided with a plurality of tilted slits and a plurality of embossments.
In addition, the present invention provides a color cathode ray tube including a generally rectangular shadow mask having a curved apertured portion having a multiplicity of electron-transmissive apertures, a curved imperforate portion surrounding and integral with said apertured portion and a skirt portion being bent back from a periphery of said curved imperforate portion; said skirt portion being provided with a plurality of tilted slits with bridge and a plurality of embossments.
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BACKGROUND OR THE INVENTION
The present device relates to a device for labelling objects, comprising a printer for printing labels, an application device for applying a printed label to the respective object to be labelled, and at least one working device in the form of a weighing device, a packaging device and/or a transport device for the objects to be labelled, wherein the working device, of which there is at least one, is arranged upstream of the application device. Furthermore, the invention relates to a method for labelling objects, comprising the following steps: printing a label by means of a printer; applying the printed label to the object to be labelled; and at least one more process step, which takes place upstream of the application of the printed label. The printer used can in particular be a thermal-direct printer or thermal-transfer printer.
Devices and methods of the type mentioned in the introduction have been known for some considerable time (see e.g. U.S. Pat. No. 4,415,048).
Depending on its design, the print head of a generic device is subject to some degree of wear. This wear has its origins in the slightly abrasive effect of the labels during the printing time.
SUMMARY OF THE INVENTION
It is thus the object of the present invention to modify a device and a method of the type mentioned in the introduction to the extent that while the highest possible throughput is achieved, the service life, in particular of a thermal printer strip, is extended when compared to that of the state of the art, and furthermore that the best print quality for the respective throughput performance is achieved.
With regard to the device, according to the invention this object is met in that a measuring and control device is used which for each object to be labelled determines the printing time that is available for printing the label to be applied to each of said objects, taking into account the required working time of the working device/s which is/are arranged upstream of the application device, and which, depending on the printing time determined, controls the printer such that printing of the label is completed within the available printing time at a matching printing speed, which is as slow as possible.
With regard to the method, according to the invention the object is met in that for each object to be labelled a calculation takes place of the printing time available for printing the label to be applied to said object, taking into account the working time required for the process step, of which there is at least one, which process step takes place upstream of the point where the printed label is applied, and in that, depending on the printing time calculated, printing of the label is controlled such that printing of the label is completed within the available printing time at a matching printing speed, which is as slow as possible.
When compared to conventional devices of the type discussed herein, in which the labels to be applied are printed at a relatively slow, constant printing time, the invention thus proposes that in respect to each individual label to be printed the work be carried out with a printing time which is matched to the timing of the device. Without reducing the throughput performance of a generic device, according to the invention the time available for printing is utilised to the full extent so that the printing speed during printing of a label can be selected to be as slow as possible, in this way being as gentle as possible on a thermal print head. Printing time is determined by the time-dependent behaviour of the devices arranged upstream and downstream. The maximum permissible printing time thus depends on the combination of the working time or working speed of the weighing device, the packaging device and the transport device which are arranged upstream; as well as on the application device, arranged downstream; and/or on other working devices arranged upstream or downstream.
A preferred embodiment of the invention consists in that the at least one working device, which is arranged upstream of the application device, comprises at least one sensor which registers the arrival, in the working device, of an object to be labelled, and issues a corresponding signal to the measuring and control device, after which said measuring and control device determines the printing time which is available for printing the label to be applied to the object, taking into account the time required by the application device for applying a label.
A further preferred embodiment of the invention consists of the measuring and control device comprising a processor which on the basis of the working speed of the working device, of which there is at least one, and on the basis of the time required for applying a label, calculates the printing time which is available for printing the label to be applied to the object.
Furthermore, in an advantageous embodiment of the invention, along a transport path for the objects to be labelled, several sensors are arranged, spaced apart from each other in the direction of transport, with said sensors registering the arrival of the object to be labelled, and issuing a corresponding signal to the measuring and control device. This embodiment makes it possible, when the respective signal is received, to determine a remaining residual printing time, and to control printing of a label, depending on the determined residual printing time, such that printing of the label is completed within the still available residual printing time at a matching printing speed, which is as slow as possible. This embodiment makes it possible, in particular, to recalculate an already calculated profile for time-dependent control of the printing speed during a printing process, and in this way to reduce the printing speed in the case of any delays which have occurred in one of the working devices arranged upstream of the application device so that, during the still available residual printing time, printing can take place at the respective minimum printing speed. In this way, the service life of a thermal printer strip can be further prolonged.
Further preferred and advantageous embodiments of the invention are disclosed in the subordinate claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Below, the invention is explained in more detail with reference to a drawing which shows one embodiment.
FIG. 1 shows a perspective view of a device according to the invention;
FIG. 2 is a vertical section view of the device according to FIG. 1 , which diagrammatically shows the operation of said device;
FIG. 3 shows a vertical section view of a label-printing unit and labelling unit of the device according to FIG. 1 ; and
FIG. 4 shows a flow chart for explaining the method according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1 to 3 of the drawing show a device for labelling foodstuffs packages 1 . The device comprises several working devices, namely a weighing device 2 ; a first transport device 3 in the form of a belt conveyor; a packaging device 4 ; a second transport device 5 , also in the form of a belt conveyor; a printer 6 for printing labels; and an application device 7 for applying a printed label to a packaged foodstuffs package 1 .
Foodstuffs portions 8 are placed into a package tray 9 and together with the tray 9 are arranged on the weighing device 2 . By way of a keyboard 10 , the tare weight of the package trays 9 , the name of the foodstuff, the price per unit of weight, as well as other goods-specific data can be entered into a memory of an input and display unit 11 . Said input and display unit 11 comprises a processor which, from the weight of the foodstuffs portion that has been determined by the weighing device 2 and the price per unit of weight, calculates the sales price of the respective foodstuffs portion.
On completion of the calculation of the sales price, the tray 9 with the foodstuffs portion 8 is transferred to the first belt conveyor 3 . To this effect, for example a pusher device (not shown) can be arranged at the weighing device 2 .
By way of the belt conveyor 3 , the tray 9 with the foodstuffs portion 8 reaches the packaging device 4 , which comprises a lifting device 12 , a film wrapping mechanism (not shown) as well as a heating device (not shown), for example an infrared radiator. In the packaging device 4 , the tray 9 with the foodstuffs portion 8 is wrapped with a transparent shrink film, and subsequently the film is shrunk by means of the heating device. The film is unrolled from a supply reel 14 .
During the packaging process, the tray 9 is lifted by means of the lifting device 12 , and after completion of the packaging process is transferred to the second belt conveyor 5 which transports the food package 1 to the unit 15 which comprises the label printer 6 as well as the label application device 7 .
The label printer 6 comprises a thermal strip within the thermal print head 16 , with labels 18 adhering to a strip of carrier tape 17 being supplied to said thermal print head 16 from a label supply reel 19 (compare FIG. 3 ). To this effect, the strip of carrier tape 17 is wound onto a reel 21 driven by an electric motor 20 . The self-adhesive labels 18 have been attached to the strip of carrier tape 17 with equal distance between said labels. Associated with the strip of carrier tape 17 made of translucent material is an optical sensor device which comprises a light-emitting transmitter diode 22 and a receiver diode 23 and which is thus able to detect sections 24 on the strip of carrier tape 17 which do not contain any labels. The signals emitted by the receiver diode 23 are used for controlling the motor 20 which is associated with the take-up reel 21 .
The thermal strip within the thermal print head 16 of the label printer 6 comprises print elements, arranged side-by-side, which are e.g. flat resistors (small heating plates) which can be controlled individually, i.e. independently of each other, and which quickly heat up and cool down. The relatively long cooling time of the resistors limits the possible printing speed. The labels 18 are made from heat-sensitive special paper. As an alternative to this, the label printer 6 can comprise a heat-sensitive thermal-transfer printer ribbon (not shown). In this case, it is possible to print onto labels made from ordinary paper.
When viewed in the direction of transport of the strip of carrier tape 17 , behind the print head 16 there is a relatively strong deflection 25 , at which the printed labels 18 , which adhere to the strip of carrier tape 17 , peel off said strip of carrier tape 17 and are transferred to the application device 7 . In the embodiment shown, the application device comprises a perforated suction area 26 at its underside, through which suction area 26 air is drawn in by means of an extractor fan (not shown) so that a printed label 18 is held to the suction area 26 . Furthermore, the application device comprises an air jet nozzle 27 with which for a period of time an air jet can be generated whose pressure exceeds the amount of the negative pressure existing at the suction area 26 . A label which is held at the suction area 26 can thus be released from the suction area 26 by means of this temporary generation of an air jet, and can be applied to a food package 1 which is situated below. 28 designates a label sensor which detects the presence of a label 18 at the suction area 26 . The time required by the application device 7 for applying a label 18 is approximately the same for each label.
In FIG. 2 , a diagrammatically shown measuring and control device is designated 29 . Connected to the measuring and control device 29 , which comprises a processor as well as a memory, are several sensors 30 - 35 , by means of which the working speed and thus the working time of the weighing device 2 , the transport device 3 , the packaging device 4 as well as the transport device 5 can be registered. The working time of the weighing device 2 corresponds to the time which passes from the point in time a package tray 9 with a foodstuffs portion 8 arranged thereon is placed on said weighing device 2 , to the point in time at which the weighing signal has stabilised, which includes transmission of the stabilised weighing signal to the processor of the input and display unit 11 . The working time of the transport device 3 corresponds to the time which passes from the point in time at which the package tray 9 with the foodstuffs portion 8 is conveyed to the transport device 3 to the point in time at which the package tray 9 with the foodstuffs portion 8 is transferred to the packaging device 4 . When a belt conveyor is used as a transport device 3 , the working time of the transport device can be determined in particular on the basis of the belt speed or the rotary speed of the belt drive roller or of the deflection roller in conjunction with the known length of the conveying distance. The working time of the packaging device 4 corresponds to the time which passes from the point in time of transfer of the package tray 9 with the foodstuffs portion 8 to the packaging device 4 to the point in time at which the packaged foodstuffs portion is transferred to the transport device 5 . The beginning and end of this time interval can for example be registered by means of photoelectric barriers 32 , 33 which are arranged at the transfer points between the transport device 3 and the packaging device 4 , and between the packaging device 4 and the transport device 5 , respectively. The working time of the transport device 5 corresponds to the time which passes from the point in time at which the packaged foodstuffs portion 8 is transferred to the second transport device 5 to the point in time at which the packaged foodstuffs portion reaches the application device 7 . As an alternative or in addition, the transport devices 3 , 5 at the respective transfer points can comprise sensors, e.g. light barriers which register the arrival or transfer of the respective tray 9 or food package 1 and which issue a corresponding signal to the measuring and control device 29 .
Expediently, the measuring and control device 29 comprises a measuring device (not shown) which registers whether the application device 7 is in its starting position (reset position) and is thus ready for applying a label 18 . This measuring device can for example utilise the label sensor 28 .
By means of the signals issued by the sensors 30 to 35 , and taking into account the time required by the application device 7 for applying a label, the measuring and control device 29 calculates for each package 1 and thus for each label 18 to be applied, the printing time which is available at maximum for printing the label at the highest possible throughput performance of the device (plant). In order to achieve the best possible throughput performance, preferably at least two elements in the operating chain which comprises the weighing device 2 , the transport device 3 , the packaging device 4 , and the transport device 5 , can be operated concurrently so that at least two process steps, for example weighing and packaging, can be carried out in parallel. However, it is in particular also possible for all process steps in the chain to be carried out parallel to each other. The maximum time available for printing a label basically depends on the working time which is required by the slowest element in the chain.
While maintaining a highest possible throughput performance of the device, the measuring and control device 29 controls the label printer 6 depending on the calculated maximum available printing time, so that completion of printing of the respective label 18 within the available printing time is at a matching printing speed, which is as slow as possible. To this effect, the measuring and control device 29 generates a time-dependent control profile, for each food package or each label, for controlling the printing speed of the printer 6 with which printing of the label 18 to be applied to the package 1 can be completed within the respectively available printing time at the slowest possible printing speed, without reducing the maximum possible throughput performance of the device.
Below, the basic process of the method according to the invention is explained again, with reference to FIG. 4 which shows logical dependencies during the method-related process.
In a device according to the invention, first of all a check is made whether a new print job is present. A new print job is, for example, present if a new package has been weighed and the weight data and price data have been generated. Subsequently, a check is made whether the systems arranged downstream of the label printer are ready for operation. This is, for example, the case if the preceding label has been applied to the associated package, and the application device is back in its starting position, in which it can take up a new printed label. After this, a check is made whether there is an allowed time for the point in time at which printing of the new label has to be completed. This time setting can, for example, be defined by the point in time at which application is to be made, with said point in time at which application is to be made being able to be calculated on the basis of the transport speed, the required position of the label on the package, as well as on other factors. When this time setting (time specification) is present, the maximum permissible printing time is calculated, and in relation to said printing time a time-dependent speed profile or control profile with all speed-dependent parameters is generated, with said profile causing printing of the respective label to be completed within the required time at the slowest possible printing speed. When the respective speed profile or control profile has been generated, printing starts and printing of the respective label is finished by the required point in time. Finally, a check is to be made whether printing has been completed and is thus finished. If this is the case, the next print job can be carried out analogously.
Implementation of the invention is not limited to the embodiment described above. Instead, a multitude of variants are imaginable which make use of the inventive step as defined in the enclosed claims, even if the design is basically different. In particular, the invention is not limited to the labelling of food packages. The invention can also be applied to the labelling of other goods packages.
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The invention relates to a device and a method for labelling objects, in particular food packages. The device comprises a printer, in particular a thermal-direct printer or thermal-transfer printer for printing labels; an application device for applying a printed label to the object to be labelled; and at least one working device, arranged upstream of the application device, in the form of a weighing device, a packaging device, and/or a transport device for the objects to be labelled. In order to prolong the service life of the print head and to improve the print quality, the provision of a measuring and control device is proposed which for each object to be labelled determines the printing time that is available for printing the label to be applied to each of said objects, taking into account the required working time of the working device/s, and which measuring and control device, depending on the printing time determined, controls the printer such that printing of the label is completed within the available printing time at a matching printing speed, which is as slow as possible.
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STATEMENT OF RELATED CASES
[0001] The following related cases are co-pending, co-owned patent applications—herein incorporated by reference—filed on even date as the present application:
[0002] Ser. No. ______ entitled “INTEGRATED DIAGNOSTIC CENTER” to Karen Capers and Michael Brooking.
[0003] Ser. No. ______ entitled “PRESENTATION SERVICES SOFTWARE DEVELOPMENT SYSTEM AND METHODS” to Karen Capers and Laura Wiggett.
BACKGROUND OF THE INVENTION
[0004] The convergence between legacy PBX, corporate IP Networks, on the one hand, and wireless communications, on the other, is continuing apace. Corporate GSM (or more generally, Office Land Mobile Network, or OLMN) systems that allow a subscribed user to roam onto a corporate wireless subsystem “campus” from the public land mobile network (PLMN) are known in the art.
[0005] With newer generations of such OLMNs rolling out, new services are being expected and demanded by the users of such systems. It is typically desirable to have such services—from new communications services to enhancing existing legacy services—seamlessly presented to the user (across the various platforms—PBX, network and wireless—within a given campus). Additionally, it is desirable to have these new services interoperating across various legacy PBX, networks and wireless subsystems—perhaps involving multiple manufacturers, protocols, operating systems and like.
[0006] It is additionally desirable to for these services to run robustly. Thus, messages can be delivered to end users even though there may be point failures in the OLMN. Additionally, it may be the case that, for communication systems developers, the location of the components that need to communicate on the network is not static, but changes often. Thus, it is desirable to have a development system that anticipates situations that require a wide variety of communication delivery modes and service. It is also desirable to have a development system that anticipates a wide variety of message formats that may differ in both their semantics and syntax.
SUMMARY OF THE INVENTION
[0007] The present invention discloses a novel system and method for providing communications between network objects (or clients) within an OLMN. The presently claimed system supports a variety of communication services to clients for delivering opaque messages on a communications network. Opaque message delivery allows users/clients to send any message format they wish. The present system allows any client—regardless of operating system and programming language—to use the Object Communication Service (OCS). Store-and-forward feature allows the client to send the message regardless of the state of the destination (e.g. whether it is down at the time). The present system also allows for multiple delivery modes; thus, there is no single point of failure.
[0008] In general, a client registers with the OCS using the present system. Once registered, the client is able to invoke the communication services offered by the system. The client is offered two modes of operation: (1) store-and-forward/broadcast communication between the client and multiple destination; and (2) peer-to-peer communication between the client and the destination.
[0009] In another aspect of the present invention, a novel method and system are herein described for enabling communications between distributed network objects. In general, a system and method for providing communications between network objects, the means and steps of said system and method comprising: registering said objects desiring communications; accepting a communications message from at least one of said objects, said communication addressing one of said plurality of network objects; determining the mode of message delivery for said message; delivering said message according to the mode of message delivery determined.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] [0010]FIG. 1 is a typical embodiment of an OLMN architecture.
[0011] [0011]FIG. 2 is a Use-Case diagram description of the name service employed by the present invention.
[0012] [0012]FIG. 3 is a Use-Case diagram description of the event component employed by the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] [0013]FIG. 1 depicts a typical architecture of an Office Land Mobile Network (e.g. Corporate GSM or “C-GSM”)—illustrating a communication system 10 in accordance with one embodiment of the present invention. The system 10 comprises a private network 12 for providing communication for a plurality of authorized subscribers. According to one embodiment, the private network 12 comprises a communication network for a particular business enterprise and the authorized subscribers comprise business personnel. The private network 12 comprises an office network 14 for providing communication between a plurality of mobile devices 16 , a private branch exchange (PBX) network 18 , and an Internet Protocol (IP) network 20 .
[0014] The office network 14 comprises a wireless subsystem 22 for communicating with the mobile devices 16 and a packet switching subsystem 24 for providing operations, administration, maintenance and provisioning (OAMP) functionality for the private network 12 . The wireless subsystem 22 comprises one or more base station subsystems (BSS) 26 . Each base system subsystem 26 comprises one or more base transceiver stations (BTS), or base stations, 28 and a corresponding wireless adjunct Internet platform (WARP) (alternatively called “IWG”) 30 . Each base station 28 is operable to provide communication between the corresponding WARP 30 and mobile devices 16 located in a specified geographical area.
[0015] Authorized mobile devices 16 are operable to provide wireless communication within the private network 12 for authorized subscribers. The mobile devices 16 may comprise cellular telephones or other suitable devices capable of providing wireless communication. According to one embodiment, the mobile devices 16 comprise Global System for Mobile communication (GSM) Phase 2 or higher mobile devices 16 . Each mobile device 16 is operable to communicate with a base station 28 over a wireless interface 32 . The wireless interface 32 may comprise any suitable wireless interface operable to transfer circuit-switched or packet-switched messages between a mobile device 16 and the base station 28 . For example, the wireless interface 32 may comprise a GSM/GPRS (GSM/general packet radio service) interface, a GSM/EDGE (GSM/enhanced data rate for GSM evolution) interface, or other suitable interface.
[0016] The WARP 30 is operable to provide authorized mobile devices 16 with access to internal and/or external voice and/or data networks by providing voice and/or data messages received from the mobile devices 16 to the IP network 20 and messages received from the IP network 20 to the mobile devices 16 . In accordance with one embodiment, the WARP 30 is operable to communicate with the mobile devices 16 through the base station 28 using a circuit-switched protocol and is operable to communicate with the IP network 20 using a packet-switched protocol. For this embodiment, the WARP 30 is operable to perform an interworking function to translate between the circuit-switched and packet-switched protocols. Thus, for example, the WARP 30 may packetize messages from the mobile devices 16 into data packets for transmission to the IP network 20 and may depacketize messages contained in data packets received from the IP network 20 for transmission to the mobile devices 16 .
[0017] The packet switching subsystem 24 comprises an integrated communication server (ICS) 40 , a network management station (NMS) 42 , and a PBX gateway (GW) 44 . The ICS 40 is operable to integrate a plurality of network elements such that an operator may perform OAMP functions for each of the network elements through the ICS 40 . Thus, for example, an operator may perform OAMP functions for the packet switching subsystem 24 through a single interface for the ICS 40 displayed at the NMS 42 .
[0018] The ICS 40 comprises a plurality of network elements. These network elements may comprise a service engine 50 for providing data services to subscribers and for providing an integrated OAMP interface for an operator, a subscriber location register (SLR) 52 for providing subscriber management functions for the office network 14 , a teleworking server (TWS) 54 for providing PBX features through Hicom Feature Access interfacing and functionality, a gatekeeper 56 for coordinating call control functionality, a wireless application protocol server (WAPS) 58 for receiving and transmitting data for WAP subscribers, a push server (PS) 60 for providing server-initiated, or push, transaction functionality for the mobile devices 16 , and/or any other suitable server 62 .
[0019] Each of the network elements 50 , 52 , 54 , 56 , 58 , 60 and 62 may comprise logic encoded in media. The logic comprises functional instructions for carrying out program tasks. The media comprises computer disks or other computer-readable media, application-specific integrated circuits (ASICs), field-programmable gate arrays (FPGAs), digital signal processors (DSPs), other suitable specific or general purpose processors, transmission media or other suitable media in which logic may be encoded and utilized. As described in more detail below, the ICS 40 may comprise one or more of the servers 54 , 58 , 60 and 62 based on the types of services to be provided by the office network 14 to subscribers as selected by an operator through the NMS 42 .
[0020] The gateway 44 is operable to transfer messages between the PBX network 18 and the IP network 20 . According to one embodiment, the gateway 44 is operable to communicate with the PBX network 18 using a circuit-switched protocol and with the IP network 20 using a packet-switched protocol. For this embodiment, the gateway 44 is operable to perform an interworking function to translate between the circuit-switched and packet-switched protocols. Thus, for example, the gateway 44 may packetize messages into data packets for transmission to the IP network 20 and may depacketize messages contained in data packets received from the IP network 20 .
[0021] The communication system 10 may also comprise the Internet 70 , a public land mobile network (PLMN) 72 , and a public switched telephone network (PSTN) 74 . The PLMN 72 is operable to provide communication for mobile devices 16 , and the PSTN 74 is operable to provide communication for telephony devices 76 , such as standard telephones, clients and computers using modems or digital subscriber line connections. The IP network 20 may be coupled to the Internet 70 and to the PLMN 72 to provide communication between the private network 12 and both the Internet 70 and the PLMN 72 . The PSTN 74 may be coupled to the PLMN 72 and to the PBX network 18 . Thus, the private network 12 may communicate with the PSTN 74 through the PBX network 18 and/or through the IP network 20 via the PLMN 72 .
[0022] The PBX network 18 is operable to process circuit-switched messages for the private network 12 . The PBX network 18 is coupled to the IP network 20 , the packet switching subsystem 24 , the PSTN 74 , and one or more PBX telephones 78 . The PBX network 18 may comprise any suitable network operable to transmit and receive circuit-switched messages. In accordance with one embodiment, the gateway 44 and the gatekeeper 56 may perform the functions of a PBX network 18 . For this embodiment, the private network 12 may not comprise a separate PBX network 18 .
[0023] The IP network 20 is operable to transmit and receive data packets to and from network addresses in the IP network 20 . The IP network 20 may comprise a local area network, a wide area network, or any other suitable packet-switched network. In addition to the PBX network 18 , the Internet 70 and the PLMN 72 , the IP network 20 is coupled to the wireless subsystem 22 and to the packet switching subsystem 24 .
[0024] The IP network 20 may also be coupled to an external data source 80 , either directly or through any other suitable network such as the Internet 70 . The external data source 80 is operable to transmit and receive data to and from the IP network 20 . The external data source 80 may comprise one or more workstations or other suitable devices that are operable to execute one or more external data applications, such as MICROSOFT EXCHANGE, LOTUS NOTES, or any other suitable external data application. The external data source 80 may also comprise one or more databases, such as a corporate database for the business enterprise, that are operable to store external data in any suitable format. The external data source 80 is external in that the data communicated between the IP network 20 and the external data source 80 is in a format other than an internal format that is processable by the ICS 40 .
[0025] The PLMN 72 comprises a home location register (HLR) 82 and an operations and maintenance center (OMC) 84 . The HLR 82 is operable to coordinate location management, authentication, service management, subscriber management, and any other suitable functions for the PLMN 72 . The HLR 82 is also operable to coordinate location management for mobile devices 16 roaming between the private network 12 and the PLMN 72 . The OMC 84 is operable to provide management functions for the WARPs 30 . The HLR 82 may be coupled to the IP network 20 through an SS7-IP interworking unit (SIU) 86 . The SIU 86 interfaces with the WARPs 30 through the IP network 20 and with the PLMN 72 via a mobility-signaling link.
[0026] Overview and Architecture
[0027] OCS (Object Communications Services) provides message-oriented point-to-point and publish-subscribe (“pub/sub”) functionality to network “objects”—ICS components, users, frameworks and perhaps to other subsystems. Thus, the term “object” is broadly interpreted to be any entity engaged in communication in the present system. Because ICS components must be location independent, all ICS components must use OCS to communicate with one another (except possibly for calling library components).
[0028] In addition to message communications, OCS also provides component “in service” and “out of service” notifications that are sent to other interested components. Any component can also query at any point in time if another component is currently in service or not.
[0029] In one embodiment, a messaging-oriented mechanism could be implemented as opposed to a remote procedure call (RPC) mechanism because loose-coupling is more desirable than tight-coupling. Messages are also highly desirable for communicating between different programming languages. However, it will be appreciated that tight-coupling messaging such as RPC could be implemented as well.
[0030] Further in the embodiment, the OCS clients communicate between each other through an OCS server. Therefore, messages that are sent between clients travel through the server. It will be appreciated, however, that another embodiment of the present invention could support and allow peer-to-peer communication to bypass the server. For example, in one peer-to-peer mode embodiment, an OCS client communicates with a peer by ending a message to the peer's Ipoint interface. In this mode, the OCS server is not involved.
[0031] In one embodiment, the OCS server can be implemented as a standalone Java application that can be started from the command line. A Startup Server also starts the OCS Server. As a design choice, TCP/IP sockets could be used for communication. Thus, if the server should be manually stopped, the client socket code will automatically reconnect to the server when it is back online.
[0032] A single instance of the OCS server should be running on some machine that is reachable over the network from the clients. An OCS jar file could be downloaded from an ICS Javadocs page and copied over to a Windows or Linux box.
[0033] For example, to start the server:
% java -cp OCS.jar com.opuswave.ics.serviceEngine.ocs.server.OCSServer
[0034] Server logging is made to the following file: /tmp/ocslog.txt
[0035] On Linux, view the log in real-time by running “tail-f/tmp/ocslog.txt”.
[0036] Log entries may look something like this: (Names that begin with an asterisk (*) are built-in system values.)
[3:51:20 PM] OCSServer started on port 54321 [3:51:26 PM] Connect C2 [3:51:30 PM] Connect C1 [3:51:30 PM] Send C1 −> C2 [3:51:30 PM] 6 items: *sender=C1 (java.lang.String) name=Peter (java.lang.String) three bytes (Java.lang.Byte) 00000 020100 days in year=365 (java.lang.Long) *seq=1 (java.lang.Long) *synchronous=true (java.lang.Boolean) [3:51:31 PM] Response C2 −> C1 [3:51:31 PM] 6 items: *sender=C2 (java.lang.String) *receiver=C1 (java.lang.String) days in year=333 (java.lang.Long) cartoon (java.lang.Object) 00000 ACED0005 73720032 636F6D2E 6F707573 ....sr.2 com.opus 00016 77617665 2E696373 2E736572 76696365 wave.ics .service 00032 456E6769 6E652E6F 63732E6D 65737361 Engine.o cs.messa 00048 67696E67 2E417070 6C65C115 98DFE4A6 ging.App le...... 00064 6A260200 014C0004 736F6E67 7400124C j&...L.. songt. .L 00080 6A617661 2F6C616E 672F5374 72696E67 java/lan g/String 00096 3B787074 000B4261 72727920 57686974 ;xpt..Ba rry Whit 00112 65 e *synchronous=false (java.lang.Boolean) *seq=1 (java.lang.Long) [3:51:46 PM] Disconnect C1 [3:51:56 PM] Disconnect C2
[0037] Client Configuration
[0038] In one possible embodiment, Java and C++ client configuration information is read from the following file: /tmp/ocsproperties.txt
[0039] This client configuration may contain the following values [default value]:
server={IP-Address} # set to “localhost” (without quotes) or IP address [localhost] trace={0|1} # set to 1 to turn on System.out.println trace [0] log={0|1} # set to 1 to log messages to /tmp log files [1] logSystemPairs={0|1} # set to 1 to log system name/value pairs [0] (those pair names that begin with asterisk (*) in message logs: *from, *to, etc.) port={number} # FUTURE: port number [54321] logObjects={0|1} # FUTURE: because object hex dumps can get long, this can be set to omit that long output [0] synchTimeoutMS={number} # FUTURE: interval to wait during a synchronous call waiting for a reply. [20000]
[0040] Clients may also write diagnostic log output to the /tmp directory. The filename format is: //tmp/ocslog_<clientName>.txt. Therefore, if two clients are running the same machine, both have distinct log files.
[0041] Programming
[0042] Before sending or receiving messages, it is desired to register with the OCSServer. It is possible to call the static method MessagingFactory.createInstance to obtain an OCS interface:
[0043] Ipoint
[0044] Ipublish
[0045] Isubscribe
[0046] Then it is possible to register your identity:
TheInterfaceReference.register(“your well-known name here”, MessagingConstants.ICS_PASSWORD);
[0047] A password is now required to authenticate ICS clients. All ICS will use the ICS_PASSWORD password.
[0048] As a shortcut, if desired
[0049] i. only receive, or
[0050] ii. send and receive
[0051] It is possible to call the listen method:
point.listen(“your well-known name here”, objectReferenceThatImplementsListenInterface);
[0052] It is possible to register more than once (subsequent registers are NO-OPS). However, it is not desired to re-register with a new identity name.
[0053] All point names registering with a particular OCS server should be unique. Otherwise, an exception will be thrown if a registration is attempted when another client has already registered under that name.
[0054] For pub/sub, the name of the point should still be registered so that the publisher and subscriber names can correctly appear in the logs.
[0055] At present it is not possible to do Point-to-Point and Pub/Sub using the same interface. In this embodiment, MessagingFactory.createInstance should be called twice to obtain both interfaces.
[0056] Filtering Messages
[0057] The ability for a point to only accept incoming messages from an approved set of source points. A new third parameter has been added to the listen( ) method:
public void listen(String point, IListen receive, String friendList) throws Exception;
[0058] The friendList is a comma-delimited list of source points to accept messages from. Messages from all other points are filtered. Example:
point.listen(“SLR”, new MyListener( ), “SubAgent,PizzaMan”); // Only accept messages from the SubAgent and PizzaMan points
[0059] Disconnecting from the Server
[0060] To disconnect from the server, it is possible to call the unregister method:
[0061] TheInterfaceReference.unregister( );
[0062] This kills the internal thread so that the application can exit.
[0063] Messages are implemented as a collection of name/value pairs stored in the OCSMap class.
[0064] The collection is a “map” data structure. Each name is a handle to a particular value. Names are not case sensitive. Subsequent setting of values overwrites previous values. Names can contain space characters.
[0065] It is possible to use the isSet( ) method to see if a name was sent.
[0066] All map assessor methods can throw the NotFoundException exception:
try { Boolean bSomeFlag = map.getBoolean(“someFlaq”); } catch (NotFoundException e) { System.out.println(“couldn't obtain value: ” + e); }
[0067] There are two possible exception message strings:
getBoolean: couldn't find %NAME% getBoolean: %NAME%: value exists but isn't a Boolean value
[0068] The OCS datatypes currently supported are:
[0069] String
[0070] Long
[0071] Int
[0072] Boolean
[0073] Byte[ ]
[0074] Object
[0075] Any number of pairs can be sent in a single OCSMap.
[0076] Currently, the total aggregate byte size of a OCSMap object cannot exceed 10,000 bytes.
[0077] Java Objects intended to be stored in an OCSMap must implement the Serializable interface.
[0078] When replying to a synchronous message, it is desired to use the incoming OCSMap structure to send back the response values—as noted below in the “Receiving Messages” discussion for an example.
[0079] Sending Incoming Values Back To The Source
[0080] The incoming name/value pairs sent to a destination point will not be sent back to the source point. However, if it is desired an incoming value to be sent back in the reply, it is possible to use the keep method.
[0081] map.keep(“some name”);
[0082] This is equivalent to the following:
[0083] map.setDATATYPE(“some name”, map.getDATATYPE(“some name”));
[0084] Here is a complete example:
public class MyListener implements Ilisten { public void onMap(boolean isSynchronous, IReply reply, OCSMap map) { if (isSynchronous) { try { // INCOMING VALUES System.out.println(“received ” + map.getString(“ColorsOfRainbow”) ); System.out.println(“received ” + map.getLong(“SLRTimeoutValue”) ); // OUTGOING VALUES map.setLong(“this is a new value sent back to source point”, new Long(654321)); // The following two values were sent here from the source point. // Send them back with the new value above. map.keep(“ColorsOfRainbow”); // send this original value back to sender map.keep(“SLRTimeoutValue”); // send this original value back to sender reply.sendMap(map); } catch (Exception e) { FATAL(“MyListener: problems setting values: ” + e); } } } }
[0085] Using a HashMap Instead of an OCSMap
[0086] It is possible to call the following two methods to export/import name/value pairs to/from a standard Java HashMap object:
[0087] public HashMap getMap( );
[0088] public void setMap(HashMap map) throws Exception;
[0089] Exporting values to a HashMap object allows passing the OCS values to parts of the system that do not have a dependency on OCS.
[0090] Here is an example where values are exported to a HashMap, then more values are added, then the values are imported back into the OCSMap object:
try { OCSMap map = new OCSMap( ); Map.setString(“mystring”, “Willie Wonka”); map.setLong(“mylong”, new Long(34)); TR(“toString=” + map.toString( )); TR(“export and iterate initial values using the HashMap”); HashMap hm = map.getMap( ); Set set = hm.keySet( ); For (Iterator i = set.iterator( ); i.hasNext( ) ; ) { String sKey = (String)i.next( ); TR(“key=” + sKey ); } TR(“add new values”); Hm.put (“NEW STRING”, “Mellick”); hm.put(“NEW LONG”, new Long(66)); hm.put(“NEW OBJECT”, new Person( ) ); hm.put(“NEW BOOLEAN”, new Boolean( true )); Byte[] two = { new Byte((byte)10), new Byte((byte)20) }; Map.setBytes(“NEW BYTES”, two); TR(“Call setMap to import values back into the OCSMap”); Map.setMap( hm ); TR(“dump all values: ” + map.toString( )); } catch (Exception e) { FATAL(“” + e); }
[0091] Sending Messages
[0092] Point-To-Point
[0093] Call the sendMap method to send a message to another point:
Public int sendMap(boolean bSynchronous, String destination, OCSMap value) throws Exception;
[0094] It may be desired to create one sending interface reference per component and share the reference between all the classes of the component.
[0095] Synchronous: Point-to-point messages can be sent synchronous by passing ‘true’. This is the most common and convenient approach as the call will block until there is an outcome. Specifically, the following cases return on the following values:
int result = point.sendMap(true, “P2”, map); // blocks switch (result) { case MessagingConstants.MESSAGE_MAP: // success! // obtain P2's returned values from same “map” object System.out.println( map.getString(“United States Capitals”) ); break; case MessagingConstants.MESSAGE_TIMEOUT: // default is 10 second window to receive response System.out.println( “OCS: didn't get reply from P2” ); break; case MessagingConstants.MESSAGE_ERROR: System.out.println( “OCS: Got error ” + map.getString(“*errorMessage”) ); }
[0096] Asynchronous: Pass ‘false’ to send messages asynchronously. This is the “fire and forget” approach. The only two outcomes are success or error:
int result = point.sendMap(false, “P2”, map); // doesn't block switch (result) { case MessagingConstants.MESSAGE_SUCCESS: // map object still only contains values that were sent to P2 (no result values) System.out.println( “A-OKAY” ); break; case MessagingConstants.MESSAGE_ERROR: System.out.println( “OCS: Got error ” + map.getString(“*errorMessage”) ); break; }
[0097] To receive responses for asynchronous messages, a listener routine should be invoked.
[0098] Pub/Sub
[0099] Call the sendMap( ) method of the IPublish interface:
[0100] pub.sendMap(“TopicA”, map);
[0101] All subscribers will receive the message in an undefined order. If there are no subscribers the message is thrown away.
[0102] Pub/sub messages are only asynchronous.
[0103] Receiving Messages
[0104] Incoming messages are handled in an event-driven programming mode, i.e., incoming messages are passed to a consumer's code via various call back-type mechanisms.
[0105] Messages are passed on OCS threads. Consumers, therefore, do not have to explicitly create threads to use OCS.
[0106] In the current embodiment, OCS does not support an event-getting mode where the consumer's code would block on a method call like “waitForIncomingMessage”.
[0107] In one embodiment, callbacks are implemented as follows:
C++: Write a class that inherits from OCSPoint.cc. Override the virtual “onMap” method. OnMap is called automatically when a message arrives. Java: Write a class that implments the IListen interface. Another class needs to instantiate this receiver class and call the “listen” method to bind the receiver with a well-known name that senders use.
[0108] Point-to-Point
[0109] With this mode of communication, it is possible to elect to have as many receiving points in a component as desired. Preferably, a new IPoint should be created for every receiving point because typically it is not possible to associate different IListen objects using a single IPoint interface.
[0110] In Java, the IListen interface is used to receive messages:
[0111] void onMap(boolean isSynchronous, Ireply reply, OCSMap value);
[0112] The onMap( ) method is called for all incoming Point-to-Point and Pub/Sub messages. For Sub/Sub the isSynchronous parameter is always false.
[0113] If it is desired to reply to a synchronous message, use the same OCSMap object to send values back to the sender:
public void onMap(boolean isSynchronous, IReply reply, OCSMap map) { try { map.setString(“reply name”, “reply value”); reply.sendMap (map); } catch (Exception e) { } }
[0114] However, it is not advisable to do this:
public void onMap(boolean isSynchronous, IReply reply, OCSMap map) { try { OCSMap replyMap = new OCSMap ( ); // DON'T CREATE NEW OCSMAP replyMap.setString(“reply name”, “reply value”); reply.sendMap(replyMap); // This will thrown an exception } catch (Exception e) { } }
[0115] Receiving Pub/Sub Messages
[0116] Unlike IPoint, when subscribing it is allowed to call listen( ) multiple times to associate different message handlers with different topics. It is possible to receive multiple subscriptions using the same ISubscribe interface reference:
sub.listen(“topicA”, listenerA ); sub.listen(“topicB”, listenerB ); sub.listen(“topicC”, listenerC );
[0117] For Pub/Sub the IReply interface can be used to send an asynchronous Point-to-Point message back to the point that published the original message. Since the reply is Point-to-Point the replied message will not be received via the ISubscribe object (if there is one) of the publisher. This is a case of a message being delivered originally as Pub/Sub and replied to as Point-to-Point.
[0118] Multithreading
[0119] Sending
[0120] For sending, it is possible to re-use a single OCSMap object when sending to several points or the same point multiple times ASYNCHRONOUSLY. It is also desirable to use distinct OCSMap objects if sending SYNCHRONOUSLY.
[0121] Receiving
[0122] Received messages can now be processed in parallel without any additional coding. Just set the new “setMaxReceiveThreads” method to set the size of the thread pool. IListen's onMap( ) is called concurrently. OCS supports automatic parallel processing of received messages by calling the following method:
[0123] point.setMaxReceiveThreads(nbrOfThreads);
[0124] A thread pool is automatically used to manage multiple receiving threads.
Public class MyListener implements IListen { public /*synchronous NO!!!*/ void onMap(boolean isSynchronous, IReply reply, OCSMap map) { // WILL BE CALLED BY MULTIPLE THREADS SIMULTANEOUSLY // Do NOT make onMap synchronous!!! This will default the multiprocessinq capabilities. } }
[0125] Point-In-Service Notifications
[0126] Automatic Point Notifications Invoke the notifyMe( ) method if it is desired to be notified when other points come in and out of service:
[0127] public void notifyMe(boolean bNotify, String point);
[0128] For example, some point wishes to watch the point named “SLR”:
[0129] point.notifyMe(true, “SLR”);
[0130] If it is desired to be notified if the OCSServer itself goes in or out of service, it is possible to pass the point name “OCSServer”.
[0131] When the SLR changes state onMap( ) will be called with the following OCSMap system name/value pairs:
*type - “notification” *event - “notifyMe” *point - e.g., “SLR” or “OCSServer” *inService - Boolean.TRUE or Boolean.FALSE *binding - “Java” or “C++”
[0132] Call the accessor methods of OCSMap to obtain these values. To discontinue being notified, call notifyMe( ) with false as the first parameter.
[0133] On Demand ‘Point In Service’ Queries
[0134] If it is desired to ask the OCS Server if another point is currently in service at a particular point in time call the inService method:
[0135] public boolean inService(String point) throws Exception;
[0136] This assertion should never fail:
point.register(“MyPointName”); // Register with the OCS Server ASSERT( point.inService(“MyPointName”) ); // Am I in service?
[0137] Again, if it is desired to ask if the OCSServer is currently running, it is possible to pass “OCSServer” as the point name.
[0138] Server Manipulation
[0139] It is possible to kill the server using the IServer interface:
IServer server = (IPoint)MessagingFactory.createInstance (“IServer”); server.register(“my name”); server.killServer( ); server.unregister( );
[0140] Documentation
[0141] The OCSMap name-value pair collection may contain some of these internal values that begin with an asterisk (*):
*type - String: Why onMap( ) is called: “p2p”, “pub/sub”, “notification”, or “system” *topic - String: if *type=“pub/Sub” then *topic is the topic of the message *from - String: The sender of the message *to - String: The recipient of the message *synchronous - Boolean: If message is synchronous: Boolean.TRUE or Boolean.FALSE. *seq - Long: Sequence number (internal unique tracking number for synchronous Point-to-Point) *origSeq - Long: Sequence number for routing synchronous response message back to original sender *errorMessage - String: Possible error message *event - String: if *type=notification then *event describes the event type like “notifyMe” *point - String: if *type=notification and *event=NotifyMe then *point is the point coming in service or out of service *inService - Boolean: if *type=notification and *event=NotifyMe then *inService tells if going in service or out of service *binding - String: The language binding of the sender: “Java” or “C++”
[0142] OCS Internal Commands:
- clientStart - The first message a client sends to the server to register. - clientStartResponse - Confirmation that the client is registered. - map - Point-to-Point OCSMap message. - mapTopic - Pub/Sub OCSMap message. - broadcast - Broadcast message sent to all clients. - subscribe - Request to subscribe to a Pub/Sub topic. - notifyme - Request to be notified when a point goes in and out of service - killServer - Request to server to exit. public class MessagingConstants { public final static int MESSAGE_SUCCESS = 10; - Asynchronous success public final static int MESSAGE_TIMEOUT = 20; - Synchronous timeout public final static int MESSAGE_MAP = 34; - Synchronous success public final static int MESSAGE_ERROR = 40; - Internal error public final static String ICS_PASSWORD = “45gh” - Registration Password for ICS users }
[0143] Extensions to the Present Embodiment:
- Increase maximum message length. - Add more datatypes. - Obtain a collection values stored in OCSMap. - Persist data if recipient if currently offline. - OCSServer up/down notifications. - Use log4j. - Skip networking if destination is in same application/JDK. - Peer to Peer direct with connection optimization (not all possibilities open) - Security Model (Registration password). - Encryption. - RMI-like stub tool. - Plug in conversions. - Compression.
[0144] Having now described the present system and its architecture, a further description—given by system Use Case Diagrams in UML—will now be discussed.
[0145] [0145]FIG. 2 is a use case diagram of a name service used by the present invention. The name service component maintains a synchronized list of services across multiple run-time spaces. In the following description, it will be appreciated that the numbers in FIG. 2 are used as headings below for typical description fashion for use cases in UML.
[0146] Name Service Use Case Diagram
[0147] System Use Case: Register Space ( 210 ):
[0148] Notify all spaces that this space is now in service. An internal message is sent to all other run-time spaces notifying them that this space is on line.
[0149] System Actors
[0150] Primary: Availability & Timer Service 202
[0151] Pre-Conditions
[0152] 1. Space unregistered
[0153] Flow of Events
[0154] Scenario: Basic Flow
[0155] 1. Availability & Timer Service recognizes that this space has “come on line” and fires “on start” type of event.
[0156] 2. Register space is called.
[0157] 3. Data services is queried to find list of all spaces.
[0158] 4. Broadcast message is sent to all spaces notifying them that this space is now online.
[0159] Post-Conditions
[0160] This space is now on line. Services residing in this space can now register themselves so that other services can use them.
[0161] System Use Case: Unregister space ( 212 ):
[0162] This notifies all spaces that this space is no longer in service. Additionally, this sends an internal message to other spaces.
[0163] System Actors
[0164] Primary: Availability & Timer Service 202
[0165] Secondary: Data Services Framework. 208
[0166] Pre-Conditions
[0167] 1. Registered space.
[0168] Flow of Events
[0169] Scenario: Basic Flow
[0170] 1. Availability & Timer Service recognizes that this space is “going offline” and fires “on stop” type of event.
[0171] 2. Unregister space is called.
[0172] 3. Data services is queried to find list of all spaces.
[0173] 4. Broadcast message is sent to all spaces notifying them that this space is now offline.
[0174] Post-Conditions
[0175] Services residing in this space are automatically unregistered.
[0176] System Use Case: Send heartbeat to all spaces ( 214 ):
[0177] This sends a communication message to all spaces reminding them that this space is operating correctly. Some type of watchdog behavior might be desirable to detect if a space goes out of service ungracefully.
[0178] System Actors
[0179] Primary: Availability & Timer Service 202
[0180] Secondary: Communications Service
[0181] Secondary: Data Services Framework 208
[0182] Flow of Events
[0183] Scenario: Basic Flow
[0184] 1. Availability & Timer Service timer fires an event at periodic intervals.
[0185] 2. Heartbeat message is sent to all other spaces.
[0186] 3. Acknowledgements are received from all spaces within a standard maximum timeframe.
[0187] Scenario: Acknowledgement not received
[0188] 1. Acknowledgment is not received within a maximum timeframe.
[0189] 2. All services within the failed space are ‘marked’ as being unavailable.
[0190] Post-Conditions
[0191] All spaces have recent information that this space is available.
[0192] System Use Case: Synchronize to all spaces ( 216 ):
[0193] This synchronizes data from this space to all other spaces. This is the mechanism for broadcasting internal messages from one space to all the others, e.g., that a space is now online, that a service is now online, etc. Individual internal messages are pushed to all the other run-time spaces.
[0194] System Actors
[0195] Primary: Availability & Timer Service 202
[0196] Secondary: Communications Service
[0197] Secondary: Data Services Framework 208
[0198] Pre-Conditions
[0199] 1. Space registered.
[0200] Post-Conditions
[0201] Information has been propagated to all registered spaces.
[0202] System Use Case: Register service ( 218 ):
[0203] This notifies all spaces that this service is available for use.
[0204] System Actors
[0205] Primary: Service Provider 204
[0206] Pre-Conditions
[0207] 1. Service is unregistered.
[0208] Post-Conditions
[0209] Other system services are now free to use the features of this service.
[0210] System Use Case: Unregister Service ( 220 )
[0211] This notifies all spaces that this service is no longer available to use.
[0212] System Actors
[0213] Primary: Service provider
[0214] Pre-Conditions
[0215] 1. Service is registered.
[0216] Post-Conditions
[0217] The service is unavailable; other system services are no longer free to use the features of this service.
[0218] System Use Case: Find Service ( 222 ):
[0219] This finds a given service so that its features can be used. The given service can be in the current space or some other space.
[0220] System Actors
[0221] Primary: Service user 206
[0222] Pre-Conditions
[0223] 1. The service should be running in a space that is currently in service. Otherwise, see alternate scenarios.
[0224] Flow of Events
[0225] Scenario: Basic Flow
[0226] 1. The given service is running and can therefore be used.
[0227] Scenario: Service not found
[0228] 1. The given service was not found in the synchronized list of available services.
[0229] Scenario: Service out of service
[0230] 1. The given service is not running because the space where the service resides is not in service.
[0231] Post-Conditions
[0232] 1. Features of the found service can now be exercised.
[0233] 2. The found service is prohibited from going out of service until all references are released.
[0234] System Use Case: Release service
[0235] This declares that the given service will no longer be used.
[0236] System Actors
[0237] Primary: Service user
[0238] Pre-Conditions
[0239] 1. Service found.
[0240] Post-conditions
[0241] 1. Features of the service can no longer be exercised.
[0242] 2. If all references are released, the service is allowed to go out of service.
[0243] Event Use Case Diagram
[0244] [0244]FIG. 3 shows the Event Use-Case diagram. The event component implements a communications mechanism between services. One possible mechanism is the asynchronous “publish-and-subscriber” (commonly called pub/sub) communications model so that objects can “fire and forget” a message to another service or collection of services via a well-known event channel name. The service does not support the point-to-point model.
[0245] System Use Case: Create All Event Channels ( 310 )
[0246] This creates an event channel so that it can be used to communicate between services. It is called when the system is started.
[0247] System Actors
[0248] Primary: Availability & Timer Service 302
[0249] Secondary: Data Services Framework 308
[0250] Flow of Events
[0251] Scenario: Basic Flow
[0252] 1. System is started causing the availability event to be fired to run any system initialization routines.
[0253] 2. Query the Data Services framework to obtain a list of all event channels.
[0254] 3. Call Create Event Channel for each.
[0255] Post-Conditions
[0256] Event channels are now ready for use.
[0257] System Use Case: Create event channel ( 312 ):
[0258] This creates an event channel so that it can be used to communicate between services.
[0259] System Actors
[0260] Secondary: Data Services Framework 308
[0261] Pre-Conditions
[0262] 1. Event channel does not already exist.
[0263] Flow of Events
[0264] Scenario: Basic Flow
[0265] 1. Create event channel
[0266] 2. Create channel calls the Communications Service to notify all run-time spaces that the channel exists.
[0267] Post-Conditions
[0268] Event channel is now ready to publish or subscribe to.
[0269] System Use Case: Destroy Event Channel ( 314 ):
[0270] This destroys an event channel so that it can be used to communicate between services.
[0271] System Actors
[0272] Secondary: Data Services Framework 308
[0273] Pre-Conditions
[0274] 1. Event channel already exists.
[0275] Flow of Events
[0276] Scenario: Basic Flow
[0277] 1. Create event channel
[0278] 2. Create channel calls the Communications Service to notify all run-time spaces that the channel no longer exists.
[0279] Post-Conditions
[0280] Event channel is no longer ready to publish or subscribe to.
[0281] System Use Case: Subscribe to event channel ( 316 ):
[0282] This subscribes to an event channel so that channel events can be received.
[0283] System Actors
[0284] Primary: Event Subscriber 304
[0285] Pre-Conditions
[0286] Event channel must exist.
[0287] Flow of Events
[0288] Scenario: Basic Flow
[0289] 1. Subscribe to event channel
[0290] Post-Conditions
[0291] The event subscriber will receive any events published to the event channel.
[0292] System Use Case: Unsubscribe From Event Channel ( 318 ):
[0293] This unsubscribes from an event channel so that the entity will no longer receive channel events.
[0294] System Actors
[0295] Primary: Event Subscriber 304
[0296] Pre-Conditions
[0297] Event channel must exist.
[0298] Post-Conditions
[0299] The event subscriber will no longer receive any events published to the event channel.
[0300] System Use Case: Post Event Object to Event Channel with Priority ( 320 ):
[0301] This posts an event to an event channel so that subscribers can receive it.
[0302] System Actors
[0303] Primary: Event Publisher 306
[0304] Secondary: Communications Service
[0305] Pre-Conditions
[0306] Event channel must exist.
[0307] Post-Conditions
[0308] 1. Object posted into queue/channel.
[0309] System Use Case: Subscriber Poll for Event Channel Event ( 322 ):
[0310] This polls to see if the event channel contains an event.
[0311] System Actors
[0312] Primary: Event Subscriber 304
[0313] Secondary: Communications Service
[0314] Pre-Conditions
[0315] Event channel must exist.
[0316] Flow of Events
[0317] Scenario: Basic Flow
[0318] 1. If an event has been published to the event channel, the event is returned.
[0319] Scenario: Empty Event Channel
[0320] 1. If Event channel is empty, a special “empty channel” event is returned.
[0321] Post-Conditions
[0322] 1. Event returned
[0323] System Use Case: Subscriber Receive Asynchronous Event Channel Event ( 324 ):
[0324] This causes an event-channel event to be received by a event channel subscriber.
[0325] System Actors
[0326] Primary: Event Subscriber 304
[0327] Secondary: Communications Service
[0328] Pre-Conditions
[0329] Event channel must exist.
[0330] Post-Conditions
[0331] 1. Event received.
[0332] It has now been described a novel method and system for allowing clients to send opaque messages to other clients using several different message delivery types—as herein disclosed—to allow for a robust means of communications. It will be appreciated that the scope of the present invention should not be limited to the recitation of the embodiments disclosed herein. Moreover, the scope of the present invention contemplates all obvious variations and extensions thereof.
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A novel method and system are herein described for enabling communications between distributed network objects. In general, a system and method for providing communications between network objects, the means and steps of said system and method comprising: registering said objects desiring communications; accepting a communications message from at least one of said objects, said communication addressing one of said plurality of network objects; determining the mode of message delivery for said message; delivering said message according to the mode of message delivery determined.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. provisional application Ser. No. 61/824,670 filed May 17, 2013, the disclosure of which is hereby incorporated in its entirety by reference herein.
TECHNICAL FIELD
[0002] This disclosure relates to the field of automotive transmissions. More particularly, the disclosure pertains to a front wheel drive transmission with a power transfer shaft configured to selectively transfer power to rear wheels.
BACKGROUND
[0003] Two vehicle powertrain configurations predominate the modern passenger vehicle market, rear wheel drive (RWD) and front wheel drive (FWD). With additional hardware, both of these configurations can be configured to direct power to all four wheels. Because traction at any particular wheel may be limited at certain times, the ability to direct power to all four vehicle improves mobility. However, the additional hardware introduces additional parasitic losses which increase fuel consumption even in conditions that do not require the additional capability.
[0004] In a typical RWD configuration, the engine is oriented longitudinally in the vehicle such that the crankshaft axis is aligned with the direction of vehicle movement. A transmission mounted to the engine drives a rear driveshaft at a speed which may be less than or greater than the speed of the engine crankshaft according to current vehicle requirements. The rear driveshaft is connected to a rear axle that changes the axis of rotation, reduces the rotational speed, and drives left and right rear axles while permitting slight speed differences between the axles as the vehicle turns a corner. A RWD configuration is adapted to also drive the front wheels by adding a transfer case between the transmission and the rear driveshaft. In addition to driving the rear driveshaft, the transfer case drives a front driveshaft that, in turn, drives a front axle. Some transfer cases include a planetary gear set that divides the torque between front and rear driveshafts while allowing slight speed differences. Other transfer cases have an actively controlled torque on demand (TOD) clutch that only drives the front driveshaft in certain conditions, such as when a controller senses loss of traction of the rear wheels.
[0005] In a typical FWD configuration, the engine is oriented transversely in the vehicle such that the crankshaft axis is aligned with the axis of wheel rotation. A transmission mounted to the engine drives a front differential at a speed suitable for current vehicle requirements. The front differential is typically integrated into a common housing with the transmission gearbox. The front differential drives left and right front axles while permitting slight speed differences between the axles as the vehicle turns a corner. A FWD configuration is adapted to also drive the rear wheels by adding a power take off unit (PTU) that drives a rear driveshaft at a speed proportional to the speed of the front differential. A rear drive unit (RDU) typically includes a TOD clutch that, when engaged drives a rear differential that, in turn, drives left and right rear axles.
SUMMARY
[0006] A vehicle powertrain includes an engine, a multiple ratio gearbox, a transfer shaft, a differential, and a disconnect clutch. A gearbox input shaft extending from the right side of the multiple ratio gearbox is driven by a crankshaft of the engine. For example, the input shaft may be driven via a torque converter having an impeller fixed to the crankshaft and a turbine fixed to the gearbox input shaft. A gearbox output shaft is supported for rotation about the gearbox input shaft and meshes with a driven transfer gear fixed to the transfer shaft. A driving transfer gear on the transfer shaft meshes with a final drive gear. The differential, axially located to the left of the driven transfer gear, transfers power from the final drive gear to left and right axle shafts. The differential may be a planetary differential with relatively short axially length. For example, the differential may be a double pinion planetary gear set with the ring gear fixed to the final drive gear, the sun gear fixed to the one front axle shaft, and the carrier fixed to the other front axle shaft. The disconnect clutch, axially located to the right of the driven transfer gear, selectively transfers power from the final drive gear to a hollow power take-off shaft supported for rotation about the right axle shaft. The disconnect clutch may be a dog clutch. The disconnect clutch may be either normally engaged or normally disengaged. The disconnect clutch may be hydraulically actuated, electro-magnetically actuated, or actuated by other means. The vehicle may further include a power take-off unit configured to transfer power from the power take-off shaft to a longitudinal driveshaft. A rear drive unit may include a torque-on-demand clutch to selectively transfer power from the driveshaft to left and right rear axles in response to loss of traction on the front wheels.
[0007] A transmission includes a planetary differential, a clutch, and a transfer shaft. The differential is configured to transfer power from a final drive gear to left and right front axle shafts. For example, the differential may be a double pinion planetary gear set with the ring gear fixed to the final drive gear, the sun gear fixed to the one front axle shaft, and the carrier fixed to the other front axle shaft. The clutch selectively transfers power from the final drive gear to a power take-off shaft. The transfer shaft includes a driving transfer gear meshing with the final drive gear and a driven transfer gear that extends between the differential and the clutch. The transmission may also include a gearbox. A gearbox input shaft of the gearbox extends from the right side of the gearbox and a gearbox output gear rotates about the gearbox input shaft and meshes with the driven transfer gear. The transmission may also include a launch device such as a torque converter having an impeller and a turbine fixed to the input shaft. The disconnect clutch may be a dog clutch. The disconnect clutch may be either normally engaged or normally disengaged. The disconnect clutch may be hydraulically actuated, electro-magnetically actuated, or actuated by other means.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a schematic representation of a vehicle powertrain.
[0009] FIG. 2 is a cross sectional view of a planetary differential suitable for use in the powertrain of FIG. 1 .
[0010] FIG. 3 is a cross sectional view of a hydraulically actuated normally engaged disconnect clutch in the engaged position.
[0011] FIG. 4 is a cross sectional view of the hydraulically actuated disconnect clutch of FIG. 3 in the disengaged position.
[0012] FIG. 5 is a cross sectional view of an electro-magnetically actuated normally disengaged disconnect clutch in the disengaged position.
[0013] FIG. 6 is a cross sectional view of the electro-magnetically actuated disconnect clutch of FIG. 5 in the engaged position.
DETAILED DESCRIPTION
[0014] Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments can take various and alternative forms. The figures are not necessarily to scale; some features could be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention. As those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures can be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations.
[0015] FIG. 1 is a schematic illustration of a FWD based all-wheel drive (AWD) powertrain configuration. Engine 10 generates power to rotate crankshaft 12 . Torque converter 14 transmits the power to gearbox input shaft 16 . Torque converter 14 includes an impeller fixed to crankshaft 12 and a turbine fixed to gearbox input shaft 16 . The torque converter serves as a launch device by transmitting power from the engine to the gearbox input shaft without requiring that the two shafts rotate at the same speed, such as when the vehicle is starting from a stationary position. Gearbox 18 transmits power from shaft 16 to output gear 20 at a speed ratio selected from among a set of available speed ratios based on vehicle speed and accelerator pedal position. Both the gearbox input shaft 16 and the output gear 20 extend from the right side of the gearbox. Output gear 20 is supported for rotation around gearbox input shaft 16 , although not necessarily supported by gearbox input shaft 16 .
[0016] Output gear 20 meshes with driven transfer gear 22 which is fixed to transfer shaft 24 . Driving transfer gear 26 , also fixed to transfer shaft 24 , meshes with final drive gear 28 which is fixed to shaft 30 for rotation about the front axle axis. Final drive gear 28 drives the ring gear 32 of a double pinion planetary differential. The double pinion planetary differential also includes a carrier 34 supporting a set of inner planet gears 36 and a set of outer planet gears 38 . Each outer planet gear 38 meshes with one of the inner planet gears 36 and with interior gear teeth of ring gear 32 . Each inner planet gear 36 also meshes with sun gear 40 . Carrier 34 drives left (driver side) front axle 42 and left front wheel 44 . Sun gear 40 drives right (passenger side) front axle 46 and right front wheel 48 .
[0017] Power take-off gear 50 is fixed to power take-off shaft 49 which is selectively coupled to shaft 30 by disconnect clutch 52 . Power take-off gear 50 meshes with gear 54 which drives beveled gear 56 . Beveled gear 56 meshes beveled gear 58 which is fixed to driveshaft 60 . Beveled gear 62 is selectively coupled to driveshaft 60 by TOD clutch 64 . Beveled gear 62 meshes with beveled gear 66 which drives rear differential 68 . Rear differential divides the power between left rear axle 70 and right rear axle 72 which drive left rear wheel 74 and right rear wheel 76 respectively.
[0018] The powertrain of FIG. 1 can be operated with disconnect clutch 52 engaged or disengaged. Power is transferred to the front wheels independent of the state of disconnect clutch 52 . When disconnect clutch 52 is engaged, the powertrain provides the advantages associated with a FWD based all-wheel drive powertrain configuration. Specifically, if a controller senses that the front wheels have lost traction, TOD clutch 64 is engaged to transfer power to the rear wheels. During a maneuvers that are likely to result in loss of traction of the front wheels, such as rapid acceleration, the TOD clutch may be engaged pre-emptively.
[0019] When disconnect clutch 52 is disengaged, many of the components no longer rotate. Specifically, power take-off gear 50 , bevel gear 56 , and driveshaft 60 no longer rotate. Any parasitic losses attributable to the rotation of these components is eliminated, improving fuel economy. Determination of whether to engage disconnect clutch 52 may be based on explicit driver or may be based on sensing of operating conditions such as temperature that are correlated with likelihood of loss of traction.
[0020] FIG. 2 shows the structure of the planetary differential in more detail. Transmission housing 80 supports shaft 30 via tapered roller bearings 82 and 84 . Transmission housing also supports left front axle 42 via roller bearings 86 and supports right front axle 46 via roller bearings 88 . Unlike a bevel gear differential, the axis of rotation of the planet gears of a planetary differential are parallel to the axle axis. The relatively short axial length of a planetary differential relative to a bevel gear differential permits packaging the differential to the left of driven transfer gear 22 , making the space on the right side of the driven transfer gears available for disconnect clutch 52 . This arrangement also accommodates a driven transfer gear with a relatively large diameter permitting a greater degree of speed reduction and torque multiplication. Although a double pinion planetary differential is illustrated, other types of planetary differential have sufficiently short axial length to package in this available space.
[0021] FIG. 3 shows a first embodiment of disconnect clutch 52 in an engaged position. Dog 90 is splined to power take-off shaft 49 at 92 such that dog 90 rotates with power take-off shaft 49 but may slide axially with respect to power take-off shaft 49 . In the axial position shown in FIG. 3 , teeth of dog 90 engage with teeth of shaft 30 such that the two shafts are forced to rotate together. Member 96 is fixed to dog 90 by snap rings 98 . Spring 100 pushes dog 90 to the left towards the position shown. Thus, this embodiment of the disconnect clutch is biased toward the engaged state. To release the disconnect clutch, pressurized fluid is routed through channel 102 to push piston 104 toward the right. Piston 104 pushes member 96 to the right through thrust bearing 106 . FIG. 4 shows this embodiment in the disengaged position. In this position, dog 90 is axially separated from shaft 30 such that the two shafts are free to rotate at different speeds. Since disconnect clutch 52 is integrated into the transmission, the same valve body that controls the flow of pressurized fluid to various clutches in gearbox 18 to select speed ratios can control the flow of hydraulic fluid to disconnect clutch 52 .
[0022] FIG. 5 shows a second embodiment of disconnect clutch 52 in a disengaged position. Dog 110 , made of a magnetically conductive material, is splined to shaft 30 at 112 such that dog 90 rotates with shaft 30 but may slide axially with respect to shaft 30 . Spring 114 pushes dog 110 to the left towards the position shown. In this position, dog 100 is axially separated from power take-off shaft 49 such that the two shafts are free to rotate at different speeds. Thus, this embodiment of the disconnect clutch is biased toward the disengaged state. Coil module 116 is fixed to transmission case 80 . To engage the disconnect clutch, electrical current is supplied to coils 118 creating a magnetic field to push dog 110 toward the right. FIG. 6 shows this embodiment in the engaged state. In the axial position shown in FIG. 6 , teeth of dog 110 engage with teeth of power take-off shaft 49 at 120 such that the power take-off shaft 49 and shaft 30 are forced to rotate together.
[0023] The clutches illustrated in FIGS. 3-6 are not designed to be engaged in the presence of relative speed between shaft 30 and shaft 49 . In order to engage clutch 52 while the vehicle is moving, engaging TOD clutch 64 synchronizes the speed of shaft 30 and shaft 49 as long as the front and rear wheels are rotating at the same speed, as they would be if both have traction. After bringing the speeds close with the TOD clutch, the TOD clutch may be released while disconnect clutch 52 is engaged. If the speed difference is small, the disconnect clutch will be able to engage as long as vehicle inertia is not restraining the driveshaft from changing speed slightly.
[0024] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. The words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments can be combined to form further embodiments of the invention that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. These attributes can include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. As such, embodiments described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics are not outside the scope of the disclosure and can be desirable for particular applications.
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A front wheel drive transmission is adapted for all-wheel drive by the addition of a selectively engageable power take-off shaft. When a disconnect clutch is engaged, power may be transferred to rear wheels via a power take-off unit and a rear drive unit to improve vehicle mobility. When the disconnect clutch is disengaged, various components of the all-wheel drive system do not rotate, reducing parasitic losses and improving fuel economy. To provide packaging space for the disconnect clutch, the differential is moved to the left (driver side) of the driven transfer gear. A planetary differential, such as a double pinion planetary differential, is suitable for this location
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit under 35 U.S.C. §119 of Korean Patent Application No. 10-2011-0054130, filed Jun. 3, 2011, which is hereby incorporated by reference in its entirety.
BACKGROUND
1. Field of the Invention
The teachings in accordance with the exemplary embodiments of this present disclosure generally relate to a camera module applicable to a smart phone.
2. Background
Recently, a mobile phone, a smart phone and a smart pad which is a type of portable personal computer, mounted with a camera module capable of storing an object in a digital image or a moving image, have been developed.
A conventional camera module includes a lens and an image sensor module converting light having passed the lens to a digital image. However, the conventional camera module has a difficulty in obtaining a high quality digital image due to lack of auto-focusing function capable of automatically adjusting a gap between the lens and the image sensor module and hand-shaking correction function in mobile phones, smart phones and smart pads.
BRIEF SUMMARY
The present disclosure has been made to solve the foregoing problems of the prior art and therefore an object of certain embodiments of the present disclosure is to provide a camera module configured to greatly improve auto focusing and shaking correction function, and ease of assembly, and to inhibit hand-shaking correction function from being decreased by main circuit substrate applied with a driving signal.
Technical subjects to be solved by the present disclosure are not restricted to the above-mentioned description, and any other technical problems not mentioned so far will be clearly appreciated from the following description by the skilled in the art. That is, the present disclosure will be understood more easily and other objects, characteristics, details and advantages thereof will become more apparent in the course of the following explanatory description, which is given, without intending to imply any limitation of the disclosure, with reference to the attached drawings.
Therefore, an object of the present disclosure is to solve at least one or more of the above problems and/or disadvantages in whole or in part and to provide at least advantages described hereinafter. In order to achieve at least the above objects, in whole or in part, and in accordance with the purposes of the invention, as embodied and broadly described, and in one general aspect of the present invention, there is provided a camera module, the camera module comprising: an auto focusing module upping and downing a lens; a hand-shaking correction module wrapping the auto focusing module to correct a hand-shaking by horizontally tilting the auto focusing module; a circuit substrate electrically connected to the hand-shaking correction module and the auto focusing module; a bottom case supporting the circuit substrate to be coupled to the auto focusing module; and a main circuit substrate secured to the bottom case to be electrically connected to the image sensor module, wherein the main circuit substrate is formed with oblong symmetrical openings along an edge of the main circuit substrate.
Preferably, the main circuit substrate includes a body unit formed with the openings, and a connection unit protruded from the body unit to be electrically connected to the circuit substrate.
Preferably, each of the openings is formed in the shape of a slit along at least three sides of the main circuit substrate, and the image sensor module is arranged at an upper surface of the main circuit substrate.
Preferably, a pair of openings is symmetrically formed based on the image sensor module.
Preferably, the image sensor module is arranged at a center of the main circuit substrate formed by the pair of opening.
Preferably, both distal ends of the main circuit substrate are coupled to the bottom case.
Preferably, the camera module further comprises a holder securing the image sensor module.
Preferably, the holder is arranged with an IR (Infrared) filter.
Preferably, the auto focusing module includes an auto focusing housing mounted with the auto focusing module, a bobbin arranged inside the auto focusing housing and mounted with the lens, and a coil wound on the bobbin.
Preferably, a magnet is arranged at an inner lateral surface of the auto focusing housing opposite to the coil.
Preferably, the hand-shaking correction module includes a housing wrapping the auto focusing module, coil blocks each arranged at a lateral wall of the housing, and a magnet formed opposite to the coil block and arranged at an external lateral surface of the auto focusing module.
Preferably, the coil block is arranged inside an accommodation groove formed at each lateral wall of the housing, and both distal ends of each coil block are electrically connected to the circuit substrate.
Preferably, the both distal ends of each coil block and the circuit substrate are soldered at an external side of the housing.
Preferably, the camera module further comprises: an external elastic unit formed in a mutually insulated pair and coupled to the hand-shaking correction module, an inner elastic unit coupled to the auto focusing module and a connection elastic unit connecting the inner and external elastic units.
Preferably, a terminal formed at the external elastic unit is electrically connected to the circuit substrate, and the inner elastic unit is electrically connected to the auto focusing module.
Preferably, the circuit substrate is formed in the shape of a frame along a bottom surface of the housing of the hand-shaking correction module.
Preferably, the circuit substrate includes a first terminal electrically connected to the hand-shaking correction module, and a second terminal connected to the auto focusing module.
Preferably, a part of the circuit substrate is protruded to an external lateral surface of the housing, and the protruded part is formed with connection terminals connected to the main circuit substrate.
Preferably, the circuit substrate includes a flexible circuit substrate.
Preferably, the camera module further comprises a cover can to accommodate the auto focusing module, the hand-shaking correction module, the circuit substrate and the main circuit substrate.
The camera module according to the present disclosure has an advantageous effect in that a lens is upped and downed by an auto focusing module, an auto focusing module is tilted by a hand-shaking correction module to perform hand-shaking correction, and an opening symmetrical to a main circuit substrate coupled to the auto focusing module is formed to inhibit a tilt operation fault of the auto focusing module.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide further understanding of the disclosure and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the disclosure and together with the description serve to explain the principle of the disclosure. In the drawings:
FIG. 1 is a cross-sectional view illustrating an auto focusing module and a hand-shaking correction module of a camera module according to an exemplary embodiment of the present disclosure;
FIG. 2 is an exploded perspective view illustrating a camera module according to an exemplary embodiment of the present disclosure;
FIG. 3 is a perspective view illustrating a main circuit substrate of FIG. 2 ;
FIG. 4 is a rear surface perspective view illustrating a bottom case and a main circuit substrate of FIG. 2 ; and
FIG. 5 is an assembled perspective view of FIG. 1 .
DETAILED DESCRIPTION
Various exemplary embodiments will be described more fully hereinafter with reference to the accompanying drawings, in which some exemplary embodiments are shown. The present inventive concept may, however, be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein. Rather, these exemplary embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the present inventive concept to those skilled in the art.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Descriptions of well-known components and processing techniques are omitted so as not to unnecessarily obscure the embodiments of the disclosure.
Hereinafter, a camera module will be described in detail with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view illustrating an auto focusing module and a hand-shaking correction module of a camera module according to an exemplary embodiment of the present disclosure, FIG. 2 is an exploded perspective view illustrating a camera module according to an exemplary embodiment of the present disclosure, FIG. 3 is a perspective view illustrating a main circuit substrate of FIG. 2 , FIG. 4 is a rear surface perspective view illustrating a bottom case and a main circuit substrate of FIG. 2 , and FIG. 5 is an assembled perspective view of FIG. 1 .
Referring to FIGS. 1 to 5 , a camera module ( 900 ) includes an auto focusing module ( 100 ), a hand-shaking correction module ( 200 ), a circuit substrate ( 300 ), an elastic member ( 400 ), a base ( 500 ), a bottom case ( 600 ), a cover can ( 700 ) and a main circuit substrate ( 800 ).
Referring to FIG. 1 , the auto focusing module ( 100 ) may include an auto focusing housing ( 105 ), a lens ( 110 ), a bobbin ( 120 ), an auto focusing coil ( 130 ) and an auto focusing magnet ( 140 ).
The auto focusing module ( 100 ) may take a shape of upper/bottom ends-opened box, for example. The bobbin ( 120 ) is arranged inside the auto focusing housing ( 105 ), the bobbin ( 120 ) may take a shape of a cylinder, for example. An inner surface of the bobbin ( 120 ) may be mounted with the lens ( 110 ).
The auto focusing coil ( 130 ) may be wound on a periphery of the bobbin ( 120 ), and may be formed by winding an insulated resin-coated long wire on the periphery of the bobbin ( 120 ). A magnetic field is generated from the auto focusing coil ( 130 ) by applying a current to the auto focusing coil ( 130 ), where direction of the magnetic field is determined by direction of the current. The auto focusing magnet ( 140 ) is mounted at an inside of the auto focusing housing ( 105 ), and is arranged opposite to the auto focusing coil ( 130 ).
The auto focusing module ( 100 ) is such that the bobbin ( 120 ) is upped and downed from the auto focusing housing ( 105 ) by attracting force or repulsive force generated by a magnetic field by the current applied to the auto focusing coil ( 130 ) and a magnetic field generated by the auto focusing magnet ( 140 ).
Referring to FIG. 2 , the hand shaking correction module ( 200 ) is coupled to the auto focusing module ( 100 ) to correct hand shaking of the auto focusing module ( 100 ), whereby a higher quality image can be obtained. The hand shaking correction module ( 200 ) includes a housing ( 210 ), a coil block ( 220 ) and a magnet ( 230 ).
The housing ( 210 ) is formed by four lateral walls, and is arranged at an external side of the auto focusing housing ( 105 ) to wrap the auto focusing module ( 100 ).
The coil block ( 220 ) is arranged inside an accommodation groove formed at an external lateral wall of each lateral wall. Each coil block ( 220 ) is formed by winding an insulated resin-coated long wire in an oblong shape, such that the coil block ( 220 ) is formed with two distal ends.
The coil block ( 220 ) can be easily assembled on the circuit substrate ( 300 , described later) by arranging the coil block ( 220 ) to the external lateral surfaces of four lateral walls of the housing ( 210 ) in the exemplary embodiment of the present disclosure.
In a case the coil block ( 220 ) is arranged at an inner lateral surface of each lateral wall of the housing ( 210 ) of very small size, assembly fault can be frequently developed due to difficulty in assemblage of the coil block ( 220 ) and the circuit substrate.
The magnet ( 230 ) is arranged at an external lateral surface of the auto focusing module ( 100 ), and magnetic field generated by the magnet ( 300 ) interacts with magnetic field generated from the coil block ( 220 ) formed at the external lateral surface of each lateral wall of the housing ( 210 ) to inhibit or restrict shaking of the auto focusing module ( 100 ) caused by hand-shaking.
In the exemplary embodiment of the present disclosure, the coil block ( 220 ) of the hand-shaking correction module ( 200 ) is inputted with a driving signal corresponding to a sensing signal inputted from a gyro sensor, for example.
Referring to FIG. 1 , the circuit substrate ( 300 ) is formed in the shape of a square frame when viewed in a top plan view, to improve assemblability of the coil block ( 220 ) and the circuit substrate ( 300 ) and to reduce assembly fault, and the circuit substrate ( 300 ) is formed along a bottom surface of the housing ( 210 ) of the hand-shaking correction module ( 200 ), for example, whereby circuit substrate ( 300 ) covers a bottom surface of the housing ( 210 ).
The circuit substrate ( 300 ) may be a flexible printed circuit board (FPCB) formed with a circuit wiring and terminals in the exemplary embodiment of the present disclosure, for example. A part of the circuit substrate ( 300 ) may be protruded to outside of the housing ( 210 ) of the hand shaking correction module ( 200 ) to be electrically connected to the main circuit substrate ( 800 ). The circuit substrate ( 300 ) is formed with first terminals ( 310 ), second terminals ( 320 ) and a connection wiring (not shown).
The first terminals ( 310 ) are positioned at a place corresponding to both distal ends of each coil block ( 220 ) thus described. The second terminals ( 320 ) is formed at a place connected to terminals of a leaf spring ( 400 ) each connected to both distal ends of the auto focusing coil ( 140 ) of the auto focusing module ( 100 ). In the exemplary embodiment of the present disclosure, if four coil blocks ( 220 ) are formed, eight first terminals ( 310 ) are formed on the circuit substrate ( 300 ), and two second terminals ( 320 ) are formed at the circuit substrate ( 300 ).
Furthermore, a part ( 301 ) protruded to outside of the housing ( 210 ) of the hand shaking correction module ( 200 ) in the circuit substrate ( 300 ) is formed with four connection terminals connected to the first terminals ( 310 ) and the two connection terminals connected to the second terminals ( 320 ). Foreign objects generated in the course of soldering process can be inhibited to enhance a product performance, because the part ( 301 ) protruded to the outside of the housing ( 210 ) is arranged to outside.
Both distal ends of each coil block ( 220 ) of the hand shaking correction module ( 200 ) in the exemplary embodiment of the present disclosure are connected to the first terminal ( 310 ), where in order to inhibit assembly fault and to improve assembly characteristic, each terminal ( 225 ) of the coil block ( 220 ) and the first terminal ( 310 ) are electrically connected from outside by soldering method.
The elastic member ( 400 ) serves to elastically support the tilting auto focusing module ( 100 ) and to electrically connect the auto focusing coil ( 140 ) of the auto focusing module ( 100 ) and the circuit substrate ( 300 ). The elastic member ( 400 ) in the exemplary embodiment of the present disclosure is formed in a mutually insulated pair, and each elastic member ( 400 ) is interposed between a bottom surface of the housing ( 210 ) of the hand shaking correction module ( 200 ) and the circuit substrate ( 300 ). Each elastic member ( 400 ) includes an external elastic unit ( 410 ), an inner elastic unit ( 420 ) and a connection elastic unit ( 430 ).
The external elastic unit ( 410 ) is formed along a bottom surface of the housing ( 210 ) of the hand shaking correction module ( 200 ) and is coupled by being inserted to a lug formed at the bottom surface of the housing ( 210 ). The external elastic unit ( 410 ) is formed with a terminal unit coupled to the second terminal ( 320 ) of the circuit substrate ( 300 ).
The terminal unit formed at the external elastic unit ( 410 ) in the exemplary embodiment of the present disclosure is electrically connected to the second terminal ( 320 ) of the circuit substrate ( 300 ) by soldering method. The terminal unit formed at the external elastic unit ( 410 ) and the second terminal ( 320 ) of the circuit substrate ( 300 ) is assembled at the outside to thereby inhibit connection fault and to improve assemblability.
The inner elastic unit ( 420 ) is coupled to a bottom surface of the auto focusing housing ( 105 ) of the auto focusing module ( 100 ) to elastically support the auto focusing housing ( 105 ) when the auto focusing module ( 100 ) corrects the hand shaking.
The connection elastic unit ( 430 ) serves to connect the external elastic unit ( 410 ) and the inner elastic unit ( 420 ), and the auto focusing module ( 100 ) is elastically supported to the hand shaking correction module ( 200 ) by the connection elastic unit ( 430 ).
The external elastic unit ( 410 ) of the elastic member ( 400 ) is electrically connected to the second terminal ( 320 ) of the circuit substrate ( 300 ), whereby a driving signal provided through the second terminal ( 320 ) is provided to the auto focusing coil ( 140 ) of the auto focusing module ( 100 ) sequentially through the external elastic unit ( 410 ), the connection elastic unit ( 430 ) and the inner elastic unit ( 420 ).
The elastic member ( 400 ) may further include a leaf spring ( 440 ) for auto focusing module, and the leaf spring ( 440 ) elastically supports a bottom surface of the bobbin ( 120 ) of the auto focusing module ( 100 ). Two leaf springs ( 440 ) are mechanically and electrically connected to the elastic member ( 400 ), and both distal ends of the auto focusing coil ( 140 ) wound on the bobbin ( 120 ) are electrically connected to the leaf spring.
The base ( 500 ) takes a shape of a frame having an opening, and is coupled to a bottom surface of the auto focusing housing ( 105 ) of the auto focusing module ( 100 ), where the inner elastic unit ( 420 ) of the elastic member ( 400 ) is secured to a bottom surface of the auto focusing housing ( 105 ) and the base ( 500 ) by the base ( 500 ).
The bottom case ( 600 ) takes a square frame having an opening and is coupled to the auto focusing module. A bottom surface of the bottom case ( 600 ) is formed with coupling units ( 610 ) for securing the main circuit substrate ( 800 , described later). A pair of coupling units ( 610 ) is formed at both sides opposite to the bottom case ( 600 ). The coupling units ( 610 ) inhibit generation of interference when the auto focusing module ( 100 ) is tilted.
Meanwhile, a rear surface of the base ( 500 ) is arranged with a holder ( 620 ) formed with an opening in order to generate a digital image using light having passed the lens ( 110 ), and the holder ( 620 ) is arranged at an inner side with an IR (Infrared) filter ( 630 ). A rear surface of the IR filter ( 630 ) is formed with an image sensor module ( 640 ) including an image sensor circuit substrate ( 648 ) coupled with an image sensor ( 635 ) generating a digital image.
The main circuit substrate ( 800 ) takes a shape of a square plate and may include a body unit ( 800 a ) and a connection unit ( 800 b ) protruded from the body unit ( 800 a ). The connection unit ( 800 b ) is electrically connected to a circuit substrate ( 320 ), and may enhance a product performance by inhibiting or blocking generation and inflow of foreign objects generated in the course of soldering due to non-performance of soldering process inside the housing ( 210 ) and due to protrusion outside of the housing ( 210 ).
An upper surface of the body unit ( 800 a ) of the main circuit substrate ( 800 ) is arranged with the image sensor module ( 640 ), and electrically connected to the image sensor circuit substrate ( 648 ) of the image sensor module ( 640 ) and the circuit substrate ( 300 ) to apply a driving signal to the image sensor module ( 640 ), the auto focusing module ( 100 ) and the hand shaking correction module ( 200 ). The main circuit substrate ( 800 ) may include a flexible printed circuit board, for example.
The body unit ( 800 a ) of the main circuit substrate ( 800 ) is formed with hook units ( 815 ), and each of the hook units ( 815 ) takes a symmetrical shape based on a center of the bottom case ( 600 ). The hook units ( 815 ) inhibit generation of interference when the auto focusing module ( 100 ) is tilted.
The main circuit substrate ( 800 ), being tilted along with the auto focusing module ( 100 ), needs a part generating elasticity, and the main circuit substrate ( 800 ) in the exemplary embodiment of the present disclosure is formed with an oblong or slit-type opening ( 810 ) to generate intrinsic elasticity. The main circuit substrate ( 800 ) is formed with a spring unit ( 820 ) by the opening ( 810 ).
The oblong or slit-type opening ( 810 ) formed at the main circuit substrate ( 800 ) may be formed in the shape of “U” along three lateral sides of the square plate-shaped main circuit substrate ( 800 ). Two symmetrically formed openings ( 810 ) are formed at the main circuit substrate ( 800 ) based on a center of the main circuit substrate ( 800 ), such that, by symmetrically forming the openings ( 810 ), the tilt failure can be solved in which tilting is not accurately performed by the main circuit substrate ( 800 ) when the main circuit substrate ( 800 ) is tilted along with the auto focusing module ( 100 ).
Meanwhile, the cover can ( 700 ) includes an upper cover can ( 710 ) and a bottom cover can ( 720 ), where the upper and bottom cover cans ( 710 , 720 ) have an accommodation space to accommodate the aforementioned constituent elements.
The previous description of the present disclosure is provided to enable any person skilled in the art to make or use the inventive concept. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to limit the examples described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The camera module according to the present invention has an industrial applicability in that a lens is upped and downed by an auto focusing module, an auto focusing module is tilted by a hand-shaking correction module to perform hand-shaking correction, and an opening symmetrical to a main circuit substrate coupled to the auto focusing module is formed to inhibit a tilt operation fault of the auto focusing module.
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The present disclosure relates to a camera module including: an auto focusing module upping and downing a lens; a hand-shaking correction module wrapping the auto focusing module to correct a hand-shaking by horizontally tilting the auto focusing module; a circuit substrate electrically connected to the hand-shaking correction module and the auto focusing module; a bottom case supporting the circuit substrate to be coupled to the auto focusing module; and a main circuit substrate secured to the bottom case to be electrically connected to the image sensor module, wherein the main circuit substrate is formed with oblong symmetrical openings along an edge of the main circuit substrate.
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FIELD OF THE INVENTION
[0001] The present invention relates to a novel process for the preparation of certain cyclopropyl carboxylic add esters and other cyclopropyl carboxylic acid derivatives; a novel process for the preparation of dimethylsulfoxonium methylide and dimethylsulfonium methylide; to the use of certain cyclopropyl carboxylic acid esters in a process for the preparation of intermediates that can be used in the synthesis of pharmaceutically active entities; and to certain intermediates provided by these processes.
DESCRIPTION OF THE INVENTION
[0002] In a first aspect the invention therefore provides a process for the preparation of a compound of formula (I):
[0000]
[0003] wherein:
[0004] is R is phenyl substituted with one or more halogen;
[0005] Y is OR 1 , where R 1 is a straight chain alkyl, branched alkyl, cyclo alkyl, or a substituted bicycloheptyl group (eg bornyl),
[0006] which comprises contacting a compound of formula (II):
[0000]
[0007] where R and Y are as defined above, with dimethylsulfoxonium methylide in the presence of a solvent.
[0008] Suitably the solvent is a polar solvent, preferably dimethyl sulfoxide. Suitably, the reaction is carried out at −10° C.-90° C., preferably 25° C.
[0009] The dimethylsulfoxonium methylide can be prepared by reacting a trimethylsulfoxonium salt with a solid strong base, preferably in solid form, in dimethyl sulfoxide at ambient or an elevated temperature. Suitably, the base is a metal hydroxide, eg NaOH, LiOH, or alkali metal hydride, eg NaH. Preferably the base is sodium hydroxide.
[0010] Preferably, trimethylsulfoxonium iodide is stirred with sodium hydroxide powder in dimethyl sulfoxide (in the absence of a phase transfer catalyst), optionally under nitrogen, at 20-25° C. for 90 minutes. Alternatively, the dimethylsulfoxonium methylide can be prepared from a trimethylsulfoxonium salt (preferably iodide or chloride) using sodium hydroxide in dimethyl sulfoxide with a phase transfer catalyst, for example tetrabutyl-n-ammonium bromide, or with other strong bases, such as alkali metal hydrides, in dimethyl sulfoxide.
[0011] A compound of formula an be prepared by reacting a compound of formula (III):
[0000]
[0012] where R is as defined above, with a suitable chlorinating agent in the presence of an inert solvent and an optional catalyst at a temperature of 0-200° C. Preferably Y is OR 1 , the chlorinating agent is thionyl chloride, the inert solvent is toluene, and the catalyst is pyridine. Suitably the reaction temperature is 70° C. The resulting acid chloride is then reacted with YH or Y − , (where Y − is an anionic species of Y), Y is as defined above, optionally at an elevated temperature, such as 100° C.
[0013] A compound of formula (III) can be prepared using standard chemistry, for example by contacting a compound of formula (IV):
[0000]
[0014] where R is as defined above, with malonic acid in the presence of pyridine and piperidine at an elevated temperature, preferably 50-90° C.
[0015] A compound of formula (1) can be hydrolysed using basic hydrolysis to yield a compound of formula (V):
[0000]
[0016] where R is as defined above. For example, ester groups are preferably removed by basic hydrolysis using an alkali metal hydroxide, such as sodium hydroxide or lithium hydroxide, or quaternary ammonium hydroxide in a solvent, such as water, an aqueous alcohol or aqueous tetrahydrofuran, at a temperature from 10-100° C. Most preferably the base is sodium hydroxide, the solvent is ethanol, and the reaction temperature is 50° C.
[0017] A compound of formula (V) can be used to generate a compound of formula (VI):
[0000]
[0018] where R is as defined above, by reaction with thionyl chloride or another suitable chlorinating agent in the presence of toluene, or another suitable solvent, and an optional catalyst, preferably pyridine, at 0-200° C. Preferably the temperature is to 65-70° C.
[0019] A compound of formula (VI) can be used in the synthesis of a compound of formula (VII):
[0000]
[0020] where R is as defined above, by reaction with an alkali metal azide (preferably sodium azide) in the presence of a phase transfer catalyst (preferably tetra-n-butylammonium bromide), aqueous potassium carbonate and an inert solvent (preferably toluene). Preferably the reaction temperature is 0-10° C.
[0021] A compound of formula (VII) can be used in the synthesis of a compound of formula (VIII):
[0000]
[0022] where R is as defined above, by rearrangement in toluene at temperatures between 0° C. and 200° C., preferably at a reaction temperature of 90-100° C., after which the isocyanate intermediate is reacted with hydrochloric acid at elevated temperatures, preferably 85-90° C.
[0023] An unprotonated parent amine (free base) of formula (IX):
[0000]
[0024] where R is as defined above, can be liberated by adjusting the pH of an aqueous solution of the salt of a compound of formula (VIII) to 10 or more. This can then be converted to other salts of organic acids or inorganic acids, preferably mandelic acid. The R-(−)-mandelic acid salt of a compound of formula (IX) can be generated by addition of R-(−)-mandelic acid at ambient or an elevated temperature to a solution of a compound of formula (IX) in a solvent, preferably ethyl acetate. Preferably the temperature is 20° C.
[0025] Suitably R is phenyl optionally substituted by one or more halogen atoms. Preferably, R is phenyl substituted by one or more fluorine atoms. More preferably R is 4-fluorophenyl or 3,4-difluorophenyl.
[0026] Preferably Y is D-menthoxy, or more preferably, L-menthoxy.
[0027] Compounds of formulae (I) to (IX) can exist in different isomeric forms (such as cis/trans, enantiomers, or diastereoisomers). The process of this invention includes all such isomeric forms and mixtures thereof in all proportions.
[0028] Where Y is chiral, a compound of formula (I) will be a mixture of diastereoisomers and can be resolved to yield a diastereomerically-enriched compound of formula (Ia):
[0000]
[0029] where R and Y are as defined above, by crystallisation or by chromatographic methods.
[0030] Preferably the crystallisation is carried out in situ following the synthesis of a compound or formula (I), as described above, by heating the crude reaction mixture until total or near-total dissolution is achieved, then cooling at an appropriate rate until sufficient crystals of the desired quality are formed. The crystals are then collected by filtration. Alternatively, the resolution can be carried out in any other suitable solvent, such as a hydrocarbon, eg heptane by extracting a compound of formula (I) into a suitable amount of the solvent, heating the extracts until total dissolution is achieved, then cooling at an appropriate rate until sufficient crystals of the desired quality are formed. Optionally the organic extracts can be washed with water, dried over magnesium sulfate and filtered prior to the crystallisation described above.
[0031] A compound of formula (Ia) can be hydrolysed to yield a compound of formula (Va):
[0000]
[0032] where R is as defined above, using the method described above for the hydrolysis of a compound of formula (I) to yield a compound of formula (V).
[0033] A compound of formula (Va) can be used to generate a compound of formula (VIa):
[0000]
[0034] where R is as defined above, using the method described above for the conversion of a compound of formula (V) to yield a compound of formula (VI).
[0035] A compound of formula (VIa) can be used in the synthesis of a compound of formula (VIIa):
[0000]
[0036] where R is as defined above, using the method described above for the conversion of a compound of formula (VI) to yield a compound of formula (VII).
[0037] A compound of formula (VIIa) can be used in the synthesis of a compound of formula (VIIIa):
[0000]
[0038] where R is as defined above, using the method described above for the conversion of a compound of formula (VII) to yield a compound of formula (VIII).
[0039] A compound of formula (Villa) can be used in the synthesis of a compound of formula (IXa):
[0000]
[0040] where R is as defined above, using the method described above for the conversion of a compound of formula (VIII) to yield a compound of formula (IX).
[0041] The R-(−)-mandelic acid salt of a compound of formula (IXa) can be generated using the method described above for the generation of the mandelic acid salt of a compound of formula (IX).
[0042] Novel compounds form a further aspect of the invention. In a further aspect the invention therefore provides compounds of formula (I), (Ia), (II), (III), (V), (Va), (VI), (VIa), (VII), (VIIa), (VIII), (VIIIa), (IX) and (IXa) as defined above.
[0043] Particularly preferred compounds include:
[0044] (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl trans-2-(3,4-difluorophenyl)cyclopropanecarboxylate;
[0045] (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans- (1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate;
[0046] (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl(E)-3-(3,4-difluorophenyl)-2-propenoate;
[0047] (E)-3-(3,4-difluorophenyl)-2-propenoic acid;
[0048] (E)-3-(3,4-difluorophenyl)-2-propenoyl chloride;
[0049] trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylic acid;
[0050] trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl chloride;
[0051] trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl azide;
[0052] trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropyl amine;
[0053] and trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropanaminium(2R)-2-hydroxy-2-phenylethanoate
EXAMPLES
[0054] The invention is illustrated by the following non-limiting examples.
Example 1
[0055] This example illustrates the preparation of (E)-3-(3,4-difluorophenyl)-2-propenoic acid
[0056] A stirred mixture of pyridine (15.5 kg) and piperidine (0.72 kg) were heated to 90° C. Malonic acid (17.6 kg) was added, followed by slow addition, over 50 minutes, of 3,4-difluorobenzaldehyde (12.0 kg). The reaction mixture was stirred at 90° C. for a further 4 hours and 36 minutes. Water (58.5 kg) was added and 32 litres of the pyridine/water mixture then was distilled out of the reactor under reduced pressure. The reaction mixture was acidified to pH 1 with 37% hydrochloric acid (6.4 kg) over a 40-minute period, then cooled to 25° C. with strong stirring. The solids were collected by filtration, washed twice with 1% hydrochloric acid (34.8 L per wash), once with water (61 L) and then deliquored thoroughly in the filter. The product was then dried under vacuum at 40° C. for 24 hours and 40 minutes, affording 13.7 kg of the crystalline product.
Example 2
[0057] This example illustrates the preparation of (E)-3-(3,4-difluorophenyl)-2-propenoyl chloride.
[0058] A stirred mixture of (E)-3-(3,4-difluorophenyl)-2-propenoic acid (8.2 kg), toluene (7.4 kg) and pyridine (0.18 kg) was heated to 65° C. and then thionyl chloride (7.4 kg) was added over 30 minutes. The reaction was stirred for a further 2 h 15 minutes after the addition was complete, then diluted with toluene (8.7 kg). Excess thionyl chloride, sulfur dioxide and hydrogen chloride were then distilled out, together with toluene (10 L), under reduced pressure, yielding a solution of the (E)-3-(3,4-difluorophenyl)-2-propenoyl chloride (approximately 9 kg) in toluene.
Example 3
[0059] This example illustrates the preparation of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl(E)-3-(3,4-difluorophenyl)-2-propenoate.
[0060] A solution of L-menthol (7.1 kg) in toluene (8.5 kg) was added over a 20 minute period to the solution of (E)-3-(3,4-difluorophenyl)-2-propenoyl chloride (prepared as in Example 2) and pyridine (0.18 kg, 2.28 mol) stirring at 65° C. The reaction mixture was stirred at 65° C. for a further 4 hours and 40 minutes after the addition was complete, then cooled to 25° C. and stirred for a 14 hours. The solution was diluted with toluene (16kg), washed with 5% aqueous sodium chloride (6.4 kg), then 6% sodium hydrogen carbonate (6.47 kg), then water (6.1 kg). The solution was dried azeotropically by distillation of the solvent (20 L) under reduced pressure. Dimethyl sulfoxide (33.9 kg) was added and the remaining toluene was distilled off under reduced pressure, affording 47.3 kg of a solution of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl (E)-3-(3,4-difluorophenyl)-2-propenoate (approx. 13.3 kg) in dimethyl sulfoxide.
Example 4
[0061] This example illustrates a method of preparing dimethylsulfoxonium methylide (dimethyl(methylene)oxo-λ 6 -sulfane).
[0062] Sodium hydroxide powder (1.2 kg), prepared by milling sodium hydroxide pellets in a rotary mill through a 1 mm metal sieve, and trimethylsulfoxonium iodide (6.2 kg) were stirred in dimethyl sulfoxide (25.2 kg) under a nitrogen atmosphere at 25° C. for 90 min. The solution was used directly in the preparation of (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl trans-2-(3,4-difluorophenyl)cyclopropanecarboxylate.
Example 5
[0063] This example illustrates a method of preparing dimethylsulfonium methylide (dimethyl(methylene)-λ 4 -sulfane).
[0064] Sodium hydroxide powder (970 mg), prepared by milling sodium hydroxide pellets in a rotary mill through a 1 mm metal sieve, and trimethylsulfonium iodide (4.66 g) were stirred in dimethyl sulfoxide (17 ml) under a nitrogen atmosphere at 20-25° C. for 10 min. The solution was used directly in the preparation of (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl trans-2-(3,4-difluorophenyl)cyclopropanecarboxylate.
Example 6
[0065] This example illustrates the preparation of (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl trans-2-(3,4-difluorophenyl)cyclopropanecarboxylate
[0066] A solution of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl3,4-difluorophenyl)-2-propenoate (approximately 8.6 kg) in dimethyl sulfoxide (approximately 27.9 kg) was added with stirring over 20 minutes to a mixture of dimethylsulfoxonium methylide (approximately 2.6 kg, prepared as described above), sodium iodide ((E)-3-(approximately 4.2 kg), water (approximately 500 g) and sodium hydroxide (approximately 56 g) in dimethylsulfoxide (27.7 kg) at 25° C. The reaction mixture was stirred for a further 2 hours and 50 minutes at 25° C., then used directly for the preparation of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate.
Example 7
[0067] This example illustrates the preparation of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate
[0068] A crude solution of (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl trans-2-(3,4-difluorophenyl)cyclopropanecarboxylate produced as described in example 6 was heated with stirring from 25° C. to 50° C. over a 1 hour period and the temperature was maintained for a further hour. The mixture was then cooled with stirring from 50° C. to 35° C. over 4 hours, kept at 35° C. for 1 hour, then cooled to 26° C. over 4 hours, kept at 26° C. for 1 hour, then cooled to 19° C. over 3 hours and kept at 19° C. for 5 hours and 10 minutes. The product crystallised and was collected by filtration, affording a crystalline solid (2.7 kg) which was shown to contain a mixture of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate (1.99 kg) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1S,2S)-2-(3,4-difluorophenyl)cyclopropanecarboxylate (85 g).
Example 8
[0069] This example illustrates an alternative method of preparing (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate
[0070] n-Heptane (82.5 L) was distilled under reduced pressure from a solution of (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl trans-2-(3,4-difluorophenyl)cyclopropanecarboxylate (14.3 kg, 44.4 mol) in heptane (128.6 L). The mixture was then cooled from 34° C. to 24° C. over a period of 3 hours and 20 minutes. Seed crystals of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate were then added and the mixture was cooled to 0° C. over a period of 5 hours and 50 minutes. Filtration afforded the product as a crystalline solvent wet solid (7.05 kg) which was shown to contain a mixture of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate (4.7 kg) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl trans-(1S,28)-2-(3,4-difluorophenyl)cyclopropanecarboxylate (1.1 kg).
Example 9
[0071] This example illustrates a method of preparing trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylic acid.
[0072] (1R,2S,5R)-2-isoPropyl-5-methylcyclohexyl trans-(1R,2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylate (9.6 kg, 91.8% diastereomeric excess) was dissolved in ethanol (13.8 kg) and heated with stirring to 46° C. 45% Aqueous sodium hydroxide (3.1 kg) was added over a 20 minute period and the mixture was stirred for a further 2 hours and 27 minutes. Solvent (28 L) was distilled out of the mixture under reduced pressure, then the mixture was cooled to 24° C. and diluted with water (29.3 kg), after which the liberated menthol was extracted into toluene (3 washes of 3.3 kg each). The remaining aqueous material was acidified to pH 2 with 37% hydrochloric acid (3.3 L) and the product was extracted into toluene (8.6 kg, then 2 more washes of 4.2 kg and 4.3 kg). The combined toluene extracts were washed with 1% hydrochloric acid (4.9 L), then diluted with further toluene (4.2 kg) and azeotropically dried by distillation of the solvent (25 L) under reduced pressure. A final dilution with toluene (24.2kg) was followed by distillation of the solvent under reduced pressure (10 L) affording a solution containing trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylic acid (approximately 3.45 kg) suitable for the production of trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl chloride.
Example 10
[0073] This example illustrates a method of preparing trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl chloride.
[0074] Pyridine (70 ml) was added to a solution of trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarboxylic acid (approximately 3.45 kg) in toluene (approximately 12-15 kg) prepared as described above,and the mixture was then heated to 65° C. Thionyl chloride (2.3 kg) was added over a period of 1 hour and the mixture was stirred at 70° C. for 3 hours. Thionyl chloride (0.5 kg) was added and the mixture was stirred a further 2 hours at 70° C. A final aliquot of thionyl chloride (0.5 kg) was added and the reaction mixture was stirred for 1 hour at 70° C., then cooled to 40° C. Periodic additions of toluene (45 kg, 3 additions of 15 kg each) were made during distillation of solvent (approximately 60 L) from the mixture under reduced pressure, then the solution of trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl chloride (approximately 3.8 kg) in toluene (approximately 6-9 L) was cooled to 20° C.
Example 11
[0075] This example illustrates a method of preparing trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl azide.
[0076] A solution of trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl chloride (approximately 3.8 kg) in toluene (approximately 6-9 L) at 1° C. was added over a period of 74 minutes to a mixture of sodium azide (1.24 kg), tetrabutylammonium bromide (56 g) and sodium carbonate (922 g,) in water (6.2 kg), stirring at 1.5° C. The mixture was stirred at 0° C. for 1 hour and 55 minutes, then the aqueous layer was diluted with cold water (3.8 kg), stirred briefly, then separated. The toluene layer was washed once more at 0° C. with water (3.8 kg), then with 20% aqueous sodium chloride (3.8 L), then stored at 3° C. for further use.
Example 12
[0077] This example illustrates a method of preparing trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine.
[0078] A cold solution of trans-(1R, 2R)-2-(3,4-difluorophenyl)cyclopropanecarbonyl azide prepared as described in Example 11 was added over a period of 41 minutes to toluene (6.0 kg) stirring at 100° C. The mixture was stirred for a further 55 minutes at 100° C., then cooled to 20° C. and added over a period of 2 hours and 15 minutes to hydrochloric acid (3M, 18.2 kg) stirring at 80° C. After 65 minutes the solution was diluted with water (34 kg) and cooled to 25° C. The toluene layer was removed and the aqueous layer was basified to pH 12 with 45% sodium hydroxide (3.8 kg) and the product was then extracted into ethyl acetate (31 kg) and washed twice with water (13.7 kg per wash), affording a solution containing trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine (2.6 kg, 91.8% enantiomeric excess) in ethyl acetate (29.5 L).
Example 13
[0079] This example illustrates a method of preparing trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropanaminium (2R)-2-hydroxy-2-phenylethanoate.
[0080] R-(−)-Mandelic acid (2.26 kg) was added to a solution containing trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine (2.6 kg, 91.8% enantiomeric excess), stirring at 17° C. in ethyl acetate (45.3 L). The mixture was stirred at 25° C. for 3 hours and 8 minutes, then filtered and washed twice with ethyl acetate (13.8 kg total). The crystalline product was dried at 40° C. under reduced pressure for 23 hours, affording trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropanaminium (2R)-2-hydroxy-2-phenylethanoate (4.45 kg).
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The invention relates to a novel process for the preparation of certain cyclopropyl carboxylic acid esters and other cyclopropyl carboxylic acid derivatives; a novel process for the preparation of dimethylsulfoxonium methylide and dimethylsulfonium methylide; to the use of certain cyclopropyl carboxylic acid esters in a process for the preparation of intermediates that can be used in the synthesis of pharmaceutically active entities; and to certain intermediates provided by these processes.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for effecting rinsing of an inverted siphon, which forms part of a sewer, and a device for performing the method.
2. Description of the Prior Art
Sewers and the like, which pass under a water course or another similar obstacle are often provided with a so called inverted siphon, i.e., a conduit which mainly in U-shape extends below the inclination line of the sewer. The inverted siphon is continuously filled with water and if the water velocity therethrough is low there is a big risk that it will be gradually silted up. Self-rinsing of inverted siphons is obtained at a certain flow velocity which is named the rinsing velocity and is dependent on the dimensions of the conduit. In the smallest inverted siphons which are generally used a water volumetric flow of about 16 l/s is required for reaching the rinsing velocity and this corresponds to the sewage volume from 300-400 small houses during the maximum period of use.
In cases where the built-up areas are smaller, which is very common, it is thus not possible to reach the criteria which are necessary for obtaining self-rinsing inverted siphons, and therefore conventional sewage pumping stations are used for giving the water a sufficient velocity through the inverted siphon to achieve rinsing. Such a pumping station is however comparatively expensive both to build and to run and it furthermore gives rise to problems for if there is any stoppage it will spill over and contaminate the receiving body of water which has often a very low discharge.
BRIEF SUMMARY OF THE INVENTION
The purpose of the present invention is to offer a simple and reliable method of effecting rinsing of the inverted siphon when the head of the discharge is low and at insufficient volumetric flow without the use of a sewage pumping station and without encountering the disadvantages mentioned hereabove and this is according to the invention achieved by arranging upstream of the inverted siphon a fluid reservoir having a reservoir volume which at least corresponds to the volume of the siphon for the length thereof requiring rinsing and by temporarily and for a short period of time at least one every twenty-four hours, giving the fluid content of the reservoir a flow velocity through the inverted siphon, which at least corresponds to the required rinsing velocity for removing sludge which has accumulated in the inverted siphon.
The invention is also in a device for accomplishing the method and this device is mainly characterized by a fluid reservoir arranged upstream of the inverted siphon having a reservoir volume between a normal pressure head curve and the least inclined pressure head curve required for maintaining the required rinsing velocity and means adapted to cause the content of the fluid reservoir to be emptied through the inverted siphon during a short period of time and at a velocity at least corresponding to the required rinsing velocity.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will hereinafter be further described with reference to the embodiment shown in the accompanying drawings wherein;
FIG. 1 is a schematic cross-sectional a view showing device for performing the method according to the invention,
FIG. 2 is a schematic detail view of part of the device according to the invention, and
FIG. 3 is a schematic circuit diagram showing an embodiment of the driving and control system of the device.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIG. 1 is shown in schematic cross section a sewer conduit 1 having a pressure head curve 2 and where it passes beneath a crossing water stream 3 is equipped with an inverted siphon 4. The waste water flows through the conduit at a speed and at a pressure head curve, which is determined by the approaching flow and by the inverted siphon material, appearance and dimension.
Upstream of the inverted siphon 4 there is arranged at a higher level than the sewer lines 1, 1a a fluid reservoir 5, which has a volume that corresponds to a water volume which is sufficient for giving the fluid during a sufficiently long time, commonly about 1 minute, a rinsing velocity, i.e. about 1 meter/sec., which for the smallest conduit area corresponds to about 16 l/s. In order to give the fluid in the reservoir 5 a sufficient velocity through the inverted siphon 4 there is in the present case a mammoth pump 6 connected as a part of the inverted siphon. The mammoth pump is driven and controlled by equipment located in a space 7, which is preferably heated and insulated and which as can be further seen from FIG. 2 encloses a compressor 8 and a tank 9 for compressed air which is charged by the compressor. In the space 7 there is furthermore arranged electric equipment, control equipment, valves, etc. (not shown).
The control equipment of the device incorporates a control member adapted at proper times to start the compressor 8, which thereby will charge the compressed air tank 9 with compressed air and thereafter again will be stopped by the control member when a sufficient volume of compressed air has been supplied to the tank. The tank 9 is connected to the mammoth pump 6 via a feed conduit 10, which has a controllable shut off valve placed therein, which valve is preferably controlled by the impulses from said control member and which thereby preferably is closed when the compressor 8 is started and which is opened when the compressor is closed down. Between the valve and the mammoth pump there is arranged a reduction valve for maintaining the air pressure to the mammoth pump constant during the entire rinse pumping process.
When the shut off valve opens the compressed air in the tank will empty through the jet tube of the mammoth pump, whereby the pressure head curve at the jet tube will drop in correspondence to the head of the discharge of the mammoth pump so that the pressure conditions necessary for the rinse pumping action are obtained. The head of discharge of the mammoth pump is equal to the difference in altitude between pressure head curves 2 and 12.
At the very starting moment a maximum inclined pressure head curve 11 is obtained. The inclination of the pressure head curve will thereafter be gradually reduced as the reservoir is emptied unitl the least inclined pressure head curve 12 required for maintaining the required rinsing velocity is reached. When this condition has been reached the compressed air in the tank 9 is also used up and the mammoth pump 6 stops pumping and will instead act as a part of the inverted siphon. When the rinse pumping process thus has terminated, the reservoir 5 will again automatically be filled up by the approaching fluid, whereby it will contain a required fluid volume when the next rinse pumping process is started. When the reservoir 5 has been filled the fluid will flow in the ordinary manner from the sewer 1 upstream of the inverted siphon 4 through the siphon and further through the sewer 1a downstream of the inverted siphon. Pressure head curve 2 is then agains established. In the sewer 1a downstream of the inverted siphon 4 there is arranged an aerating tube 13, which will aerate the tube system.
In FIG. 3 is shown in a schematic circuit diagram preferred driving and control equipment for the device according to the embodiment of the invention shown in FIGS. 1 and 2.
As can be seen from the figure the equipment incorporates a time switch 14 which is connected to an electric current source and which forms the main part of the control means and is adapted at certain intervals, e.g. each twelfth or twenty-fourth hour, to close a switch 15, whereby a first relay 16 operates and starts a motor 17, which runs the compressor 8, which will thereby pump air into the compressed air tank 9. When the switch 15 is closed a second relay 18 is simultaneously acted upon which second relay switches a magnetic valve 19 from a position, in which the feed conduit 10 from the tank 9 to the jet tube of the mammoth pump is held open to an alternative position in which it closes the conduit 10. When the time switch opens the switch 15 after a certain time, which corresponds to time required for charging the pressure air tank 9, the relays 16 and 18 will both be deenergized, whereby the compressor 8 is stopped and the magnetic valve 19 is switched over to allow the air in the tank 9 to pass to the mammoth pump via a reduction valve 20.
Although the invention hereinbefore has been shown and described as a preferred embodiment it is to be understood that a modifications are possible within the scope of the claims attached to this application.
The mammoth pump 6 can thus be substituted for by other components for giving the fluid such a high velocity that the rinsing velocity is reached and exceeded. As an example on such a component can be mentioned pneumatic driving or it is also possible to place the reservoir 5 so high that the fluid therein can reach rinsing velocity by the aid of self-pressure when the conduit is open. The driving power supplied is then used for raising the fluid up to the reservoir. Another solution is to drive the fluid by aid of compressed air acting inside the reservoir.
It is furthermore possible to govern the driving means and the valves in other ways then by the time switch, e.g. by sensing pressure, velocity and/or level.
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In an inverted siphon (4) in a sewer (1, 1a) where the approaching flow of sewage is insufficient for producing self-rinsing, a fluid reservoir (5) is arranged upstream of the inverted siphon which has sufficient volume for effecting rinsing, and the fluid content of the reservoir intermittently by means of driving members (6, 8, 9) is emptied through the inverted siphon at a velocity which corresponds to and at least during a certain time exceeds the required rinsing velocity.
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This is a division of application Ser. No. 07/974,057 filed Nov. 10, 1992, now abandoned which is a continuation in part of U.S. application Ser. No. 07/956,522, filed Oct. 5, 1992 (now abandoned).
FIELD OF THE INVENTION
This invention relates to biocatalytic methods for the synthesis of various oxygenated compounds, such methods comprising enantiomerically selective functionalization of arene cis-diol starting materials to potentially all of the nine known inositols, shown below. More particularly this invention relates to the synthesis of specific compounds including but not limited to D-chiro-3-inosose 10, and D-chiro-inositol 6, shown below, and also relates to the necessary methods of synthesis for at least three other inositols, neo-, muco-, and allo-inositols. ##STR1## (+)-D-chiro-inositol 6 is of particular interest due to its perceived potential as an antidiabetic agent (See for example: Kennington, A. S.; Hill, C. R.; Craig, J. Bogardus, C.; Raz, I.; Ortmeyer, H. K.; Hansen, B.C.; Romero, G.; Larner, J. New England J. Med. 1990, 323, 373). ##STR2##
BACKGROUND OF THE INVENTION
The expression of arene cis-diols was originally discovered and described by Gibson twenty-three years ago (Gibson, D. T. et al. Biochemistry 1970, 9, 1626). Since that time, use of such arene cis-diols in enantiocontrolled synthesis of oxygenated compounds has gained increasing acceptance by those skilled in the art. Many examples of applications to total synthesis of carbohydrates, cyclitols, and oxygenated alkaloids can be found in the literature, however much of the work done within this area has been with the more traditional approach of attaining optically pure compounds from the carbohydrate chiral pool. (Hanessian, S. in Total Synthesis of Natural Products: The Chiron Approach, 1983, Pergamon Press (Oxford)). Furthermore, none of the work done with these arene cis-diols teaches or suggests the synthesis of the oxygenated compounds which are the subject of the present invention.
In the present invention, unlike in the previous attempts to utilize these arene cis-diols, emphasis has been placed on the application of precise symmetry-based planning to further functionalization of arene cis-diols in enantiodivergent fashion. This approach has previously been successfully applied for the synthesis of cyclitols and sugars. See for example, commonly owned patent applications PCT/US91/02594 (WO 91/16290) and PCT/US91/01040 (WO 91/112257), the disclosure of which is incorporated herein by reference.
Compounds which can be made by the processes set forth herein include oxygenated compounds, however the present processes are particularly useful for the synthesis of compounds such as D-chiro-inositol 6. This compound is potentially an important pharmaceutical agent for the treatment of diabetes. (See for example: a) Kennington, A. S.; Hill, C. R.; Craig, J.; Bogardus, C.; Raz, I.; Ortmeyer, H. K.; Hansen, B.C.; Romero, G.; Larner, J. New England J. Med. 1990, 323, 373; b) Huang, L. C.; Zhang, L.; Larner, J. FASEB, 1992, A1629, Abstr. #4009; c) Pak, Y.; Huang, L. C.; Larner, J. FASEB, 1992, A1629, Abstr. #4008; Larner, Huang, L. C.; Schwartz, C. F. W.; Oswald, A. S.; Shen, T.-Y.; Kinter, M.; Tang, G.; Zeller, K. Biochem. and Biophys. Commun. 1988, 151, 1416.).
While the therapeutic potential of D-chiro-inositol 6 is immense, its availability is limited. It is currently available from various sources which are not economically feasible for bulk supply of the drug to the pharmaceutical industry. For example, D-chiro-inositol 6 can be obtained as the demethylation product from (+)-Pinitol. (+)-Pinitol can be made from chlorobenzene via a six step synthetic process as previously described in commonly owned application PCT/US91/02594 incorporated herein. In addition (+)-Pinitol can be obtained by the extraction of wood dust. (Anderson, A. B. Ind. and Eng. Chem. 1953, 593). The compound 6 may also be obtained by either cleavage of the natural antibiotic kasugamycin (Umezawa, H.; Okami, Y.; Hashimoto, T.; Suhara, Y.; Hamada, M. Takeuchi, T. J. Antibiotics (Tokyo)1965, Ser. A, 18, 101), or by a possible enzymatic inversion of C-3 of the readily available myo-inositol 8. (Umezawa, H.; Okami, Y.; Hashimoto, T.; Suhara, Y.; Hamada, M. Takeuchi, T. J. Antibiotics (Tokyo) 1965, Ser. A, 18, 101.7. Umezawa, H.; Okami, Y.; Hashimoto, T.; Suhara, Y.; Hamada, M. Takeuchi, T. J. Antibiotics (Tokyo) 1965, Ser. A, 18, 101).
While these methods for synthesis of D-chiro-inositol 6 have been described they are not optimal for either clinical or bulk supply of the drug candidate.
Specifically, the known methods of synthesis are not amenable to scaleup or are too lengthy. One of the methods involves extraction of pinitol from wood dust (Anderson, A. B. Ind. and Eng. Chem. 1953, 593) and its chemical conversion to D-chiro-inositol. This procedure, applied to ton-scale would use large volumes of solvents and large quantities of other chemicals and would be either impractical or costly or both. The preparation of D-chiro-inositol from the antibiotic kasugamycin (Umezawa, H.; Okami, Y.; Hashimoto, T.; Suhara, Y.; Hamada, M. Takeuchi, T. J. Antibiotics (Tokyo) 1965, Ser. A, 18, 101) also suffers from drawbacks because, on a large scale, about half of the acquired mass of product would be committed to waste (the undesired amino sugar portion of kasugamycin), not to mention the expense with the development of the large scale fermentation process for this antibiotic. The inversion of one center in the available and inexpensive myo-inositol can in principle be accomplished enzymatically (Umezawa, H.; Okami, Y.; Hashimoto, T.; Suhara, Y.; Hamada, M. Takeuchi, T. J. Antibiotics (Tokyo) 1965, Ser. A, 18, 101.7. Umezawa, H.; Okami, Y.; Hashimoto, T.; Suhara, Y.; Hamada, M. Takeuchi, T. J. Antibiotics (Tokyo) 1965, Ser. A, 18, 101), however no further details on the commercial feasibility of this process have surfaced since 1965.
Based on the shortcomings of the above processes, there is a need for a biocatalytic approach to compound 6 that is an improvement over the above described processes. Such an approach should be environmentally benign as well as amenable to multi-kilogram scale. The currently disclosed process shown in Scheme 1, below is exceedingly brief and efficient in that it provides the epoxydiol 12 in one pot procedure without the necessity of isolation of protected derivative 11. This is an extremely advantageous transformation because it creates four chiral centers in a medium containing water, acetone, magnesium sulfate and manganese dioxide (a naturally occurring mineral), thus making this transformation more efficient and environmentally sound from the point of waste removal. ##STR3## Methods for the synthesis of an epoxydiol 14, which is useful as a synthon, have previously been described (Hudlicky, T.; Price, J. D; Rulin F.; Tsunoda, T. J. Am. Chem. Soc 1990, 112, 9439) This synthon, which was previously used in the preparation of pinitols, as shown in Scheme 2 below, is now prepared by the controlled oxidation of 11 with potassium permanganate (KMnO 4 ) and a subsequent dehalogenation to 14 rather than previous methods described by Hudlicky et al., and is useful in the synthesis of various other compounds as shown in Scheme 1. ##STR4##
SUMMARY OF THE INVENTION
Following the biocatalytic production of arene cis-diols, there are described chemical processes for the synthesis of various oxygenated compounds such as those represented by compounds 6,10-28 herein. Further, there are described methods for the synthesis of a substituted epoxydiol 12 useful as a synthon. This synthon 12, prepared by the controlled oxidation of 11 with potassium permanganate (KMnO 4 ) is useful in the synthesis of various other compounds. The synthesis of the unusual epoxydiol 12 is accomplished as illustrated in Scheme 1.
There are described, chemical processes for the synthesis of various oxygenated compounds such as those represented in Scheme 3 below. Specifically, there are described processes for the preparation of an epoxydiol or an acceptable salt thereof having the formula: ##STR5## wherein X is defined as hydrogen, halogen, alkyl of 1-5 carbon atoms, aryl or CN; the process comprising:
reacting an acetonide of the formula: ##STR6## wherein X is as defined above; with permanganate in an appropriate solvent at a temperature from about -78° C. to about 40° C. and at a pH of from about 4-8. Preferably, X is Cl, Br, methyl, phenyl or CN.
There is also described a process for the preparation of D-chiro-inositol 6 or a pharmaceutically acceptable salt thereof, comprising reducing the epoxydiol 12 (X═Cl, Br) with a reducing agent to yield compound 14 and then hydrolyzing epoxydiol 14 with a hydrolyzing agent including but not limited to water, an alkaline catalyst, an acidic catalyst, Al 2 O 3 or a basic or acidic ion exchange resin.
Also described is a process for the direct hydrolysis of the epoxydiol 12 (X═Cl, Br) to the rare D-chiro-3-inosose 10 and its further reduction to D-chiro-inositol 6, the process comprising hydrolysis of the epoxydiol 12 with a hydrolyzing agent, including but not limited to water, alkaline catalyst, acidic catalyst, basic or acidic ion exchange resin, and then reduction of inosose 10 with a reducing agent.
Additional embodiments of the present invention are related to the synthesis of various oxygenated compounds using the epoxydiol (12) described above as a synthon and as illustrated in schemes 1 and 3 herein.
DETAILED DESCRIPTION OF THE INVENTION
As used in the present invention "suitable or appropriate solvents" include but are not limited to water, water miscible solvents such as dialkylketones with 2-4 carbon atoms, lower alcohols with 1-3 carbon atoms, cyclic ethers and ethers with 2-6 carbon atoms or mixtures thereof.
As used herein "reducing agent" includes but is not limited to a transition metal reagent, a hydride reagent or trialkysilane, preferably Sml 2 , tributyltinhydride or tris(trimethylsilyl)silane. These reducing agents may be used in combination with radical initiation agents such as UV light and/or AlBN or dibenzoylperoxide or a similar initiator.
As used herein "acid catalyst" includes but is not limited to mineral acids, such as HCl; organic acids such as p-toluene sulfonic acid; acid ion exchange resin such as Amberlyst 15, Amberlyst IR 118, Amberlite CG-50, Dowex 50X8-100; all commercially available from Aldrich or similar acidic ion exchange resins.
As used herein "alkaline catalyst" includes but is not limited to alkaline metal hydroxide or alkaline earth metal hydroxides, such as LiOH, NaOH, KOH, or Ba(OH) 2 ; carbonate or bicarbonate of alkaline metal, such as Na 2 CO 3 or K 2 CO 3 ; Al 2 O 3 or basic ion exchange resin such as Amberlite IRA-400, Amberlyst A26, Amberlyst A21, Dowex 1X2-200 or other ion exchange resins.
in an embodiment of the present invention, the compound 12 can be synthesized by forming an acetonide such as compound 11 wherein X is as defined as a substituent selected from the group consisting of, but not limited to hydrogen, halogen, alkyl of 1-5 carbon atoms, aryl or CN., preferably X is Cl, Br, methyl, phenyl or CN. The acetonide 11 is then exposed (contacted) to permanganate in an appropriate solvent at an appropriate temperature to yield the epoxydiol. In a preferred embodiment of the present invention, at least about 1.5 equivalents of KMnO 4 are used and more preferably between about 1.5-2.5 equivalents. When less equivalents of permanganate are used and higher temperatures are used, a side product of this reaction may be formed to a larger extent. Such side product is the diol 13 shown in scheme 1.
As used in this invention, an appropriate solvent for the synthesis of compound 12 includes but is not limited to water, dialkylketones with 2-4 carbon atoms, lower alcohols with 1-3 carbon atoms, cyclic ethers such as tetrahydrofuran (THF) or dioxane and mixtures thereof. Preferred solvents are mixtures of water and acetone or water and an alcohol.
As used in this invention, an appropriate temperature range for the synthesis of compound 12 is from about -78° C. to +40° C., preferably from about -15° C. to about +10° C. It is further understood that depending on the pH range of the reaction mixture, the stability of the desired compound may be effected. Therefore, in a preferred embodiment of the present invention, and particularly a preferred method for the synthesis of compound 12 the pH of the reaction should be maintained between about 4-8.
Any known method for controlling pH can be used, for example a buffering agent or system can be used to maintain such pH range, or one could saturate the reaction mixture with CO 2 or buffer the reaction mixture using some organic or inorganic weak acid such as acetic or boric acid, or by using a buffer working in the region of pH from about 4-8, such as phosphate buffer, acetate buffer, tetraborate buffer or borate buffer. In a preferred process for synthesizing compound 12, magnesium sulfate (MgSO 4 ) is used to maintain the pH between about 4-8. If the reaction mixture is allowed to go above about pH 8, the desired product 12 will be made, although it may be subject to rapid decomposition.
As demonstrated in scheme 1, the exposure of acetonide 11 to 2 eq of aqueous KMnO 4 /MgSO 4 at -10° to 5° C. gave an 8:1 mixture of diols 12 and 13 in 60% yield, while higher temperature and lower concentration of the reagent afforded the expected diol 13 as a major product. The formation of 12 is both unexpected and unusual based on: a) the precedent in the literature regarding the oxidation of simple dienes with permanganate [See: Lee, D. G. in The Oxidation of Organic Compounds by Permanganate Ion and Hexavalent Chromium, Open Court Publishing Company, (La Salle),1980. Two examples of formation of epoxydiols in low yields from permanganate oxidation of conjugated dienes not containing halogens have been reported: von Rudloff, E. Tetrahedron Lett. 1966, 993; and Sable, H. Z.; Anderson, T.; Tolbert, B.; Posternak, T. Helv. Chim. Acta 1963, 46, 1157]; b) the known instability of a-haloepoxides, [See: Carless, H. A. J.; Oak, O. Z. J. Chem. Soc. Chem. Commun., 1991, 61 ;Ganey, M. V.; Padykula, R. E.; and Berchtold, G. A. J. Org. Chem. 1989, 54, 2787]; and c) the unavailability of data concerning direct and controlled oxidation of 1-chloro-1,3-dienes with KMnO 4 or OsO 4 . ##STR7##
As shown in scheme 3 above, the synthon 12 can be used to make several oxygenated compounds. Although applicants have illustrated and/or exemplified a finite number of compounds which can be made using the synthon 12, as a starting material, it is understood that those skilled in the art could readily prepare additional compounds. For example, see scheme 4 below which shows the synthesis of insoitols 3,4 and 5 from the synthon 12. These additional compounds are contemplated by the present invention. ##STR8##
Depending on the desired product, compound 12 can be reacted with a reducing agent such as a hydride reagent or trialkysilane and preferably with tributyltinhydride or tris(trimethylsilyl)silane. This reaction, if necessary as understood by those skilled in the art, may be carried out under conditions of radical initiation such as UV light and/or in the presence of an appropriate radical initiator such as AlBN or dibenzoylperoxide or a radical initiator of a similar nature. Following reduction of the epoxide 12 as described above, the epoxide 14 can be opened and deprotected using pure water, an acid catalyzed hydrolysis with mineral acid, (HCl), an organic acid p-toluene sulfonic acid) or an acidic ion exchange resin including but not limited to Amberlyst 15, Amberlyst IR 118, Amberlite CG-50, Dowex 50 X 8-100, or an alkaline catalysed hydrolysis with weak bases such as a salt of organic acid, preferably sodium benzoate, sodium acetate or sodium citrate, or an alkaline ion exchange resin included but not limited to Amberlyst A 21 or organic bases including but not limited to aliphatic amines such as triethylamine or diisopropylamine. Reaction temperatures range from about -10° C. to about 110° C., and preferably from about 50° C. to about 90° C., in water or an appropriate solvent mixture such as water with a water miscible solvent such as lower ketones with 2-4 carbon atoms, lower alcohols with 1-3 carbon atoms, or cyclic ethers with 4 carbon atoms or ethers with 2-6 carbon atoms.
Compound 12 proved remarkably stable (t 1/2 at 110° C.=approximately 50 hr) and was transformed to the known epoxide 14 [See: Hudlicky, T.; Price, J. D.; Rulin, F.; Tsunoda, T. J. Am. Chem. Soc. 1990, 112, 9439; and Hudlicky, T.; Price, J. Luna, H.; Andersen, C. M. Isr. J. Chem. 1991, 31, 229.] upon reduction with tris(trimethylsilyl)silane/AlBN [Chatgilialoglu, C.; Griller, D.; Lesage, M. J. Org. Chem. 1988, 53, 3642] in 50% yield. The opening of this epoxide with H 2 O in the presence of small amount of sodium benzoate gave, in unoptimized runs, almost pure D-chiro-inositol, identical with authentic samples ( 1 H-NMR and GC) ##STR9##
Direct hydrolysis of 12 with H 2 O in the presence of Al 2 O 3 furnished almost quantitatively the rare inosose 10. This reaction can be carried out using water or using an alkaline catalysis with alkaline ion exchange resin such as Amberlite IRA-400, Amberlyst A 26, Amberlyst A 21, Dowex IX2-200 or ion exchange resin of similar nature, or Al 2 O 3 or a mixture of these; or using acid catalysis by mineral acid such as HCl or organic acid such as acetic acid, or p-toluenesulfonic acid (pTSA) or an acidic ion exchange resin including but not limited to Amberlyst 15, Amberlyst IR 118, Amberlite CG-50, Dowex 50X8-100, or using SiO 2 . Reaction temperatures range from about -10° C. to about 110° C., and preferably are from about 50° C. to 100° C., and the reaction can be carried out in water or an appropriate solvent mixture such as water with a water miscible solvent such as lower ketones with 2-4 carbon atoms, lower alcohols with 1-3 carbon atoms; or cyclic ethers with 4 carbon atoms; or ethers with 2-6 carbon atoms. The resulting inosose 10 from such direct hydrolysis and deprotection can then be reduced to 6 using reducing agent such as hydride reagents, preferably zinc borohydride or sodium borohydride, in an appropriate solvent such as water, lower alcohols with 1-3 carbon atoms, cyclic ethers with 4 carbon atoms, or ethers with 2-6 carbon atoms or a mixture thereof at a temperature of from about -10° C. to about 110° C. Reaction product of such reduction contains a significant amount of 6 (about 25%) separable by using known methods (See Loewus, F. A. Methods in Plant Biochemistry 1990, 2, 219; Honda, S. Anal. Biochem 1984, 140,1)
These results constitute remarkably short and effective synthesis of D-chiro-inositol 6: five chemical steps, all but two performed in aqueous media, with a potential of further shortening of this sequence to four steps upon optimization of the reactions involved. For example, it is comtemplated that the number of steps in this synthesis may be reduced. It is clear that an attractive industrial preparation of 6 will ensue as a result of such an optimization, as will other applications to the synthesis of functionalized cyclitols. There are nine stereoisomers for hexahydroxy cyclohexanes, some of which are important as either free hydroxyls or phosphates, in the communication at the cellular level. (Posternak, T. in The Cyclitols, Hermann, Paris, 1962.) These nine compounds and all of their derivatives can be prepared by controlled functionalization of arene cis diols which are now available through biocatalysis on a commercial scale.
Experimental:
(1S,2R,3S,4S,5R,6S)-2-Chloro-5-dihydroxy-8,8-dimethyl-2,3-oxa-7,9-dioxabicyclo[4.3.0]nonane (12a). To a stirred solution of 1-chloro-2,3-dihydroxycyclohexa-4,6-diene (20.0 g, 0.138 mol) in a mixture of dry acetone (210 ml) and 2,2-dimethoxypropane (23.8 ml, 0,194 mol), placed in a water bath, was added pTSA (0.80 g, 4.20 mmol). After 15 min a saturated solution of Na 2 CO 3 (10 ml) was added and the mixture was cooled to -5° C. (solution A). KMnO 4 (50.0 g, 0.316 mol) and MgSO 4 (21.0 g, 0.175 mol) were dissolved in water (1250 ml) and cooled to 5° C. (solution B). To a mixture of ice (250 g) and acetone (300 ml) cooled to -15° C. was added 50 ml of solution B. Then solutions A and B were simultaneously added over 25 min, maintaining a small excess of KMnO 4 in the reaction mixture and temperature under 5° C. Precipitated MnO 2 was filtered off and washed with water and acetone. The resulting colorless solution was extracted with CHCl 3 , the extract was dried and evaporated under reduced pressure to give 19.1 g of white solid containing 80% of 12a, 10% of 13 and 10% of 27. Recrystallization of the crude product from the mixture of EtOAc/hexane/Et 2 O yielded in two crops 10.5 g (32%) of pure 12a. M.p.=113°-114.5° C.; [α] D 20 =+29.2° (c 1, CHCl 3 ); IR (CHCl 3 ) n 3392; 2983; 2914; 1374; 1220; 1167, 1045 cm -1 ; 1 H NMR (CDCl 3 ) d 4.63 (dd, J=5.9, 1.1 Hz, 1H), 4.56 (dd, J=5.8, 3.3, Hz, 1H), 4.29 (ddd, J=9.5, 4.3, 1.0 Hz, 1H), 4.07 (dddd, J=12.0, 4.3, 3.3., 1.0, 1H), 3.84 (ddd, J=1.1, 1.0, 1.0 Hz, 1H), 2.84 (bd, J=9.6 Hz, 1H), 2.41 (bd, J=12.1 Hz, 1H), 1.48 (s, 3H), 1.40 (s, 3H); 13 C NMR (CHCl 3 )d 110.4 (C), 78.5 (C), 77.1 (CH), 73.3 (CH), 67.8 (CH), 65.9 (CH), 63.7 (CH), 27.0 (CH 3 ), 24.9 (CH 3 ); MS (Cl) m/z (rel. intensity) 237 (M + , 100), 221 (18), 161 (6), 143 (6): Anal. calcd for C 9 H 13 ClO 5 : C, 45.68; H, 5.54;0 Found: C, 45.69; H, 5.49.
(1S,2R,3S,4S,5R,6S)-2-Bromo-4,5-dihydroxy-2,3-oxa-8,8-dimethyl-7,9-dioxabicyclo[4.3.0]nonane (12b). 1-Bromo-2,3-dihydroxycyclohexa-4,6-diene (4.8 g, 0.026 mol) was treated with 2,2-dimethoxypropane as described in preparation of 12a. The resulting mixture was diluted with acetone (75 ml) and cooled to 0° C. Then, maintaining the temperature under 5° C., the solution of KMnO 4 (6.20 g, 0.03 mol) and MgSO 4 (3.00 g, 0.025 mol) in a mixture of water (130 ml) and acetone (60 ml), cooled to 5° C., was added over 30 min. Precipitated MnO 2 was filtered off and washed with water and acetone. The filtrate was then saturated with NaCl and extracted with EtOAc. Drying and evaporation of the extract under reduced pressure yielded crude crystalline product (3.3 g), recrystallization of which (EtOAc/hexane/Et 2 O) gave 1.63 g (22%) of pure 12b. Mother liquor was evaporated under reduced pressure and purified by flash chromatography (10% deactivated silica gel, CHCl 3 :MeOH, 95:5) to furnish 90 mg (1.3%) of 12b, 380 mg (3.8%) of the bromo derivative 13 and 55 mg (1.1%) of 27. For 12b: IR (KBr) n 3390, 2910, 2830, 1380, 1225, 1170, 1070, 1045 cm -1 ; 1 H NMR (CDCl 3 ) d4.65 (dd, J=5.8, 1.3 Hz, 1H), 4.56 (dd, J=5.7, 3.4 Hz, 1H, 4.32 (bdd, J=10.1, 4.3 Hz, 1H), 4.11 (dm, J=12.0 Hz, 1H), 3.91 (m, 1H), 2.81 (bd, J=10.2 Hz, 1H), 2.38 (bd, J=12.1 Hz, 1H), 1.49 (s, 3H), 1.39 (s, 3H); 13 C NMR (CDCl 3 ) d 110.5 (C), 77.2 (C), 74.2 (CH), 71.6 (CH), 67.9 (CH), 66.5 (CH), 63.7 (CH), 27.1 (CH3), 25.1 (CH 3 ); and
For (1S,3R,4R,5R,6S)-8.8-dimethyl-3-hydroxy-4,5-oxa-2-oxo-7,9-di-oxabicyclo[4.3.0]nonane (27): M.p.=126°-127° C.; [a] D 20=+61.1° (c 1, CHCl 3 ); IR (KBr) n 3555, 3045, 2995, 1755, 1440, 1405, 1263, 1235, 1110, 1073 cm -1 ; 1 H NMR (CDCl 3 ) d 5.13 (dd, J=5.8, 1.4 Hz, 1H), 4.86 (ddd, J=5.9, 1.4, 1.4 Hz, 1H), 4.42 (dd, J=5.9, 1.5 Hz, 1H), 3.67 (ddd, J=3.8, 1.4, 1.4 Hz, 1H), 3.39 (ddd, J=3.8, 1.4, 1.4 Hz, 1H), 3.31 (bd, J=5.8 Hz, 1H), 1.60 (s, 3H), 1.39 (s, 3H); 13 C NMR (CDCl 3 ) d 202.4 (C),113.2 (C), 78.2 (CH), 77.4 (CH), 70.0 (CH), 59.5 (CH), 54.0 (CH), 27.3 (CH 3 ), 25.3 (CH 3 ); MS (Cl) m/z (rel. intensity) 201 (M+, 100), 143 (12), 125 (14), 111 (14); Anal. calcd for C 9 H 12 O 5 : C, 54.00; H, 6.04; Found: C, 53.83; H, 6.03.
(1S,2S,3S,4S,8R,9R )-2-Chloro-2.3-oxa-6,6,11,11-tetramethyl-3,7,10,12-tetraoxatricyclo[7.3.0.0 4 ,8 ]dodecane (18a). To a stirred solution of 12a (1.14 g, 4.82 mmol) in dichloromethane (6.0 ml) and 2,2-dimethoxypropane (1.8 ml, 14.6 mmol) was added pTSA (10 mg, 0.053 mmol). After 2.5 h was added a saturated solution of Na 2 CO 3 (0.5 ml) and water (25 ml) and the reaction mixture was extracted with petroleum ether. The extract was dried and evaporated under reduced pressure to give 1.24 g (93%) of colorless crystalline 18a. M.p.=59°-62.5° C.; [a] D 20=+23.1° (c 1, CHCl 3 ); IR (KBr) n 2981, 2930, 1378, 1261, 1214, 1162, 1072, 1053 cm -1 ; 1 H NMR (CDCl 3 ) d 4.62 (m, 3H), 4.35 (ddd, J=6.3, 1.7, 1.0 Hz, 1H), 3.64 (ddd, J=1.8, 1.0, 1.0 Hz, 1H), 1.48+1.47 (s, 6H), 1.40 (s, 3H), 1.36 (s, 3H); 13 C NMR (CDCl 3 ) d 111.0 (C), 110.6 (C), 79.0 (C), 76.2 (CH), 74.7 (CH), 74.2 (CH), 72.1 (CH), 62.2 (CH), 27.4 (CH 3 ), 26.8 (CH 3 ), 25.8 (CH 3 ), 25.3 (CH 3 ); MS (Cl) m/z (rel. intensity) 277 (M+, 63), 261 (80), 245 (10), 219 (15), 183 (40), 161 (43), 143 (72), 133 (62), 125 (45), 115 (75); Anal. calcd for C 12 H 17 ClO 5 : C, 52.09; H, 6.19; Found: C, 52.24;H, 6.22.
(1R,2S,3R,4R,8S,9S )-2,3-Oxa-6,6,11,11-tetramethyl-3,7,10,12-tetraoxatricyclo[7.3.0.0 4 ,8 ]dodecane (19). A solution of 18a (60.0 mg, 0.239 mmol), tri-n-butyltinhydride (76.3 mg, 0.262 mmol) and AlBN (19.6 mg, 0.119 mmol) in benzene (1.5 ml) was heated for 2.5 h under argone to 75° C. The reaction mixture was then diluted with petroleum ether (5 ml) and filtered through 10% deactivated silica gel. Washing of the silica gel with EtOAc and evaporation of the eluent under reduced pressure yielded waxy crystalline product (75 mg), whose flash chromatography (10% deactivated silica gel, hexane:EtOAc, 7:1) furnished 19 (25 mg, 43%). M.p=109°-110° C.; IR (KBr) n 3035, 2980, 1395, 1380, 1250, 1225, 1095, 1075, 1045 cm -1 ; 1 H NMR (CDCl 3 ) d 4.57 (m, 3H), 4.34 (bd, J=6.5 Hz, 1H), 3.34 (m, 2H). 1.52 (s, 3H) 1.41 (s, 3H), 1.37 (s, 6H); 13 C NMR (CDCl 3 ) d 109.3 (C), 108.9 (C), 74.5 (CH), 72.5 (CH), 71.5 (CH), 69.9 (CH), 55.1 (CH), 52.3 (CH), 27.4 (CH 3 ), 26.5 (CH 3 ), 25.8 (CH 3 ), 25.0 (CH 3 ); MS (Cl) m/z (rel. intensity) 243 (M+, 37), 227 (50), 185 (100), 169 (10), 127 (40); Anal calc. for C 12 H 18 O 9 : C, 59.49: H, 7.49; Found: C, 59.58: H, 7.52.
Reduction of haloepoxides 12a,b with tris(trimethylsilyl)silane
A) A solution of 12b (112 mg, 0.398 mmol), tris(trimethylsilyl)silane (147 mg, 0.477 mmol) and AlBN (25 mg, 0.152 mmol)in toluene (2 ml) was heated under argon for 1.5 h to 110° C. Then the reaction mixture was evaporated under reduced pressure to dryness and the residue was flash chromatographed (10% deact. silica gel, CHCl 3 :MeOH, 95:5) to furnish 38.4 mg (48%) of crystalline 14 and 3.9 mg (5%) of 21. B) The solution of 12a (130 mg, 0.522 mmol) and AlBN (25 mg, 0.152 mmol) in toluene (1.5 ml) was heated for 6 h under argon to 105° C. Flash chromatography (10% deact. silica gel, CHCl 3 ;MeOH, 95:5) of under reduced pressure evaporated reaction mixture yielded 37.1 mg (42%) of 14 and 16.2 mg (13%) of 22. For (1S,3R,4S,5R,6S)-3-chloro-4,5-dihydroxy-8,8-dimethyl-2-oxo-7,9-dioxa[4.3.0]nonane (14): M.p.:105°-108° C.; [a] D 20 =110.5° (c 1, CHCl 3 ), IR (KBr) n 3600-3100, 3030, 2955, 1755, 1385, 1245, 1170, 1085 cm -1 ;1H NMR (CDCl 3 ) d 4.93 (dd, J=10.7, 0.7 Hz, 1H), 4.63 (d, J=5.2 Hz, 1H), 4.56 (dd, J=2.9, 2.6 Hz, 1H), 4.53 (dd, J=5.2, 2.9 Hz, 1H), 3.97 (dd, J=10.7, 2.6 Hz, 1H), 2.93 (bs, 2H), 1.41+1.40 (s, 6H); 13 C NMR (CDCl 3 ) d 201.7 (C), 117.3 (C), 86.8 (CH), 74.9 (CH), 70.8 (CH), 66.3 (CH), 27.6 (CH 3 ), 26.2 (CH 3 ).
Reduction of 12a with Sml 2
A) To a solution of 12a (52.1 mg, 0.220 mmol)in a mixture of THF (1 ml) and MeOH (0.3 ml) under argon, was added dropwise over the period of 30 min at -90° C. a solution of Sml 2 (0.1M in THF, 2.5 ml, 0.230 mmol). After 1 h of stirring without cooling a saturated solution of K 2 CO 3 (1 ml) was added and the reaction mixture was stirred for an additional 15 min. Extraction with EtOAc, drying and evaporation of the extract under reduced pressure gave the crude solid product. Flash chromatography (10% deact. silica gel. CHCl 3 :MeOH, 95:5, then 9:1) furnished 7.2 mg (18%) of 20 and 22 mg (49%) of 21. For (1S,4R,5R,6S)-3,4-dihydroxy-8,8-dimethyl-2-oxo-7,9-dioxabicyclo[4.3.0]nonane (21): IR (KBr) n 3450, 3060, 2970, 1750, 1155, 1100 cm -1 ; 1 H NMR (CDCl 3 ) d 4.45 (dd. J=6.3, 3.6 Hz, 1H), 4.49 (bd, 6.5 Hz, 1H), 4,29 (m, 1H), 4.17 (m, 1H), 2.81 (ddd, J=15.0, 8.2, 1.0 Hz, 1H), 2.67 (dd, 15.0, 5.3 Hz, 1H), 2.51 (bd, J=3.3 Hz, 1H), 2.22 (bd, J=4.6 Hz, 1H), 1.44 (s, 3H), 1.41 (s, 3H); 13 C NMR (CDCl 3 ) d 206.7 (C), 110.5 (C), 78.2 (CH), 77.0 (CH), 70.8 (CH), 68.1 (CH), 42.6 (CH 2 ), 26.7 (CH 3 ), 25.1(CH 3 ); MS (Cl) m/z (rel. intensity) 203 (M+, 70), 187 (35), 159 (15), 145 (30), 127 (100); Anal. calcd for C 9 H 14 O 5 : C,53.46; H, 6,98; Found: C, 53.25; H. 6.93. B) Analogous treatment of 12a (420 mg, 1.78 mmol) with solution of Sml 2 (0.1M in THF, 18.0 ml, 1.95 mmol) added over the period of 2 min yielded after chromatography (10% deact. silica gel, CHCl 3 :MeOH, 95:5) 77 mg (22%) of 21 and a complex mixture of products (190 mg). Chromatography (10% deact. silica gel. EtOAc:hexane, 1:1) of this mixture furnished 110 mg (31%) of 23. For (1S,3S,4S,5R)-8,8-dimethyl-5-hydroxy-3,4-oxa-2-oxo-7,9-dioxabicyclo[4.3.0]nonane (23): [a] D 20 =-84.8° (c 1.6, CHCl 3 ); IR (KBr) n 3590, 3060, 3030, 2980, 1760, 1405, 1240, 1185, 1100, 895 cm -1 ; 1 H NMR (CDCl 3 ) d 4.75 (bd, J=9.1, 1H). 4.53 (dd, J=9.1, 6.6 Hz, 1H), 4.10 (dd, 6.5, 4.3 Hz, 1H), 3.70 (d, J=4.6 Hz, 1H), 3.61 (d, J=4.4 Hz, 1H), 2.75 (m, 1H), 1.49 (s, 3H), 1.37 (s, 3H); 13 C NMR (CDCl 3 ) d 201.1 (C), 109.8 (C), 78.0 (CH), 76.0 (CH), 71.5 (CH), 58.6 (CH), 54.9 (CH), 26.3 (CH 3 ), 23.9 (CH 3 ); MS (Cl) m/z (rel. intensity) 201 (M+, 100), 185 (20), 143 (15), 125 (15).
(1S,3R,4S,5R,6S)-4,5-Dihydroxy-8,8-dimethyl-3-methoxy-2-oxo-7,9-dioxabicyclo[4.3.0]nonane (24). A mixture of 12a (141 mg, 0.596 mmol), Zn powder (100 mg) and MeOH (5 ml) was refluxed under argon for 1.5 h. The solid was filtered off and washed with EtOAc. After the addition of Na 2 CO 3 (0.5 ml of saturated solution) and water, the filtrate was extracted with EtOAc. Evaporation and drying of the extract under the reduced pressure furnished 110 mg of crude product. Flash chromatography (10% deactivated silica gel, CHCl 3 : MeOH, 95:5) furnished 77 mg (56%) of 24, 27 mg (21%) of 25 and 8 mg (6%) of staring material 12a. For (1S,3R,4S,5R,6S)-4,5-dihydroxy-8,8-dimethyl-3-methoxy-2-oxo-7,9-dioxabicyclo[4.3.0]nonane (24): IR (CHCl 3 ) n 3457, 2989, 2936, 1742, 1384, 1226, 1158, 1078 cm -1 ; 1 H NMR (CDCl 3 ) d 4.59 (bd, J=4.9 Hz, 1H), 4.51 (m, 2H), 4.19 (bd, J=10.4 Hz, 1H), 3.93 (bd, J=10.3 Hz, 1H), 3.56 (s, 3H), 2.92 (bs, 2H), 1.39 (s, 6H); 13 C NMR (CD 3 OD) d 207.8 (C), 129.3 (CH), 111.6 (C), 85.1 (CH), 79.5 (CH), 73.2 (CH), 69.7 (CH), 59.7 (CH 3 ), 27.4 (CH 3 ), 26.1 (CH 3 ); MS (Cl) m/z (rel. intensity) 233 (M+, 12), 215 (15), 201 (12), 183 (63), 174 (25), 157 (70), 143 (90), 125 (100); Anal. calcd for C 10 H 16 O 6 : C, 51.72; H, 6.94; Found: C, 51.64; H, 6.98.
For (1S,5R,6S)-8,8-dimethyl-5-hydroxy-3-methoxy-2-oxo-7,9-dioxabicyc-lo[4.3.0]non-3-ene (25): IR n (CHCl 3 ) 3520, 3050, 2995, 1720, 1655, 1395, 1245, 1180, 1160, 1095 cm -1 ; 1 H NMR (CDCl 3 ) d 5.80 (dd, J=5.4, 1.2 Hz, 1H), 4.79 (ddd, J=5.5, 5.0, 3.0 Hz, 1H), 4.59 (d, J=5.5 Hz, 1H), 4.51 (ddd, J=5.3, 3.0, 1.2 Hz, 1H); 3.69 (s, 3H), 2.22 (bs, J=5.0 Hz, 2H), 1.42 (s, 3H), 1.39 (s, 3H); 13 C NMR (CD 3 OD) d 192.4 (C), 151.9 (C), 115.5 (CH), 111.2 (C), 80.0 (CH), 76.6 (CH), 65.0 (CH), 55.8 (CH 3 ), 27.0 (CH 3 ), 26.0 (CH 3 ); MS (Cl) m/z (rel. intensity) 215 (M+, 10), 197 (75), 169 (20), 157 (100), 139 (100), 127 (100); Anal. calcd for C 10 H 14 O 5 : C, 56.07; H, 6.59: Found: C, 55.95; H, 6.63.
(1S,6S)-8,8-Dimethyl-3-ethoxy-4-hydroxy-2-oxo-7,9-dioxabicyclo[4.3.0]-non-3-ene (26). A mixture of 12a (375 mg, 1.59 mmol), benzylamine (340 mg, 3.17 mmol) and THF (2 ml) was stirred at -25° C. for 10 h. Then acetone (6 ml) was added and precipitated benzylamine hydrochloride was filtered off at -25° C. To the filtrate at -20° C. was added oxalic acid (142 mg, 1.59 mmol) and after 10 min the mixture was filtered to give 430 mg of white solid. This solid (188 mg) was then heated to reflux in ethanol (5 ml). Precipitated benzylamine oxalate was filtered off and evaporation of the filtrate under reduced pressure yielded 110 mg of the crude product. By flash chromatography (10% deactivated silica gel, CHCl 3 :MeOH, 95:5) was obtained 46.8 mg (26%) of 26 and 16 mg of 28 were obtained. For 26: M.p.=107°-110° C. (dec); [a] D 20 =+102° (c 0.5, MeOH); IR (CHCl 3 ) n 3450, 3050, 3035, 1670, 1650, 1400, 1320, 1275, 1230, 1140, 1115, 1045 cm -1 ; 1 H NMR (CDCl 3 ) d 5.51 (bs, 1H) 4.89 (d, J=8.4 Hz, 1H), 3.83 (ddd, J=11.4, 8.4, 5.2 Hz, 1H), 3.75 (dq, J=9.2, 7.1 Hz, 1H), 3.64 (dq, J=9.3, 7.1 Hz, 1H), 2.93 (ABq, J=16.8, 5.2 Hz, 1H), 2.41 (ABq, J=16.8, 11.5 Hz, 1H), 1.69 (s, 3H), 1.60 (s, 3H), 1.24 (t, J=7.0 Hz, 3H); 13 C NMR (CDCl 3 ) d 189.9 (C), 148.0 (C), 126.3 (C), 117.9 (C), 80.3 (CH), 77.1 (CH), 65.6 (CH 2 ), 39.2 (CH 2 ), 26.6 (CH 3 ), 24.3 (CH 3 ), 15.3 (CH 3 ); MS (Cl) m/z (rel. intensity) 229 (M+, 100), 183 (30), 170 (20), 143 (25), 127 (10); Anal. calcd for C 11 H 16 O 5 : C, 57.89; H, 7.07; Found: C, 57.98; H, 6.98.
(1S,6S)-8,8-Dimethyl-3,4-dihydroxy-2-oxo-7,9-dioxabicyclo[4.3.0]non-3-ene (28). A mixture of 27 (0.23 g), 10% deactivated silica gel (5 g, Silica Gel 60, EM Science), ethylacetate (12 ml) and hexane (8 ml) was stirred at room temperature for 2 h. The mixture was then filtered and the filtrate was evaporated under reduced pressure. Flash chromatography (10% deact. silica gel, ethylacetate:hexane, 6:4) furnished 25 mg (11%) of 28. M.p.=153°-154° C.; [a] D 20 =+102° (c 0.5, MeOH); IR (KBr) n 3295, 2465, 1635, 1410, 1335, 1175, 1140 cm -1 ; 1 H NMR (CDCl 3 ) d 5.45 (bs, 1H), 4.85 (d, J=8.3 Hz, 1H), 4.18 (m, 1H), 2.88 (d, J=16.7, 5.4 Hz, 1H), 2.49 (dd, J=16.8, 11.6 Hz, 1H), 2.43 (bs, 1H), 1.69 (s, 3H), 1.61 (s, 3H); 13 C NMR (CD 3 OD) d 192.5 (C), 151.9 (C), 128.2 (C), 120.0 (C), 86.1 (CH), 82.2 (CH), 43.4 (CH 2 ), 26.9 (CH 3 ), 24.4 (CH 3 ); MS (Cl) m/z (rel. intensity) 201 (M+,100), 85 (23), 81 (15), 69 (23).
D-chiro-inositol (6) A) A mixture of 14 (16.2 mg, 0.080 mmol), ion exchange resin Amberlyst 15 (100 mg) and water (1.5 ml) was heated for 3.5 h to 80° C. Filtering off the resin, washing with water and evaporation of the filtrate under reduced pressure yielded 12 mg of crystalline product containing 70% of 6 (based on 1 H NMR). B) A mixture of 14 (9.7 g, 44.05 mmol), sodium benzoate (30 mg, 0. 21 mmol) and water (150 ml) was refluxed in darkness, under argon for 83 h. The reaction mixture was evaporated, dissolved in a mixture of water and methanol and the mixture was filtered with charcoal. The obtained colorless solution was evaporated to dryness. Recrystallization from the mixture of water and ethanol furnished 6.13 g (77%) of pure 6, identical with the natural product. C) The mixture of 10 (97 mg, 0.545 mmol), NaBH 4 (50 mg, 1.32 mmol) and acetonitrile (5 ml) was stirred at room temperature for 2 h. Then diluted HCl (1:1, 0.2 ml) was added, After an additional 1 h of stirring the reaction mixture was evaporated to dryness to give 180 mg of the product containing 15% of 6 ( 1 H NMR, GC).
D-Chiro-3-inosose (10). A mixture of 12a (93.7 mg, 0.396 mmol), Al 2 O 3 (activated, basic, Brockmann I, 150 mg) and 2 ml of water was heated while stirring for 0.5 h to 80° C. After filtering off the Al 2 O 3 , washing it and evaporation of the filtrate under reduced pressure, 72 mg (84%) of 10 was obtained. IR (KBr) n 3346, 3006, 1735, 1576, 1420, 1302, 1132, 1078, 1005 cm -1 ; 1 H NMR (D 2 O) d 4.40 (dd, J=3.4, 1.3 Hz, 1H), 4.16 (dd, J=9.7, 1.3 Hz, 1H), 3.94 (dd, J=4.1, 3.0 Hz, 1H), 3.84 (dd, J=4.1, 3.2 Hz, 1H), 3.59 (dd, J=9.7, 3.1 Hz, 1H); 13 C NMR (D 2 O) d 208.0 (C), 75,7 (CH), 74.1 (CH), 73.6 (CH), 73.3 (CH), 71.1 (CH).
Neo-inositol (5). A mixture of epoxide 14 (0.69 g, 3.41 mmol), Amberlyst IR-118 (1.5 g) and water (10 ml) was stirred when heated to about 100° C. for 30 min. The solid was filtered off, the solution was filtered with charcoal and evaporated to give 0.54 g (87%) of the mixture containing 70% of 6 and 25% of 5. Recrystallization of this product from aqueous ethanol furnished 96 mg of 5.
Muco-inositol (4). A mixture of epoxide 14 (0.58 g, 2.86 mmol), Amberlyst 15 (0.66 g) and water (20 ml) was stirred at room temperature for 24 h. The solid was filtered off, the solution was filtered with charcoal and evaporated to give 0.43 g (83%) of colorless product containing >90% of 4. Recrystallization of the crude product from aqueous ethanol furnished 4 (0.34 g) of >95% purity.
Allo-inositol (3). A mixture of inosose 10 (1.15 g, 6.45 mmol), Raney nickel (0.5 g) and methanol (15 ml) was hydrogenated at 60 psi for 24 h. The reaction mixture was then diluted with water, filtered with charcoal and evaporated to dryness to furnish 0.91 g (78%) of the crude yellow product containing >90% of 3. Recrystallization of this product (0.626 g) from aqueous ethanol gave 0.24 g of 3.
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There are described novel biocatalytic and chemical processes for the synthesis of various oxygenated compounds. Particularly, there are described processes for the synthesis of a useful synthon 12 made by reacting a protected diol (acetonide) with permaganate under appropriate conditions. Such synthon is useful of the synthesis of various pharmaceutically important compounds such as D-chiro-inositol and D-chiro-3-inosose. Also, there are disclosed novel compounds, including specifically the synthon 12 and compounds derived therefrom.
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FIELD OF THE INVENTION
This invention relates to a method of aseptically producing, harvesting and packaging a pharmaceutical product as well as an apparatus for performing the method.
BACKGROUND OF THE INVENTION
During the production of a powdered product and effecting a packaging of same, care is required in dosing the product in a manner that will not cause the powdered product to contaminate the local environment. It has, of course, been known to orient dosing equipment in sealed chambers which are subjected to a pressure control. As a result, any powdered product intending to escape the dosing apparatus will be limited to the sealed chamber and any filtering equipment utilized to filter the air as it exits the sealed chamber. Nevertheless, powdered product has a tendency to pollute the room, its content and to gather on the exterior surface of the packages into which the powdered product is placed and, therefore, makes the subsequent handling of the packaging a delicate matter.
Accordingly, it is an object of the invention to provide a method and apparatus for aseptically producing, harvesting and packaging of a pharmaceutical product wherein methodology and apparatus has been provided for making the handling of the packaging following a filling thereof with pharmaceutical product less critical.
It is a further object of the invention to provide a method and apparatus, as aforesaid, wherein the powdered product is placed into a transportable bin encased inside a sealed and sterile bag.
It is a further object of the invention to provide a method and an apparatus, as aforesaid, wherein the powdered product is weighed before it is filled into the transportable bin so that the quantity of product placed into the transportable bin can be easily monitored.
It is a further object of the invention to provide a method and an apparatus, as aforesaid, wherein, and in series, an aseptic reactor is provided for producing pharmaceutical product, an aseptic filter/dryer being provided for harvesting the powdered product, an aseptic hammer mill being provided for delumping or micronizing mill for calibration the recovered pharmaceutical product to produce a final powdered product, an aseptic dosing device being provided for facilitating a dosing to an aseptic filling station so that the final powdered product can be introduced into a transportable bin, which transportable bin encased inside a sealed and sterile bag.
SUMMARY OF THE INVENTION
In general, the objects and purposes of the invention are met by providing a method and an apparatus for aseptically producing, harvesting and packaging a pharmaceutical product. A section of the apparatus includes an aseptic reactor and structure for introducing a reactant thereinto so that a reaction can be conducted for the purpose of producing a pharmaceutical product. The pharmaceutical product is subsequently introduced into a filter/dryer for the purpose of recovering the pharmaceutical product. Thereafter, the filtered/dried pharmaceutical product is delivered to a hammer mill for delumping the recovered product to produce a final powdered product. Thereafter, the final powdered product is aseptically introduced into a dosing device and into a transportable bin.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and purposes of this invention will be apparent to persons acquainted with apparatus of this general type upon reading the following specification and inspecting the accompanying drawings, in which:
FIG. 1 is a schematic block diagram setting forth a methodology for aseptically producing, harvesting, and packaging a pharmaceutical product in accordance with the invention;
FIG. 2 is a schematic block diagram of a method for repackaging an aseptically produced pharmaceutical product;
FIG. 3 is a side elevational view of an apparatus for aseptically producing, harvesting and packaging a pharmaceutical product;
FIG. 4 is a side elevational view of an apparatus for aseptically repackaging a pharmaceutical product;
FIGS. 5-14 illustrate an apparatus for performing a sequence of method steps for effecting an aseptic dosing of pharmaceutical powdered product into a presterilized transportable bin and effecting an encasement and sealing of the transportable bin inside the sterile bag;
FIG. 15 is an enlarged cross section of a transportable bin sealed inside a sealed and sterile bag;
FIG. 16 is an enlarged sectional view illustrating the structure for effecting a removal and replacement of a binstopper and in a first position thereof;
FIGS. 17A and 17B illustrate the structure of FIG. 16 in alternate positions; and
FIG. 18 is a sectional view of the dosing section of the apparatus and at an angle oriented at 90° to the illustrations of FIGS. 5-14.
DETAILED DESCRIPTION
Certain terminology will be used in the following description for convenience in reference only and will not be limiting. The words "up", "down", "right" and "left" will designate directions in the drawings to which reference is made. The words "in" and "out" will refer to directions toward and away from, respectively, the geometric center of the device and designated parts thereof. Such terminology will include the words above specifically mentioned, derivatives thereof and words of similar import.
FIG. 3 illustrates a side elevational view of an apparatus 10 for aseptically producing, harvesting and packaging a pharmaceutical product. The apparatus is housed within a building 11 which, in this particular embodiment, includes an upper level 12 and a lower level 13. The upper level 12 includes a room 14 in which is housed an aseptic reactor 16 of any conventional variety adapted to receive therein a reactant. The reactor 16 has an outlet 17 through which produced pharmaceutical product and other by-products can be conveyed. The room 14 also includes an aseptic filter/dryer 18 having an inlet port at any convenient location, as at 19 and an outlet port as at 21. Produced pharmaceutical product produced aseptically in the reactor 16 can, when the appropriate time has arrived, be conveyed out of the outlet port 17 of the reactor 16 into the inlet port 19 through a not illustrated connection whereat it is aseptically filtered and/or dried in the filter/dryer 18 so that the produced pharmaceutical product can be recovered and delivered through the outlet port 21 to the next phase of the process. Since the aseptic reactor 16 and the aseptic filter/dryer are of a conventional construction, no further discussion concerning same is believed to be necessary.
A hole 22 is provided in the flooring 23 between the upper level 12 and the lower lever 13 so as to facilitate the passage of a pipe 24 therethrough, the upper end of the pipe 24 being connected in circuit with the outlet 21 of the aseptic filter/dryer 18 and the lower end thereof being connected to an inlet 27 to an aseptic hammer mill 26. The aseptic hammer mill 26 is conventional and effects a delumping of the recovered pharmaceutical product to produce a final powdered product at the outlet 28 therefrom. Since the aseptic hammer mill 26 is of a conventional construction, no further discussion pertaining to it is believed necessary.
The recovered pharmaceutical product, following its being reduced to a powdered product in the hammer mill 26, is delivered to an aseptic hopper 29 beneath which there is provided an aseptic dosing device 31. The dosing device 31 is housed within an aseptically maintained sealed chamber 32, the sealed chamber 32 being maintained at a pressure less than atmospheric pressure by a filtered air supply and air exhaust system 33.
The apparatus that has been described heretofore also includes circuitry for introducing a substance for rendering the reactor 16, the filter/dryer 18, the piping 24, the hammer mill 26, the storage hopper 29 and the dosing device 31 aseptic without necessitating a disconnecting of the various components from one another. Valving and timing controls (not shown) are provided for this purpose.
While FIG. 3 illustrates a presterilized 600 liter transportable bin 34 oriented beneath the dosing device 31, FIGS. 5-14 will be referenced for illustrating the methodology of filling the transportable bin, but utilizing a smaller variety transportable bin, such as a 16 liter transportable bin 36. The transportable bin 36 is oriented in an aseptic filling station 37 which includes a plurality of upstanding support members 38 mounted on an elevatable platform 39. Each of the upstanding support members 38 includes an elongated guide bar 41 extending generally parallel thereto. A guide mechanism 42 is adapted to move lengthwise along the length of the guide bars 41 so as to cause a secondary platform 43 provided thereon to become elevatable. The secondary platform 43 houses a scale 46 so that it becomes movable with the secondary platform 43. A drive mechanism 44 is provided for moving the secondary platform 43 up and down.
The elevatable platform 39 is supported on a drive mechanism 47 which is, in turn, mounted on the floor or a convenient support surface 48 of the lower level 13 of the building 11.
A plurality of support pins 49 are provided at the upper ends of each of the upstanding support members 38. The purpose of these upstanding pins 49 will become apparent below.
Prior to a placement of the transportable bin 36 onto the upper surface of the secondary platform 43, the transportable bin is preassembled with the binstopper 51 placed sealingly into the open upper end of the transportable bin 36 and placed into the interior of the open top plastic bag 53. The plate 57 closed at the upper end with a bagstopper 58 has a depending cylindrical shell 56 used to hold and secure the open end of the plastic bag 53 by means of a plurality of elastic O-rings 54. This subassembly is sterilized in a dry heat oven at a temperature of 150° to bring all interior parts and the exterior into an aseptic condition. The bagstopper 58 is releasably secured to the plate 57 and provides a double protection for the aseptic condition inside the transportable bin 36.
This subassembly is brought to the filling station, installed on the secondary platform, the plate 57 resting on the upper ends of the support and the preguiding pins 49 so as to be correctly positioned and aligned with the disposing opening 79 and the aseptic dosing device 31.
The sealed chamber 32 has therein an upstanding support 61 mounted on a bottom wall 62 of the chamber 32 for supporting a vertically upstanding rod 63. A linear actuator mechanism 64 is supported for movement along the length of the rod 63 and carries therewith a bracket member 65.
The dosing mechanism 31 includes a slide gate mechanism 66 that is supported for reciprocal movement so as to open and close the lower end of the storage hopper 29 in a conventional manner. When the slide gate mechanism 66 is in the opened condition, powdered product will dump down into a housing 67 having an extendable sleeve 68 oriented at the lower side thereof. The sleeve 68 can be extended and retracted due to its connection to the bracket assembly 65.
A pair of upstanding supports 69 are mounted on the bottom wall 62 of the sealed chamber 32 and each support an elongated shaft 71 extending horizontally therebetween. A linear actuator 72 is mounted for longitudinal movement along the length of the shaft 71. The linear actuator 72 has a bracket assembly 73 thereon which carries a further linear actuator 74, which linear actuator 74 has an elongated reciprocal rod 76 extending therefrom which has attached to the distal end thereof a further bracket assembly 77. A suction activated gripper 78 is secured to the bracket assembly 77.
The bottom wall 62 (FIG. 16) of the sealed chamber 32 includes a centrally disposed opening 79 oriented beneath the outlet of the sleeve 68. The opening 79 is covered or closed off by a plate 81 secured by a plurality of fasteners 82 to the bottom wall 62. The plate 81 has a centrally disposed opening 83 therein which is covered by a removable cover 84. As a result, and prior to a removal of the cover 84, the interior of the sealed chamber 32 remains sealed from the outside environment. The left half of FIG. 16 illustrates the arrangement prior to the placement of a bin 36 and its accompanying plate 57 onto the upper surface of the secondary platform 43. The right half of FIG. 16 illustrates the presence of the transportable bin 36 and its associated plate 57.
OPERATION
Although the operation of the apparatus embodying the invention has been indicated somewhat above, the operation will be described in detail hereinbelow to assure a more complete understanding of the invention.
As depicted in FIG. 3, reactants are introduced into the aseptic reactor 16 for the purpose of producing a pharmaceutical product. Thereafter, the pharmaceutical product is delivered through the outlet 17 into an inlet port 19 of the filter/dryer mechanism 18 for the purpose of recovering the pharmaceutical product. The pharmaceutical product is extracted from the filter/dryer 18 through an outlet port 21 and delivered through piping 24 to the inlet port 27 of the aseptic hammer mill 26 for the purpose of delumping the pharmaceutical product to produce a final powder product. Thereafter, the final powder product is delivered through an outlet port 28 into the storage hopper 29 and thence to the aseptic dosing device 31 for controlling an amount of final powder product to be dispensed into a transportable bin. A transportable bin 36 and its associated plate 57 supporting a sterile bag 53 are placed onto the upper surface of the secondary platform 43 so as to orient the open upper end 52 of the transportable bin 36 in axial alignment with the extendable sleeve 68 connected to the outlet from the aseptic dosing device 31. At this point in the operation, the system is in the configuration illustrated in FIG. 5 with the upper surface of the plate 57 being spaced from the lower surface of the plate 81.
The drive mechanism 47 is next activated to raise the platform 39 from the position illustrated in FIG. 5 to the position illustrated in FIG. 6. This causes the upper surface of the plate 57 to come into engagement with the lower surface of the plate 81 as illustrated in FIG. 6 and the right half of FIG. 16 and causes the cover 84 to become engaged with the cover 58. In this position, the suction activated gripper 78 is activated to simultaneously effect a gripping of the cover 58 on the plate 57 and a removal of the cover 84 from its engagement with the plate 81. Thereafter, the linear actuator 74 is activated to raise the cover 84 with the cover 58 being fastened thereto until the configuration illustrated in FIG. 7 is achieved. The linear actuator 74 has been cross hatched in FIG. 7 for the purpose of symbolizing its activation. Similarly, the linear actuator 72 is also activated to move the pair of covers 84 and 58 away from the plane of the drawing for FIG. 7, namely, to the right illustrated in FIG. 18. The pair of covers 84 and 58 are delivered to a holding apparatus 86 adapted to hold the pair of covers 84 and 58 in a parked condition out of the way. FIG. 17A also illustrates the simultaneous lifting of the pair of covers 84 and 58 by the suction activated gripper 78. FIG. 17A also illustrates a rail construction 87 extending parallel to the shaft 71 and a pair of vertically spaced wheels 88 riding on opposite upper and lower edges of the rail 87 for facilitating a movement of the bracket assembly 73 in a precisely controlled manner parallel to the longitudinal axis of the shaft 71 so as to bring the pair of covers 84 and 58 to the holding apparatus 86 illustrated in FIG. 18. FIG. 8 purposefully deletes the illustration of the suction activated gripper 78 to symbolize that it is out of the plane of FIG. 8.
Next, the drive mechanism 44 is activated as shown in FIG. 8 to lift the transportable bin 36 relative to the plate 57. The outer tapered surface 89 of the transportable bin 36 is brought into engagement with a tapered surface 91 encircling the opening 92 through the plate 57 as illustrated in FIG. 17A. The engagement between the exterior tapered surface 89 on the bin 36 and the tapered surface 91 of the opening 92 effects a sealed connection therebetween.
Thereafter, the linear actuator 72 is again activated to bring the suction activated gripper 78 back into the plane of the drawing and particularly the configuration illustrated in FIG. 9. The linear actuator 74 is again activated to lower the suction activated gripper 78 into engagement of the upper surface of the binstopper 51 and through a manipulation of the suction activation mechanism, grip the binstopper 51. Upon a reversal of the linear actuator 74, the suction activated gripper 78 is lifted carrying therewith the binstopper 51 from the now open upper end 52 of the transportable bin 36. The linear actuator 72 is activated to take the suction activated gripper 78 and binstopper 51 to a location out of the plane illustrated in FIG. 9 and to the configuration generally depicted in FIG. 10. Thereafter, the linear actuator 64 is activated to lower the bracket 65 carrying therewith the extendable sleeve 68 downwardly and projecting it into the open upper end 52 of the transportable bin 36. Thereafter, the slide gate mechanism 66 on the dosing device 31 can be activated to the open position to allow aseptic pharmaceutical product to leave the storage hopper 29 and enter the transportable bin 36. The scale 46 is activated during this time period to weight the contents as they enter the transportable bin. The tare weight is defined before the transportable bin 36 is moved into its centering position. Following the placement of a designated amount of pharmaceutical product into the transportable bin 36, the slide gate mechanism 66 is moved to the closed position to stop the further flow of pharmaceutical product out of the storage hopper 29 and into the transportable bin 36.
Next, the linear actuator 64 is activated to retract the sleeve 68 to the FIG. 11 configuration. Similarly, the linear actuator 72 is activated to bring the linear actuator 74 and suction activated gripper 78 carrying the binstopper 51 into the plane of the drawing as depicted in FIG. 11 so as to orient the suction activated gripper 78 and binstopper 51 over the open upper end 52 of the transportable bin 36. The linear actuator 74 then effects a movement of the binstopper 51 downwardly and into the open upper end 52 of the transportable bin 36 and thereafter raises the gripper 78, following a release of the binstopper 51, and moves the gripper 78 to a position out of the plane of the drawing as symbolized by the configuration in FIG. 12.
Thereafter, and as shown in FIG. 13, the drive mechanism 44 is operated to lower the transportable bin 36. At the same time, the linear actuator 74 and gripper 78 fastened thereto has reacquired the pair of coupled together covers 84 and 58 from the holding apparatus 86. The linear actuator 72 will, upon an appropriate activation thereof, bring the pair of covers 84 and 58 secured to the suction activated gripper 78 into the configuration illustrated in FIG. 13. Appropriate operation of the linear actuator 74 will cause a placement of the pair of covers 84 and 58 back into their original position closing off the respective openings 83 and 92. Thereafter, the drive mechanism 47 is activated to lower the secondary platform 43 to separate the upper surface of the plate 57 from its engagement with the lower surface of the plate 81. The covers 84 and 58 also become uncoupled during a deactivation of the gripper 78. The sealed chamber 32 remains now closed off from the outside.
Prior to an operation of the drive mechanism 47, and if desired, an operator can access the sealed chamber 32 through a gloved wall (not illustrated) for the purpose of fastening a clip C (FIG. 15) onto the binstopper 51 so as to lockingly secure the binstopper 51 to the transportable bin 36. Thereafter, the pair of covers 84 and 58 can be placed into their closed position with respect to the respective openings 83 and 92 as aforesaid.
Next, the transportable bin 36 can be removed from the filling station 37 along with the associated plate 57 and the cylindrical shell 56 to which the upper end of the sterile bag 53 is secured by the pair of O-rings 54. The assembly consisting of the transportable bin 36 inside of the sterile bag 53 can be taken to a bag sealing station whereat a pair of bag sealing anvils 93 can be employed to effect a sealed closing of the bag intermediate the upper end of the transportable bin 36 and the lower edge of the cylindrical shell 56 as schematically depicted in FIG. 15. Now the powder product P inside the transportable bin 36, which bin is in turn inside of the sterile bag 53 sealingly closed as at 94, is now ready for transport.
The aforesaid methodology, depicted in FIG. 1, and apparatus have accomplished the filling of a transportable bin with no ability for the powdered product to escape into the local environment. Further, the aseptic condition of the equipment prior to and during the filling operation preserves the integrity of the powdered product inside of the transportable bin 36.
ALTERNATE CONSTRUCTION (FIG. 4)
In some instances, other processes than delumping e.g. micronization are in need to meet final product requirements. In this instance, the set up will be as in FIG. 3. A 600 liter bin 34 equipped with the same cover 58 and matching cap plate 57 design will be presterilized inside before filling. After aseptic harvesting, using the same method as described before, the bin 34 will be transported to the workcenter designed as shown in FIG. 4.
The bin 34 containing the aseptically harvested product, will be lifted inverted and installed on the docking system 96. The same cover 58 lifting system is used to allow the feeding of the product through the piping to the micronizing mill. Further operations take place as described before, for filling into the transportable 16 liter bin enclosed in a sterile bag or into a 600 liter presterilized bin for further aseptic bulk handling. As a result, the process depicted in FIG. 2 has been performed.
Although particular preferred embodiments of the invention have been disclosed in detail for illustrative purposes, it will be recognized that variations or modifications of the disclosed apparatuses, including the rearrangement of parts, lie within the scope of the present invention.
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A method and an apparatus for aseptically producing, harvesting and packaging a pharmaceutical product. A section of the apparatus includes an aseptic reactor and structure for introducing a reactant thereinto so that a reaction can be conducted for the purpose of producing a pharmaceutical product. The pharmaceutical product is subsequently introduced into a filter/dryer for the purpose of recovering the pharmaceutical product. Thereafter, the filtered/dried pharmaceutical product is delivered to a hammer mill for delumping or a micronizing mill for calibration and sizing the recovered product to produce a final powdered product. Thereafter, the final powdered product is introduced into a dosing device and aseptically introduced into a transportable bin. The small bins are encased inside of a sterile bag for transport and further aseptic handling.
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The U.S. Government may have rights in the present application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention generally relates to electronic devices. More particularly, a digital logic voltage level shifter with user-definable voltage levels is presented.
2. Description of the Related Art
The majority of digital devices today employ voltage-sensitive binary logic. In binary logic devices, one voltage level represents a logic `0` or `low` while a different voltage level represents a logic `1` or `high`. In positive logic, the lower voltage level represents the logic `0` and the higher voltage level represents a logic `1`. In negative logic, the reverse is true. Typically, the minimum output drive voltage levels exceed the maximum input switching threshold voltage levels by some minimum amount to guarantee error-free operation in the presence of noise and part-to-part variation.
Digital logic devices are fabricated from various materials, such as silicon (Si), germanium (Ge) and gallium arsenide (GaAs), using different process technologies. Typically, each digital logic device is designed to operate around a fixed set of input switching threshold and output drive voltage levels. These voltage levels are determined by design and by the particular combination of materials and process technology used to fabricate that device. To accommodate the large number of possible materials and process technology combinations, several different sets of logic voltage levels have been standardized. Devices constructed from similar materials and process technologies that operate to the same set of input switching threshold and output drive voltage levels are referred to as a logic family, such as 5.0 volt and 3.3 volt CMOS and TTL. The number and type of digital logic families are continuously changing in response to both changing technologies and market demands.
Often, digital devices from different logic families must communicate with each other. Unfortunately, the logic voltage levels of different logic families are often incompatible with each other. Directly connecting devices from different logic families can result in unreliable or even non-functional interfaces. It shall also be noted that newer components of a logic family are sometimes not compatible with the older components.
A few logic level shifters have been designed to interface devices from dissimilar logic families, but each is designed for a single specific interface (e.g. 3.3 volt and 5.0 volt CMOS). With the ever-changing and growing number of logic families on the market today, fixed logic level shifters cannot hope to keep up with the number of possible logic family interface requirements. A design that mixes two or more dissimilar logic families can require several different logic level shifters to satisfy all interface requirements. Unfortunately, this increases the number of part types, the total part count and system cost.
When a large number of devices are connected together on a single net, such as multiple boards connected across a backplane, the capacitance of that net becomes considerable. The amount of power necessary to drive digital data across any net is a function of the total net capacitance, the data switching frequency and the difference between the high and low logic voltage levels. Transceivers are high-drive bi-directional logic buffer devices that are typically used to drive large nets and to buffer other devices from those nets. Some transceiver devices also act as level shifters in that they provide a standard full-swing logic interface on the low-capacitance daughterboard side and a special reduced-swing logic interface on the high-capacitance backplane side. This is done to reduce the power necessary to transmit data across the backplane. Several different sets of reduced swing backplane voltage levels have been standardized. Table 1 lists the logic voltage levels of some standard reduced-swing backplane voltage specifications. Like the low-drive level shifters, each of these high-drive level shifters is designed for a single specific interface, such as 5.0 volt TTL on the board side to BTL on the backplane side. Unfortunately, these devices are too specific to be used for more than a single specific interface.
TABLE 1______________________________________Standard Reduced-Swing Backplane Logic Voltage Levels Input Threshold Output DriveBackplane Voltage VoltageSpecification Levels LevelsName VIL VIH VOL VOH______________________________________Backplane Transceiver Logic (BTL) 1.475 1.625 1.100 2.100Center-Tapped Termination (CTT) 1.300 1.700 1.100 1.900Enhanced Transceiver Logic (ETL) 1.400 1.600 0.400 2.400Gunning Transceiver Logic (GTL) 0.750 0.850 0.400 1.200Kuo Transceiver Logic (KTL) 0.950 1.050 0.600 1.400Lipp Transceiver Logic (LTL) 1.700 2.100 0.000 3.300Low Voltage Swing CMOS (LVSC) 0.475 1.625 1.100 2.100Low Voltage TTL (LVTTL) 0.800 2.000 0.400 2.400______________________________________
SUMMARY OF THE INVENTION
A voltage level shifter is disclosed having an input and an output. The input receives a first signal capable of fluctuating between at least two voltages. The voltage level shifter produces a second signal, at the output, based on the voltage of the input signal and two or more user-defined reference voltages.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram depicting a voltage level shifter having user-definable switching threshold voltage levels.
FIG. 2 is a schematic diagram depicting a voltage level shifter with user-definable output drive and clamp voltage levels.
FIG. 3 is a schematic diagram depicting a bi-directional voltage level shifter.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 schematically depicts the preferred configuration of a voltage level shifter 200 with user-definable switching threshold voltage levels. In the preferred embodiment, voltage level shifter 200 is comprised of an analog voltage comparator 205, a two-to-one (2:1) analog multiplexer 204 (having a select input, a first input and a second input), a VIL (voltage input low) analog input port 202, a VIH (voltage input high) analog input port 203, a digital IN (input) port 201 and a digital OUT (output) port 206.
The first input of multiplexer 204 is connected to the VIL input port 202, while the second input of multiplexer 204 is tied to the VIH input port 203. The positive (+) input of comparator 205 is connected to the input port 201. The negative (-) input of comparator 205 is connected to the output of multiplexer 204. The output of comparator 205 is connected to the select input of multiplexer 204 and to output port 206. The output of comparator 205 and the select input of multiplexer 204 are designed to be compatible with standard logic voltage levels.
In the preferred embodiment, digital data is applied to input port 201, while user-defined dc reference voltages are applied to VIL input port 202 and VIH input port 203, such that V(VIL)<V(VIH). V(VIL) and V(VIH) directly define the low and high input switching threshold voltage levels of comparator 205 relative to V(IN). Please refer to Table 5 for the preferred values of VIL and VIH for common backplane standards.
When the output of comparator 205 is low, multiplexer 204 connects V(VIH) to the negative input of comparator 205. When the output of comparator 205 is high, multiplexer 204 connects V(VIL) to the negative input of comparator 205. The OUT output port 206 (output of comparator 205) switches from low to high when V(IN)>V(VIH). Conversely, output port 206 switches from high to low when V(IN)<V(VIL). When V(VIL)<V(IN)<V(VIH), the output of comparator 205 remains in its last driven state.
Feedback from output port 206 and the difference in voltage between V(VIL) and V(VIH) introduce a Schmidt trigger-like hysteresis into the input switching threshold voltage levels. This improves input noise immunity and output switching speeds. Table 2 is the truth table depicting the operation of voltage level shifter 200.
TABLE 2______________________________________Voltage Level Shifter 200 Truth TableIN OUT______________________________________V(IN) < V(VIL) 0V(IN) > V(VIH) 1V(VIL) < V(IN) < V(VIH) Last State______________________________________
It should be noted that digital output port 206 can be designed to switch between any two voltage levels. In the preferred embodiment, the high and low voltage levels are selected to match the operating voltages of the device or devices connected to digital output port 206. Such devices include a printed circuit board or a core of an integrated circuit. V(VIL) and V(VIH) can be set by the user to match that of any digital logic family and can be changed at anytime.
FIG. 2 schematically depicts a voltage level shifter 300 having user-definable output drive and clamp voltage levels. In the preferred embodiment, level shifter 300 is comprised of a first voltage operational amplifier 317, a second voltage operational amplifier 318, a first 2:1 analog multiplexer 310 to a second 2:1 analog multiplexer 311, a first AND gate 308, a second AND gate 309, an inverter gate 303, a p-channel transistor 320, an n-channel transistor 322, a first resistor 312, a second resistor 316, a first capacitor 313, a second capacitor 315, a power connection 319, a ground connection 314, a VCL (voltage clamp low) analog input port 305, a VOL (voltage output low) analog input port 306, a VOH (voltage output high) analog input port 304, a VCH (voltage clamp high) analog input port 307, an IN (input) digital input port 301, an EN (enable) digital input port 302 and an OUT (output) digital output port 321.
Herein, user-defined voltages VOL, VOH, VCL and VCH are referred to as reference voltages. V(VCL), V(VOL), V(VOH) and V(VCH) can be set by the user to match those of any logic family as described in Table 5. In this invention, the voltages can be changed depending on the application.
The first input of multiplexer 311 is connected to VCH input port 307, while the second input is connected to VOL input port 306. The first input of multiplexer 310 is connected to VCL input port 305, while the second input is connected to VOH input port 304. The output of multiplexer 310 is connected through a first R-C low-pass filter, comprised of resistor 312 and capacitor 313, to the negative (-) input of op amp 317. The output of multiplexer 311 is connected through a second R-C low-pass filter, comprised of resistor 316 and capacitor 315, to the negative (-) input of op amp 318. Capacitors 313 and 315 are referenced to ground 314. The output of op amp 318 is connected to the gate of n-channel transistor 322. The output of op amp 317 is connected to the gate of p-channel transistor 320. The drains of both n-channel transistor 322 and p-channel transistor 320, the positive (+) input of op amps 317 and 318, and output port 321 are electrically connected. The source of p-channel transistor 320 is connected to power 3 19. The source of n-channel transistor 322 is connected to ground 3 14. IN input port 301 is connected to the first input of AND gate 308 and to the input of inverter gate 303. The output of inverter gate 303 is connected to the first input of AND gate 309. EN input port 302 is connected to the second input of AND gates 308 and 309. The output of AND gate 309 is connected to the select input of multiplexer 311. The output of AND gate 308 is connected to the select input of multiplexer 310. One skilled in the art will recognize that the select input of multiplexers 310 and 311 and the inputs and output of AND gates 308 and 309 and inverter gate 303 can be designed to be compatible with any number of standard logic voltage levels.
In the preferred embodiment, digital data is applied to IN input port 301 and EN input port 302, while user-defined reference voltages are applied to VCL input port 305, VOL input port 306, VOH input port 304 and VCH input port 307, such that V(VCL)<V(VOL)<V(VOH)<V(VCH). Voltage level shifter 300 uses voltage feedback and amplification to drive or clamp the voltage at output port 321 to the reference voltages selected by the multiplexers 310 and 311. The digital logic levels applied to IN input port 301 and EN input port 302 select the logic state (tristate, low or high) applied at OUT output port 321. V(VCL) and V(VCH) directly define the low and high output clamp voltages at OUT output port 321. V(VOL) and V(VOH) directly define the low and high output drive voltages at OUT output port 321.
When V(EN) is a logic low, V(VCL) is connected through multiplexer 310 and the first R-C low pass filter to the negative (-) input of the op amp 317, and V(VCH) is connected through multiplexer 311 and the second R-C low pass filter to the negative (-) input of op amp 318. If V(VCL)<V(OUT)<V(VCH), the output of op amp 317 is high and the output of op amp 318 is low and transistors 320 and 322 are both off. If V(OUT)<V(VCL), the output of op amp 317 goes low which turns on p-channel transistor 320 until V(OUT)>V(VCL). If V(OUT)>V(VCH), the output of op amp 318 goes high, which turns on n-channel transistor 322 until V(OUT)<V(VCH). Thus, voltage level shifter 300 presents a high impedance at OUT output port 321 for V(VCL)<V(OUT)<V(VCH) and clamps V(OUT) between V(VCL) and V(VCH).
When V(EN) is a logic high and V(IN) is a logic low, V(VCL) is connected through multiplexer 310 and the first R-C low pass filter to the negative (-) input of op amp 317, and V(VOL) is connected through multiplexer 311 and the second R-C low pass filter to the negative (-) input of op amp 318. If V(VCL)<V(OUT)<V(VOL), the output of op amp 317 is high and the output of op amp 318 is low and output transistors 320 and 322 are both off. If V(OUT)<V(VCL), the output of op amp 317 goes low which turns on p-channel transistor 320 until V(OUT)>V(VCL). If V(OUT)>V(VOL), the output of op amp 318 goes high which turns on n-channel transistor 322 until V(OUT)<V(VOL). Thus, voltage level shifter 300 drives V(OUT) to a logic low and then clamps V(OUT) between V(VOL) and V(VCL).
When V(EN) is a logic high and V(IN) is a logic high, V(VOH) is connected through multiplexer 310 and the first R-C low pass filter to the negative (-) input of op amp 317, and V(VCH) is connected through multiplexer 311 and the second R-C low pass filter to the negative (-) input of op amp 318. If V(VOH)<V(OUT)<V(VCH), the output of op amp 317 is high and the output of op amp 318 is low and both output transistors 320 and 322 are off. If V(OUT)<V(VOH), the output of op amp 317 goes low which turns on p-channel transistor 320 until V(OUT)>V(VOH). If V(OUT)>V(VCH), the output of op amp 318 goes high which turns on n-channel (or npn) transistor 322 until V(OUT)<V(VCH). Thus, voltage level shifter 300 drives V(OUT) to a logic high and then clamps V(OUT) between V(VOH) and V(VCH).
The first and second R-C low-pass filters limit the rate of the reference voltage change at the negative (-) inputs of op amps 317 and 318, respectively. This limits the voltage slew rate at OUT output port 321. The high speed feedback loop from OUT output port 321 to the positive (+) input of the op amps 317 and 318 provides for fast output voltage regulation independent of the R-C voltage slew rate control. It should be noted that resistor 312 and 316 must not be so large as to affect the drive input to op amps 317 and 318, respectively. In most situations, this will not be a problem, as op amps 317 and 318 will typically have a high input impedance.
Table 3 is the truth table for the output path of voltage level shifter 300 from IN input port 301 and EN input port 302 to OUT output port 321.
TABLE 3______________________________________Voltage Level Shifter 300 Truth TableIN EN OUT______________________________________0 0 V(VCL) < V(OUT) < V(VCH)0 1 V(VCL) < V(OUT) < V(VOL)1 0 V(VCL) < V(OUT) < V(VCH)1 1 V(VOH) < V(OUT) < V(VCH)______________________________________
It should be noted that inverter 303 ensures that transistors 320 and 322 are not on at the same time. Furthermore, one skilled in the art will recognize that other circuitry configurations can be used consistent with the teachings of this invention. Particularly, CMOS transistors 320 and 322 can be replaced with corresponding bi-polar components. Furthermore, other circuitry can be utilized to replace inverter 303, AND gates 308 and 309, multiplexers 310 and 311, resistors 312 and 3 16, and capacitors 3 13 and 315 so long as op-amps 317 and 318 are provided signals in substantially the same manner as described above.
FIG. 3 schematically depicts the preferred embodiment of a bi-directional voltage level shifter 400 with user-definable input switching and output drive and clamp voltage levels. It should be noted that components having the same function as described in the previous figures have retained the same numerical identification.
In the preferred embodiment, bi-directional voltage level shifter 400 is comprised of a voltage level shifter 200 described in FIG. 1 and a voltage level shifter 300 described in FIG. 2. IN input port 201 of voltage level shifter 200 is connected to OUT output port 321 of voltage level shifter 300. Thus, output port 321 functions as a bi-directional (I/O)port.
Digital data is applied to IN input port 301 and EN input port 302, while the user-defined dc reference voltages are applied to VCL input port 305, VOL input port 306, VIL input port 202, VIH input port 203, VOH input port 304 and VCH input port 307, such that V(VCL)<V(VOL)<V(VIL)<V(VIH)<V(VOH)<V(VCH). Bi-directional voltage level shifter 400 uses voltage feedback and amplification to drive or clamp the voltage at bi-directional port 323 to the reference voltages selected by the multiplexers 310 and 311. The digital logic levels applied to IN input port 301 and EN input port 302 select the logic state (tristate, low or high) applied at IO bi-directional port 323. V(VCL) and V(VCH) directly define the low and high output clamp voltages at IO bi-directional port 323. V(VOL) and V(VOH) directly define the low and high output drive voltages at IO bi-directional port 323. V(VIL) and V(VIH) directly define the low and high input switching threshold voltage levels of comparator 205 relative to V(IO). Table 4a is the truth table depicting the operation of the bi-directional voltage level shifter 400 input path from bi-directional port 323 to OUT output port 321. Table 4b is the truth table depicting the operation of bi-directional voltage level shifter 400 from IN input port 301 and EN input port 302 to bi-directional port 323.
TABLE 4a______________________________________Bi-directional Voltage Level Shifter Input Truth TableIO OUT______________________________________V(IO) < V(VIL) 0V(IO) > V(VIH) 1V(VIL) < V(IO) < V(VIH) Last______________________________________
TABLE 4b______________________________________Bi-directional Voltage Level Shifter Output Truth TableIN EN IO______________________________________0 0 V(VCL) < V(IO) < V(VCH)0 1 V(VCL) < V(IO) < V(VOL)1 0 V(VCL) < V(IO) < V(VCH)1 1 V(VOH) < V(IO) < V(VCH)______________________________________
Table 5 depicts the preferred voltage levels for VIL, VIH, VOL, VOH, VCL and VCH for the present invention as they relate to standard backplane specifications. In the preferred embodiment, VCL is selected to be approximately 0.5 volts less than VIL when VCH is selected to be approximately 0.5 volts above VOH. It should be noted, however, that a voltage range from 0.5 to 0.7 volts above VOL or above VOH can be utilized without degrading performance.
TABLE 5______________________________________Preferred Voltage Levels for VIL, VIH, VOL, VOH, VCL,VCH Input Output Threshold Drive ClampBackplane Voltage Voltage VoltageSpecification Levels Levels LevelsName VIL VIH VOL VOH VCL VCH______________________________________Backplane Trans- 1.475 1.625 1.100 2.100 0.600 2.600ceiver Logic (BTL)Center-Tapped 1.300 1.700 1.100 1.900 0.600 2.100Termination (CTT)Enhanced Trans- 1.400 1.600 0.400 2.400 -0.100 2.900ceiver Logic (ETL)Gunning Trans- 0.750 0.850 0.400 1.200 -0.100 1.700ceiver Logic (GTL)Kuo Transceiver 0.950 1.050 0.600 1.400 0.100 1.900Logic (KTL)Lipp Transceiver 1.700 2.100 0.000 3.300 -0.500 3.800Logic (LTL)Low Voltage Swing 0.475 1.625 1.100 2.100 0.600 2.600CMOS (LVSC)Low Voltage TTL 0.800 2.000 0.400 2.400 -0.100 2.900(LVTTL)______________________________________
Although the present invention has been described with reference to preferred embodiments, those skilled in the art will recognize changes that may be made in form or detail without departing from the spirit and scope of the invention. For example, the reference voltages VIL, VIH, VOL, VOH, VCL and VCH can be derived directly from a single reference voltage or system power supply by using a simple resistor ladder widely known in the art. In such a configuration, the reference voltages will track the supply or reference voltage from which they are derived. This allows all reference voltages to be altered simultaneously by changing the supply voltage. One skilled in the art will recognize that this would be particularly advantageous for level shifters that are designed to be used with several different backplane specifications. Such a device could have the voltage reference input parts connected to a different power supply depending upon which specification is in use. It should also be noted that the reference voltages can be altered individually by connecting each to a single supply voltage.
It should also be noted that several level shifters constructed in accordance with the present invention could be used on a data bus having a plurality of data lines. In such a configuration, each level shifter's enable terminal could be tied to a single terminal. Likewise, each of the reference voltages could also be tied together, thus allowing the voltage shifters to remain matched.
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A voltage level shifter is disclosed having an input and an output. The input receives a first signal capable of fluctuating between at least two voltages. The voltage level shifter produces a second signal, at the output, based on the voltage of the input signal and two or more user-defined reference voltages.
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CROSS REFERENCE TO RELATED APPLICATION
This application is based upon and claims the benefit of priority from the prior Japanese application No. 2002-49125, filed on Feb. 26, 2002; the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a semiconductor integrated circuit comprised of a plurality of transistors in combination, and more particularly, it relates to an improved technology for reduced power consumption and accelerated signal transmission rate.
To attain acceleration of a reduced power consumption complementary metal oxide semiconductor (CMOS) logic circuit, it is required that the circuit is comprised of low threshold voltage transistors. However, there arises a problem that as a threshold voltage in the transistors is reduced, leak current during standby state is increased.
An improved multiple threshold voltage CMOS circuit (MT-CMOS circuit) has been proposed which effectively avoids this problem and is capable of attaining accelerated circuit operation and reduced leak current during standby state simultaneously.
FIG. 10 is a circuit diagram showing the prior art MT-CMOS circuit. The circuit in FIG. 10 is comprised of a virtual power supply line VDD 1 connected to a power supply line VDD with an intervening high threshold voltage transistor Q 1 , and a virtual ground line VSS 1 connected to a ground line VSS with an intervening low threshold voltage transistor Q 2 .
A low-Vth block 100 , which has low threshold voltage transistors, is connected between the virtual power supply line VDD 1 and the virtual ground line VSS 1 .
The low-Vth block 100 functions as an OR circuit, for example, and includes two P channel MOS transistors Q 3 and Q 4 which receive input signals IN 1 and IN 2 from respective gate electrodes thereof, and are connected in parallel between the virtual power supply line VDD 1 and a node N, and two N channel MOS transistors Q 5 and Q 6 which similarly receive input signals IN 1 and IN 2 from respective gate electrodes thereof and are connected in series between the virtual power supply line VSS 1 and the node N. Also, connected to the node N is an inverter comprised of a P channel transistor Q 7 and an N channel transistor Q 8 connected in series and having their respective gates connected to the node N in common.
Operation of the circuit will be detailed below.
During an operation (when the circuit is activated), both the transistors Q 1 and Q 2 are turned on to supply the low-Vth block 100 with supply voltage. The low-Vth block 100 operates at high speed since it is comprised of low threshold voltage transistors.
On the contrary, during a standby state, both the transistors Q 1 and Q 2 are turned off to break a leak path from the power supply line VDD to the ground line VSS, and hence, leak current is reduced.
In such a method, however, amounts of current supplied during the operation from the power supply line VDD to the virtual power supply line VDD 1 and from the virtual ground line VSS 1 to the ground line VSS depend upon a resistance (ON-resistance) at the activated high threshold voltage transistors Q 1 and Q 2 . Thus, the ON-resistance should be reduced to attain an acceleration of the operation. For that purpose, it is required to enlarge gate widths of the high threshold voltage transistors Q 1 and Q 2 , and this leads to an adverse effect of an increase in a chip area.
SUMMARY OF THE INVENTION
According to an embodiment of the present invention, there is provided a semiconductor integrated circuit, comprising:
a first reference voltage line;
a second reference voltage line;
a plurality of single logic circuits each including a plurality of transistors;
a first switch having a first transistor provided between said first reference voltage line and said logic circuits, said first transistor having a higher threshold voltage than that of transistors in the logic circuits; and
a second switch having a second transistor provided a between said second transistor having a higher threshold voltage than that of transistors in the logic circuits,
said first and second switches being turned on when at least one of said single logic circuits is in operation, while said first and second switches being turned off when all of said single logic circuits are in standby state.
According to further embodiment of the present invention, there is provided a semiconductor integrated circuit, comprising:
a first reference voltage line;
a second reference voltage line;
a plurality of single logic circuits each comprised of combined transistors having first and second virtual power supply lines;
a first shared switch interposed between said first reference voltage line and said first virtual power supply line for the single logic circuits, the first shared switch being a transistor having higher threshold voltage than that of the transistors of said single logic circuits; and
a second shared switch interposed between the second reference voltage line and the second virtual power supply line for the single logic circuits, the second shared switch being a transistor having higher threshold voltage than that of the transistors of said single logic circuits;
said first and second shared switches being turned on when at least one of said single logic circuits is in operation, while said first and second shared switches being turned off when all of said single logic circuits are in standby state.
According to still further embodiment of the present invention, there is provided a semiconductor integrated circuit, comprising:
a first reference voltage line;
a second reference voltage line;
a plurality of single logic circuits each comprised of transistors having first and second virtual power supply lines;
a first shared switch interposed between the first reference voltage line and the first virtual power supply line for the single logic circuits, the first shared switch being a transistor higher in threshold voltage than the transistors of the single logic circuits; and
a second shared switch interposed between the second reference voltage line and the second virtual power supply line for the single logic circuits, the second shared switch being a transistor higher in threshold voltage than the transistors of the single logic circuits,
said at least one of the single logic circuits is in a transition state, no transition of the output voltage being developed in the remaining single logic circuits.
According to further embodiment of the present invention, there is provided a semiconductor integrated circuit, comprising:
a first reference voltage line;
a second reference voltage line;
a plurality of single logic circuits each comprised of transistors in combination having first and second virtual power supply lines, the single logic circuits being segmented into three or more groups;
a first shared switch interposed between the first reference voltage line and the first virtual power supply line for the single logic circuits in odd-numbered segments, the first shared switch being a transistor higher in threshold voltage than the transistors of the single logic circuits; and
a second shared switch interposed between the second reference voltage line and the second virtual power supply line for the single logic circuits in the odd-numbered segments, the second shared switch being a transistor higher in threshold voltage than the transistors of the single logic circuits,
the single logic circuits in even numbered segments being capable of delaying transition of output voltage so that output voltages from the single logic circuits in the odd numbered segments would not simultaneously be in a sate of transition.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a circuit diagram showing a first embodiment of a semiconductor integrated circuit according to the present invention;
FIG. 2 depicts an exemplary MT gate cell for gate circuitry in FIG. 1;
FIG. 3 is a circuit diagram showing the first embodiment of the semiconductor integrated circuit according to the present invention;
FIG. 4 depicts an exemplary circuit of the first embodiment of the semiconductor integrated circuit according to the present invention;
FIGS. 5A to 5 H are diagrams showing a time-varying voltage or current at the circuit in FIG. 4;
FIG. 6 is a circuit diagram showing a second embodiment of the semiconductor integrated circuit according to the present invention;
FIG. 7 is a circuit diagram showing the second embodiment of the semiconductor integrated circuit according to the present invention;
FIG. 8 is a circuit diagram showing a third embodiment of the semiconductor integrated circuit according to the present invention;
FIG. 9 is an exemplary MT gate cell for gate circuitry in FIG. 8; and
FIG. 10 is a circuit diagram showing a prior art MT-CMOS.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of semiconductor integrated circuits according to the present invention will be described with reference to the attached drawings.
In embodiments disclosed below, a semiconductor integrated circuit is designed in a configuration where most of its gate circuits consist of high threshold voltage transistors while only part of them consist of high and low threshold voltage transistors in combination, which is called “selective multiple threshold voltage complementary metal oxide semiconductor (SMT-CMOS) circuit”, and this SMT-CMOS is advantageous in an acceleration of signal transmission and a reduction of power consumption. Hereinafter, gate circuitry configured of high threshold voltage transistors (serving as switches) and low threshold voltage transistors in combination is termed “MT gate cell”.
First Embodiment
A first embodiment of the present invention will be described with reference to FIGS. 1 to 5 . A circuit in FIG. 1 includes gate circuitry 1 in a design where part of the circuitry on a critical path are comprised of relatively low threshold voltage transistors and relatively high threshold voltage transistors (switches) in combination to serve as gate cells or MT gate cells, and the remaining part of the gate circuitry is comprised of relatively high threshold voltage transistors.
Referring to FIG. 1, MT gate cells 2 on the critical path are hatched. Each of the hatched MT gate cells 2 is under control of a control circuit 3 that uses the relatively high threshold voltage transistors (serving as switches) to switch between supply and break of supply voltage to gate cells (serving as single logic circuits) of the relatively low threshold transistors. The control circuit 3 control ON-OFF state of the power supply transistors within the MT gate cells.
As shown in FIG. 1, since the gate cells on the critical path are replaced with the MT gate cells 2 within the gate circuitry 1 , signal transmission on the critical path can be accelerated. The remaining part of the circuitry is comprised of high threshold voltage transistors, and this brings about a precise control of leak current during operation.
An example of the MT gate cells 2 for the gate circuitry 1 is shown in FIG. 2 . The circuitry in FIG. 2 includes a NAND circuit 4 having low threshold voltage transistors Q 3 to Q 6 connected between a virtual power supply line VDD 1 and a virtual ground line VSS 1 , and transistors Q 1 and Q 2 functioning to switch between supply and break of supply voltage to the NAND circuit 4 . The transistor Q 1 is interposed between a power supply line VDD and the virtual power supply line VDD 1 while the transistor Q 2 is interposed between a ground line VSS and the virtual ground line VSS 1 , and both of the transistors are high threshold voltage transistors serving as switches, respectively.
In the circuitry in FIG. 2, as the transistors Q 1 and Q 2 are turned on, supply voltage is applied to the NAND circuit 4 , and the circuit operates at high speed because it operates with low threshold voltage. On the contrary, as the transistors Q 1 and Q 2 are turned off, the leak path of the NAND circuit 4 will be broken so as to reduce leak current. The MT gate cell configuration can be applied to any single logic circuit as well as the NAND circuit as described in conjunction with FIG. 2 .
The circuit shown in FIG. 3 is an exemplary circuit in which the MT gate cells and standard cells randomly arranged along the critical path in the gate circuitry 1 .
In this case, a plurality of gate cells (single logic circuits) are connected in series between flip-flops 6 . Hatched ones of the gate cells (single logic circuits), 5 a , represent gate cells (single logic circuits) having low threshold voltage transistors connected with the virtual power supply line VDD 1 and the virtual ground line VSS 1 while the remaining ones of the gate cells, 5 b , are comprised of high threshold voltage transistors.
Two of those cells which have low threshold voltage transistors, M 1 and M 3 , include shared high threshold voltage transistors (switches) 7 a and 7 b interposed between the virtual power supply line VDD 1 and the power supply line VDD and between the virtual ground lines VSS 1 and the ground line VSS, respectively. Another pair of the cells which have low threshold voltage transistors, M 2 and M 4 , are similarly connected to both the virtual power supply line VDD 1 and the virtual ground line VSS 1 which are connected to the power supply line VDD and the ground line VSS, respectively, with interposing high threshold voltage transistors (switches) 8 a and 8 b shared between the cells. The cell M 1 combined with the cell M 3 and the cell M 2 combined with the cell M 4 are cell pairs that show transition of output voltage “at different timing” from each other. Such transition “at different timing” means a relative state of the cell pairs of which output voltage transition would not occur simultaneously or at approximate timing.
FIG. 4 depicts an example of the circuitry in FIG. 3, having inverters connected in series.
FIGS. 5A to 5 H are time-varying levels of output voltage or pass-through current from the power supply to the ground in the circuitry in FIG. 4 . During transition of the output voltage or while the pass-through current occurs, the cell is in a transition state, varying from one phase to another, but at constant output voltage or with almost zero pass-through current, the cell is in a stationary state.
Referring to the drawings in an alphabetical order from FIG. 5A to FIG. 5H, it is obvious that the transition of the output voltage or the occurrence of the pass-through current successively propagates from the leftmost cell M 11 toward the rightmost cell M 18 . In other words, the transition state starting from the leftmost cell M 11 is serially followed toward the rightmost cell M 18 .
During the transition of the output voltage in the cell M 11 , the cell M 12 is also turned to a transition state at tight timing, and this situation is expressed like “the cell M 11 and the cell M 12 are in a transition state simultaneous with each other.” During the transition of the output voltage in the cell M 11 , the cell M 13 is not in a transition state, but almost simultaneous with cell's (M 11 ) turning from its transition state to a stationary state, the cell M 13 turns to a transition state. This relation of the cell M 11 with the cell M 13 can be expressed like “they are in a transition state, respectively, at close timing.”
In this embodiment, the cells “in a transition state at different timing” as mentioned above must have shared switches. As can be perceived in a relation of the cell M 11 with the cell M 15 , the cell M 15 is always in a stationary state during the transition of the output voltage in the cell M 11 , and reversely, the cell M 11 is in a stationary state during the transition of the output voltage in the cell M 15 .
An analyzation of the timing as in the above will be helpful in distinguishing the first segment of the cells M 11 and M 12 , the second segment of the cells M 13 and M 14 , the third segment of the cells M 15 and M 16 , and the fourth segment of the cells M 17 and M 18 , from one another. The cells in the first and third segments, and the cells in the second and fourth segments can respectively share the high threshold voltage transistors (switches) with each other. It is also certain that the cells in the first and fourth segments can share the high threshold voltage transistors (switches) with each other.
When two of the cells that develop transition of the output voltage simultaneously or at approximate timing are supplied with power through the single shared transistor, a potential at the virtual power supply line VDD 1 for the cells varies due to the transition of the output voltage in both the cells and would never be fixed depending upon a single factor or component. On the contrary, as for two of the cells that develop transition of the output voltage at different timing, the transition of the output voltage in one cell means a stationary state of the other without exception. Thus, in the latter case, it is ensured that only one cell is supplied with power, and the potential at the virtual power supply lien VDD 1 for the cells is fixed depending upon the single factor or component.
As has been recognized, for two of the MT gate cells, the single pair of the high threshold voltage transistors can serve as shared switches for power supply, and this brings about a reduction of the number of devices, which in turn leads to a decrease in a required chip area. The cells sharing the same switches are not limited to two in number but may be three or more.
Embodiment 2
A second embodiment of the present invention will be described in detail in conjunction with FIG. 6. A decoder circuit 9 has its output terminals to which cells (single logic circuits) M 21 to M 2 n are respectively connected. All the gate cells M 21 to M 2 n are respectively comprised low threshold voltage transistors that are connected to a virtual power supply line VDD 1 and a virtual ground line VSS 1 . The virtual power supply lines VDD 1 connected to the gate cells (single logic circuits) M 21 to M 2 n are commonly connected to a drain terminal of a high threshold voltage transistor 10 a serving as a switch. The source of the transistor 10 a is connected to power supply line VDD. The virtual power ground lines VSS 1 connected to the gate cells (single logic circuits) M 21 to M 2 n are commonly connected to a source terminal of a high threshold voltage transistor 10 b serving as a switch. The drain of the transistor 10 b is connected to ground power supply line VSS.
Another high threshold voltage transistor 10 b serving as a switch has its source connected to the gate cells M 21 to M 2 n in common through the virtual ground line VSS 1 , and has its drain grounded.
The operation of this embodiment will now be explained.
Merely the gate cell (single logic circuits) that receives an output signal from the decoder circuit 9 will be turned to a transition state while the remaining gate cells that do not receive the output signal maintain their stationary state. Thus, power is supplied to the virtual power supply line VDD 1 from the power supply line VDD and to the virtual ground line VSS 1 from the ground line VSS while the remaining gate cells would not supplied with power from the power line VDD and the ground line VSS. Thus, the plurality of the gate cells M 21 to M 2 n can share the single pair of the switches, and this leads to a reduction of a chip area.
This embodiment can be applied to circuitry as shown in FIG. 7, which has a bus line 11 and a plurality of bus drivers (single logic circuits) M 31 to M 3 n connected to the bus line 11 . These bus drivers M 31 to M 3 n are respectively comprised of low threshold voltage transistors connected to a virtual power supply line VDD 1 and a virtual ground line VSS 1 , respectively. A high threshold voltage transistor 12 a serving as a switch has its drain connected to the bus drivers (single logic circuits) M 31 to M 3 n in common through the virtual power supply line VDD 1 , and has its source connected to a power supply line VDD. Another high threshold voltage transistor 12 b serving as a switch has its drain connected to the bus drivers M 31 to M 3 n in common through the virtual ground line VSS 1 , and has its source grounded.
Among the bus drivers M 31 to M 3 n connected on the single bus line 11 , only selected one of them is turned to a transition state while the remaining bus drivers maintain themselves in a stationary state, so that signals to and from the bus drivers M 31 to M 3 n can be prevented from colliding on the bus line 11 .
Each of the bus drivers (single logic circuits) M 31 to M 3 n has low threshold voltage transistors connected to the virtual power supply line VDD 1 and the virtual ground line VSS 1 . A high threshold voltage transistor 12 a serving as a switch has its drain connected to the bus drivers M 31 to M 3 n in common through the virtual power supply line VDD 1 , and its source connected to the power supply line VDD. Another high threshold voltage transistor 12 b serving as a switch has its source connected to the bus drivers M 31 to M 3 n in common through the virtual ground line VSS 1 , and has its drain grounded.
Only selected one of the bus drivers (single logic circuits) M 31 to M 3 n is supplied with power through the virtual power supply line VDD 1 and the virtual ground line VSS 1 from the power supply line VDD and the ground line VSS while the remaining bus drivers would not be supplied with power from the power supply line VDD and the ground line VSS. As has been described, in the circuitry of the bus line 11 and the bus drivers M 31 to M 3 n in FIG. 7, the plurality of the bas drivers M 31 to M 3 n can share the single pair of the switches 12 a and 12 b , and this brings about a reduction of a chip area.
Embodiment 3
A third embodiment of the present invention will be described in conjunction with FIG. 8 . Circuitry in FIG. 8 has two flip-flops 16 on a critical path and a plurality of gate cells (single logic circuits) 13 connected in series between them. The hatched gate cells are single stage gate inverting logic circuits that have low threshold voltage transistors connected to a virtual power supply line VDD 1 and a virtual ground line VSS 1 . Gate cells 14 and 15 , which are the single stage gate inverting logic circuits juxtaposed with each other, can share a pair of high threshold voltage transistors (switches) interposed between the virtual power supply line VDD 1 and a power supply line VDD and between the virtual ground line VSS 1 and a ground line VSS, respectively.
FIG. 9 is an embodied circuit diagram of one application where the juxtaposed gate cells (single stage gate inverting circuits) 14 and 15 in FIG. 8 function to be inverter circuits. The gate cell 14 , when receiving a high-level voltage at an input terminal, has its PMOS transistor M 41 turned off and its NMOS transistor M 42 turned on, respectively. Thus, the gate cell 14 produces a low-level voltage from an output terminal while the gate cell 15 receives the low-level voltage at an input terminal. The gate cell 15 has its PMOS transistor M 43 turned on and its NMOS transistor M 44 turned off.
Thus, the PMOS transistors M 41 and M 43 of the gate cells (single stage gate inverting logic circuits) 14 and 15 would never turn on simultaneous with each other or at approximate timing, and neither would do the NMOS transistors M 42 and M 44 of the gate cells 14 and 15 . In this way, potential variations at nodes with the switches can be determined uniquely, it is certain that the gate cells can share the switches. This brings about a reduction of the number of the high threshold voltage transistors serving as the switches, and eventually, a chip area can be reduced.
Although, in the above-mentioned embodiments, the cells on the single critical path are addressed, the present invention can be effected in an application where the cells on the different critical paths share the switches.
As has been described, in accordance with the embodiments of the present invention, a design of the shared switches of the plurality of the MT gate cells contributes to an implementation of a semiconductor integrated circuit where, without an increase in a chip area, accelerated operation and reduced leak current can be accomplished.
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A semiconductor integrated circuit, comprises a first reference voltage line; a second reference voltage line;
a plurality of single logic circuits each including a plurality of transistors; a first switch having a first transistor provided between said first reference voltage line and said logic circuits, said first transistor having a higher threshold voltage than that of transistors in the logic circuits; and a second switch having a second transistor provided a between said second transistor having a higher threshold voltage than that of transistors in the logic circuits, said first and second switches being turned on when at least one of said single logic circuits is in operation, while said first and second switches being turned off when all of said single logic circuits are in standby state.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Design Application No. 29466535, filed Sep. 9, 2013 and Mexican Application No. MX/E/2014/092558, filed Dec. 19, 2014, which are hereby incorporated by reference, to the extent that they are not conflicting with the present application.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates generally to assembly systems and methods and more particularly to a non-penetrating assembly system and method using grooves and wedges.
[0004] 2. Description of the Related Art
[0005] With today's living spaces becoming smaller and storage space at a premium, the need for efficient use of those spaces has become more important. Additionally, with the costs of fuel and transportation increasing, it is ever more important to realize efficiencies in the shipping of goods. The less air shipped in a package the better.
[0006] Thus, there is a need for furniture (or other similar goods) of all kinds that use an innovative assembly system that allows the furniture to be easily assembled and disassembled multiple times so you can transport it or store it flat; to introduce or remove it in complicated and reduced current spaces; to lower the costs of transportation and storage; to make all of this easy without discrediting its aesthetic appearance and good functionality.
BRIEF SUMMARY OF THE INVENTION
[0007] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key aspects or essential aspects of the claimed subject matter. Moreover, this Summary is not intended for use as an aid in determining the scope of the claimed subject matter.
[0008] In one exemplary embodiment, an assembly system and method is provided that allows one to join for example two flat pieces at 90 degrees (perpendicular), without cutting all the way through the receiving piece, by simply using grooves and wedges. The unique feature of the system is the way in which the pieces are joined. No full penetration of a piece with the other, no glued parts or screws or nails, rivets or any metal clips.
[0009] Using the system and method disclosed herein, a strong and rigid assembly is accomplished by the use of grooves that are locked together and are secured by a wedge inserted into a recess with a ramp with an inclination of, for example, 5 degrees. This rigid assembly is achieved only with the use of grooves and wedges and in most cases requires only one wedge, so that you can easily assemble and disassemble pieces multiple times without damage or wear to the furniture.
[0010] The system and method disclosed may be used for furniture assembly to obtain economical, flat transport and storage, and easy installation that requires no hardware. It can be used for all kinds of furniture such as chairs, tables, benches, shelves, and so on. For example, it can be used to attach a table top with the table legs or any number of pieces of furniture where it is required to have a firm assembly without one of the surfaces being perforated completely by another.
[0011] The above embodiments and advantages, as well as other embodiments and advantages, will become apparent from the ensuing description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] For exemplification purposes, and not for limitation purposes, embodiments of the invention are illustrated in the figures of the accompanying drawings, in which:
[0013] FIG. 1 is an isometric view of a recess of a first assembly element, according to an embodiment.
[0014] FIG. 2 is a top view of the recess from FIG. 1 .
[0015] FIG. 3 is a cross section view of the recess from FIG. 2 along cutting plane A: A.
[0016] FIG. 4 is an isometric view of a second assembly element, according to an embodiment.
[0017] FIG. 5 is a top view of the front face of the second assembly element from FIG. 4 .
[0018] FIG. 6 is a cross section view of the second assembly element from FIG. 5 along cutting plane B: B.
[0019] FIGS. 7-9 illustrate the process of joining the first and the second assembly elements, according to an embodiment.
[0020] FIG. 10 is a top view of the assembly resulting from joining the first and the second assembly elements as depicted in FIGS. 7-9 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] What follows is a detailed description of the preferred embodiments of the invention in which the invention may be practiced. Reference will be made to the attached drawings, and the information included in the drawings is part of this detailed description. The specific preferred embodiments of the invention, which will be described herein, are presented for exemplification purposes, and not for limitation purposes. It should be understood that structural and/or logical modifications could be made by someone of ordinary skills in the art without departing from the scope of the invention. Therefore, the scope of the invention is defined by the accompanying claims and their equivalents.
[0022] Reference will now be made to FIGS. 1-3 . FIG. 1 is an isometric view of a recess of a first assembly element, according to an embodiment. FIG. 2 is a top view of the recess from FIG. 1 . FIG. 3 is a cross section view of the recess from FIG. 2 along cutting plane A: A.
[0023] As can be seen in FIGS. 1-3 , the recess 10 has a floor 15 , which is preferably flat, a straight edge of greater length 11 and, opposite to it, an edge 12 with a ramp 13 having a certain inclination 13 a (preferably 5 degrees). Preferably over its entire length, as shown, the longest straight edge 11 is preferably configured to have a fluting/undercut 16 . It should be noted that the undercut/fluting 16 creates a lip 14 extending inwards, as better seen in FIG. 3 .
[0024] It should be noted in FIG. 3 that some examples of dimensional relationships between elements of the recess 10 and a dimension (e.g., thickness) of the first assembly element 17 are provided. Again, these are examples only, thus other sizes for the recess 10 and its elements (e.g., lip 14 or fluting/undercut 16 ) may be adopted depending on such factors as the strength or thickness of the materials from which the first assembly element 17 is made (e.g., wood, aluminum, plastic, glass, etc.).
[0025] It should be observed that the recess 10 is formed into the first assembly element 17 such that it does not penetrate completely the first assembly element 17 . Because of that, the recess 10 has a floor 15 , and, while the recess 10 can be seen from one side 17 a of the first assembly element 17 , it cannot be seen from the opposite side 17 b, if the first assembly element 17 is made from an opaque material. This has significant advantages, such as to mask the joint created using recess 10 , when, for example the joint is used in a furniture piece. Another advantage is that floor 15 may contribute to the strength of the resulting joint, as it will be apparent from the below description referring to FIGS. 7-9 .
[0026] One of ordinary skill in the art would understand that various suitable processes may be adopted to form the recess 10 into the first assembly element 17 . The list of such processes may include cutting, carving, casting, and so on. Also, it should be noted that an overcut 80 ( FIG. 2 ) may be used to facilitate the insertion of the second assembly element 20 into the recess 10 .
[0027] One of ordinary skill in the art would further understand that the recess 10 could for example also be a structure associated with and/or extending from one of the faces (e.g., 17 a ) of the first assembly element 17 , thus not being embodied into the first assembly element 17 as preferred and depicted in FIG. 3 , while still fulfilling a similar function. Such variation and other similar variations would not depart from the scope of this disclosure.
[0028] Reference will now be made to FIGS. 4-6 . FIG. 4 is an isometric view of a second assembly element, according to an embodiment. FIG. 5 is a top view of the front face of the second assembly element from FIG. 4 . FIG. 6 is a cross section view of the second assembly element from FIG. 5 along cutting plane B: B.
[0029] The second assembly element 20 is the other piece that will form the assembly by joining with the first assembly element 10 , as it will be described in detail hereinafter when referring to FIGS. 7-10 . As shown, the second assembly element 20 may have a front face 21 and a back face 22 , and a longitudinal slot/groove 23 on its front face 21 and near the bottom 29 of the second assembly element 20 . As shown, the presence of the longitudinal slot/groove 23 creates a flange 24 between the bottom 29 and the longitudinal slot 23 of the second assembly element 20 .
[0030] The longitudinal slot/groove 23 of the second assembly element 20 is preferably shaped and sized to fit snugly over the lip 14 of the first assembly element 10 . The flange 24 is preferably shaped and sized to fit snugly into the fluting 16 of the first assembly element 10 .
[0031] As shown, the back face 22 has a shoulder 25 , which is preferably shaped and sized to receive snugly a portion of the wedge 30 (see FIG. 9 ), in order to lock the assembly, as it will be described hereinafter when referring to FIGS. 7-10 . Element 25 , prevents the wedge from falling out, should it loosen.
[0032] It should be noted that in FIGS. 5-6 some examples of dimensional relationships between elements of the second assembly element 20 are provided. Again, these are examples only, thus other sizes may be adopted depending on such factors as the strength of the material and the thickness from which the second assembly element 20 is made (e.g., wood, aluminum, plastic, glass, etc.).
[0033] Reference will now be made to FIGS. 7-10 . FIGS. 7-9 illustrate the process of joining the first and the second assembly elements, according to an embodiment. FIG. 10 is a top view of the assembly resulting from joining the first and the second assembly elements as depicted in FIGS. 7-9 .
[0034] FIG. 7 is an isometric view where the first step of the assembly process is shown. As shown, first, the second assembly element 20 is inserted into the recess 10 of the first assembly element 17 ( FIG. 3 ), such that preferably the bottom 29 of the second assembly element 20 touches the floor 15 of recess 10 . Next, as shown in FIG. 8 , the second assembly element is pushed to slide toward the straight edge of greater length 11 of recess 10 and until the lip 14 of the first assembly element 10 enters the longitudinal slot 23 (see FIG. 7 ) of the second assembly element 20 , and the flange 24 of the second assembly element 20 enter the fluting/undercut 16 of the first assembly element 10 . Next, as shown in FIG. 9 , for securing the assembly 40 of both pieces, a wedge 30 is inserted into the recess 10 between the recess 25 of the second assembly element 20 and the ramp 13 of recess 10 and pushed to slide (from left to right (B) in FIG. 9 ) to press hard enough onto the second assembly element 20 , to keep it in place and thus make the assembly 40 secure. As it can be seen in the top view in FIG. 10 , angle 13 a (e.g., 5 degrees) of ramp 13 corresponds and cooperates with the slope of the wedge 30 to create enough pressure to be introduced to second assembly element 20 . It should be also noted that recess 25 contributes to preventing the wedge 30 from escaping the construct. It should be noted as well that more than one wedge 30 may be used if the parts are configured appropriately.
[0035] Thus, it should be apparent that the system and method disclosed herein allows one to join for example two flat pieces of different or similar thicknesses at 90 degrees (perpendicular), without puncture or penetration, by simply using one or more wedges. The unique feature of the system is the way in which the pieces are joined. No full penetration of a piece with the other, no glued parts or screws or nails, rivets or any metal clips.
[0036] Using the system and method disclosed herein, a strong and rigid assembly may be accomplished by the use of grooves that are locked together and are secured by a wedge inserted in a recess with a ramp with an inclination of, for example, 5 degrees.
[0037] Again, the system and method disclosed herein may be used to assemble furniture. For example, the first assembly element 17 having the recess 10 may be the flat top of a table and the second assembly element 20 may be a leg or a leg set of the table. However, it should be understood that the system and method disclosed herein may also be used to assemble other items such as art pieces, toys, and so on.
[0038] It should be noted that a ninety degrees (perpendicular) joint was disclosed herein. However, it should be understood that a deviation from the perpendicular configuration (e.g., 95 degrees) may be adopted if needed, by correspondingly adjusting the surfaces of the interlocking elements described.
[0039] It may be advantageous to set forth definitions of certain words and phrases used in this patent document. The phrases “associated with” and “associated therewith,” as well as derivatives thereof, may mean to include, be included within, interconnect with, contain, be contained within, connect to or with, couple to or with, be communicable with, cooperate with, interweave, juxtapose, be proximate to, be bound to or with, have, have a property of, or the like.
[0040] As used in this application, “plurality” means two or more. A “set” of items may include one or more of such items. Whether in the written description or the claims, the terms “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of,” respectively, are closed or semi-closed transitional phrases with respect to claims. Use of ordinal terms such as “first,” “second,” “third,” etc., in the claims to modify a claim element does not by itself connote any priority, precedence or order of one claim element over another or the temporal order in which acts of a method are performed. These terms are used merely as labels to distinguish one claim element having a certain name from another element having the same name (but for use of the ordinal term) to distinguish the claim elements. As used in this application, “and/or” means that the listed items are alternatives, but the alternatives also include any combination of the listed items.
[0041] Throughout this description, the embodiments and examples shown should be considered as exemplars, rather than limitations on the apparatus and procedures disclosed or claimed. Although many of the examples involve specific combinations of method acts or system elements, it should be understood that those acts and those elements may be combined in other ways to accomplish the same objectives. With regard to flowcharts, additional and fewer steps may be taken, and the steps as shown may be combined or further refined to achieve the described methods. Acts, elements and features discussed only in connection with one embodiment are not intended to be excluded from a similar role in other embodiments.
[0042] Although specific embodiments have been illustrated and described herein for the purpose of disclosing the preferred embodiments, someone of ordinary skills in the art will easily detect alternate embodiments and/or equivalent variations, which may be capable of achieving the same results, and which may be substituted for the specific embodiments illustrated and described herein without departing from the scope of the invention. Therefore, the scope of this application is intended to cover alternate embodiments and/or equivalent variations of the specific embodiments illustrated and/or described herein. Hence, the scope of the invention is defined by the accompanying claims and their equivalents. Furthermore, each and every claim is incorporated as further disclosure into the specification and the claims are embodiment(s) of the invention.
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A method of attaching a first assembly element with a second assembly element comprising the steps of: inserting an end of the second assembly element having a groove into a recess associated with the first assembly element; causing the second assembly element to slide toward an edge of the recess having an undercut until the undercut engages the groove; and driving a wedge against a ramp of the recess and a face of the second assembly element which is opposite to the face having the groove.
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This application is a continuation of application Ser. No. 633,595, filed July 23, 1984, now abandoned.
The present invention relates to a latch needle for a knitting or textile machine, having a needle shank and a needle latch with a pivot bore which is supported in a longitudinal slot of the needle shank such as to pivot freely. In the closed position, the latch rests with its spoon on the needle hook, and in the open or rear position the latch spine rests on seating surfaces in the vicinity of the upper edge of the needle shank.
BACKGROUND
In high-speed textile machines, such as circular knitting machines, the needle latch is subjected to very great stresses. When the latch pivots between its closed position and its open or rear position with a frequency of up to 60 Hz and higher, as is usually the case at present, large forces of acceleration and deceleration arise at the needle latch. These forces not only stress needle latch by bending, but when the spoon strikes the hook or when the latch spine strikes the seating surfaces provided on the needle shank, considerably energies must be absorbed by resilient, elastic deformation and nullified by friction. As a consequence of these severe stresses, not only can the spoon and the hook be damaged, but the latch can also break, or damage can occur to the latch pivot and the needle shank.
It is known (U.S. Pat. No. 4,294,086, to which German Patent 27 14 607 corresponds) to dampen the impact of the needle latch in the rear position by means of a special arrangement of the longitudinal slot of the needle and thereby to avoid damage to the needle latch and the needle itself that might occur in the rear position of the latch. As a result of the cooperation between the needle shank side portions flanking the longitudinal slot of the needle and the wedge-shaped converging flanks of the seating surface on the latch spine, the side portions of the needle shank are spread apart elastically upon the impact of the needle latch, and at the same time friction is produced at the seating surfaces upon engagement with one another on the latch spine and the side portions of the needle shank. The overall result is that the needle latch is braked and damped. The elastic spreading of the needle shank side portions is limited, however, by the fact that the elasticity of the side portions of the shank decreases with increasing needle shank thickness.
Needles with pivoted blades, also known as Stelos point needles, are used for mending stockings or other knitted goods, see U.S. Pat. No. 2,596,311, Vitoux. In these needles, the forces of the pivoting blade acting on the hook are reduced by through- or penetrating holes or recesses, reduced thicknesses, or lightweight materials. In the Stelos point needles, the blade has a formed-on extension which is several times longer than the distance between the pivot and the hook, to project substantially beyond a nose which cooperates with the needle hook. Because this long extension end naturally places great stress on the needle latch, and in particular on that part of the latch which cooperates with the needle hook, it is formed with through-holes, or has an overall reduced wall thickness in comparison to the portion between the pivot and the hook, in order to reduce its weight. The blade of these Stelos point needles, which cannot be compared with standard knitting machine latch needles, is relatively massive and is not formed with a latch spoon.
THE INVENTION
It is an object of the present invention to devise a latch needle suitable particularly for high-speed knitting machines, in which the latch can absorb greater stresses than heretofore without the danger of damage to the needle latch or to other parts of the needle.
Briefly, the needle latch has at least one through opening in the area between its pivot bore and the spoon.
The inert mass of the needle latch is thereby decreased, so that the stress on the needle latch from the forces of acceleration and deceleration that occur is reduced and the impact energy when the spoon strikes the hook or the latch spine strikes the associated seating surfaces is reduced; further, the elastic flexing characteristics of the needle latch are simultaneously improved thereby, with the result that local peaks in stress that otherwise occur, particularly upon impact, are diminished. The latch needle is thus capable of absorbing the stresses arising over long periods in operation without the danger of damage to the needle latch or the latch pivot, even when used in very high-speed machines, such as circular knitting machines.
A form of embodiment which has provided to be very advantageous is one in which the through hole has a slit-like, elongated form; it may be wider in the vicinity of the bearing bore than in the vicinity of the spoon, so as to provide for adaptation to the somewhat wedge-shaped cross-sectional the needle latch. In another form of embodiment, the latch may also have a number of openings, e.g. circular holes located in a row and spaced from each other. It is suitable for the opening or openings to be disposed symmetrically with respect to the central longitudinal plane of the needle latch containing the bearing bore axis.
DRAWINGS
FIG. 1 is a fragmentary side view, partially in an axial section, of a latch needle according to the invention;
FIG. 2 is a side view of the latch needle of FIG. 1, in a section taken on the line II--II of FIG. 1;
FIG. 3 shows a latch needle according to the invention in a view corresponding to FIG. 1 but of another form of embodiment; and
FIG. 4 is a side view of the latch needle of FIG. 3, in a section taken on the line IV--IV of FIG. 3.
DETAILED DESCRIPTION
The latch needle shown in various forms of embodiment in the drawings has a needle shank 1 with a needle hook 2 disposed on its end. A longitudinal slot 3 is disposed in the needle shank 1 and is provided with a slit or aperture 4 leading to the lower edge of the needle shank, and a needle latch 5 is supported in the longitudinal slot 3 such that it pivots freely, i.e. undamped about a latch pivot 6. The latch pivot 6 is formed by two bearing tangs 7 extending out of the side portions laterally defining the longitudinal slot 3. The needle latch 5 is supported on the bearing tang 7 by means of a pivot bore 8. The needle latch 5 has a spoon 9 on one end. The spoon 9 just overlaps the tip of the needle hook 2 when it is in its closed position. In the rear or open position, it rests with seating surfaces, embodied on wedge-shaped convergent flanks of its spine, on seating surfaces 10 adapted to the shape of its spine which are located in the region of the upper edge of the side faces of the needle shank 1 defining the longitudinal slot 3. The rear position and the closed position of the needle latch are shown in dashed lines in FIGS. 1 and 3, respectively.
In accordance with the invention, the latch 5, in the region between the pivot bore 8 and the spool 9, is provided with at least one through opening, or hole, in all the forms of embodiment shown:
In the form of embodiment shown in FIGS. 1, 2, a through hole 11 of elongated, slit-like shape is provided in the needle latch 5 in the region shown. In the vicinity of the pivot bore 8, this recess 11 is wider than in the vicinity of the spoon 9, and with the adjacent side faces 12 of the needle latch 5, which in side view is somewhat wedge-shaped, it therefore defines thin ribs 13, which are joined to one another at the end by the material comprising the needle latch 5 and in turn effect a connection between the portion of the needle latch 5 containing the pivot bore 8 and the spoon 9 thereof.
The elongated opening, or recess, 11 not only effects a reduction of the inert mass of the needle latch 5 but also results in a favorably dynamic flexing behavior on the part of the needle latch.
The form of embodiment shown in FIGS. 3, 4 corresponds substantially to that of FIGS. 1, 2. Identical elements are therefore provided with the same reference numerals and need no further description.
In this form of embodiment of FIGS. 3, 4, the needle latch 5 is provided with a number of circular holes or apertures 19 in the region between the pivot bore 8 and the spoon 9. These apertures 19 are formed as cylindrical holes and are disposed spaced apart from one another in a row, with their axes located in the plane 18 containing the latch pivot 6. The circular holes 19 may have identical diameters, or else their diameters may become progressively smaller from the pivot bore 8 toward the spoon 9. Instead of the cross-sectional shape shown here, the holes 19 may also have a different shape, for instance oblong. It is also possible for them to be disposed not in one row, with their axes located in the common plane 18, but rather distributed over the associated side surfaces of the needle latch 5.
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To enable the latch (5) of a latch needle to be capable of absorbing greattresses without danger of damage to the needle latch, or to the needle itself, the latch has at least one through-aperture (11, 19) or opening in the region between its pivot bore (8) and the latch spoon (9).
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BACKGROUND OF INVENTION
This invention relates to a powder for plasma spray applications.
These powders require various agglomerations methods to make free flowing powders from normally non-flowing small particles. One such agglomeration method is spray drying. Agglomerates are formed in spray drying by atomizing a slurry of powder, binder and liquid into a drying chamber where the liquid is evaporated. The result is a generally spherical agglomerate held together by the binder. U.S. Pat. No. 3,617,358 describes an agglomeration process using an organic binder.
Other agglomeration processes have been developed to overcome what may be undesirable effects caused by the presence of organic binders. In some cases, the organic binder may cause fouling of the plasma gun due to vaporization of the organic. The presence of organics may even decrease the apparent density of the powder or affect the flame spray coating. In U.S. Pat. No. 3,881,911 to Cheney et al., the agglomerates are presintered to remove the binder. U.S. Pat. No. 3,973,948 to Laferty et al uses a water soluble ammonia complex as a binder and U.S. Pat. No. 4,025,334 to Cheney et al. uses an aqueous nitrate solution.
Because of their relatively large size and low surface area as compared with the original small particles which are often irregular in shape, the agglomerates have improved flow properties. However, the increased particle size and lower density resulting from agglomeration can be a disadvantage. Hence, plasma densification may be employed to produce spherical, dense, and homogeneous particles. According to this process, the agglomerated powder is entrained in a carrier gas and fed through a high temperature plasma reactor to melt the agglomerated particles. The melted particles are cooled to avoid coalescence so as to produce spherical dense particles. The use of the dense particle in flame spray applications can result in a dense, smooth coating which requires little or no finishing by grinding or machining as compared to coatings produced from the agglomerated particles. Further, the densified particles have improved flow characteristics which allow the use of a reduced volume of material leading to decreased processing time and improved efficiencies in plasma spraying. U.S. Pat. Nos. 3,909,241 and 3,974,245, both to Cheney et al., relate to such densification processes and the powders produced therefrom.
Tungsten carbide-cobalt powders are commonly used for hard surfacing as well as other applications. As a result of the potentially low availability and high cost of cobalt in relation to the demand, a need for substitutes exists.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a plasma spray powder consisting essentially of a metal selected from the group consisting of nickel, iron, cobalt, or mixtures and alloys thereof, with the balance being from about 50 to about 90 percent by weight tungsten and carbon, said tungsten and carbon being present in a one to one molar ratio and said nickel, iron, or mixture or alloy thereof, being present in a weight ratio of at least about 4 parts by weight to about one part by weight cobalt.
The resulting powders comprising tungsten carbide with iron or nickel substituted for at least a portion of the cobalt may be used as substitutes for powders consisting essentially of cobalt and tungsten carbide for many applications.
DETAILED DESCRIPTION
The powders of the present invention include iron or nickel as a substitute for at least a portion of cobalt. The weight ratio of cobalt to the nickel and iron combined is less than about 1 to about 4.
In some applications, nickel and iron may be a combined substitute. Since cobalt imparts the desirable properties of high temperature strength and oxidation resistance to the final coating, it is desirable to use a small proportion of cobalt in applications above 700° F. However, for low temperature applications the need for cobalt may be totally eliminated.
Due to the method of preparing the plasma spray powder of the present invention the powder particles may be dense. Although the individual particles may have compositions that vary from particle to particle, the overall composition of the powder is substantially uniform. The plasma densification of the particles preferably results in a prealloying of individual agglomerates to produce substantially homogeneous composite particles.
The plasma spray powder may be produced in two particle size ranges depending upon the desired final application technique. As a coarse powder the majority of the particles are within a -200+325 U.S. standard sieve particle size range.
As a fine plasma spray powder, it has a particle size distribution wherein at least 70 percent of the particles have a size less than 20 microns. Substantially all the particles pass through a 270 U.S. screen mesh. A typical particle size distribution has less than 10 percent of the particles below about 10 microns. The bulk density is from about 6 to about 7 grams/cc. Preferably, for the coarse powder distribution the Hall flow is within the range of from about 9 to 21 seconds/50 g. Powder with the fine particle size distribution does not flow.
In preparing the plasma spray powder of the present invention, a powder blend is prepared consisting essentially of the weight percent of components to give the desired final alloy powder composition. The powders are mixed by methods known in the art, such as by a blender, tumbler, or even, if size reduction is desired, by milling to obtain a suitable particle size. Preferably the overall powder blend has an average particle size less than about 10 microns.
The uniform power blend is next agglomerated by methods known in the art. For example, powder compacts can be formed and then crushed and screened to yield the desired particle size. Alternatively the powders can be mixed with a binder in the presence of moisture. However, agglomeration by spray drying is in general preferred for its flexibility and economy of operation on a production scale. The particular conditions under which the slurries are formed and spray dried are well known. U.S. Pat. No. 3,617,358, issued Nov. 2, 1971 describes formation of slurries. Other suitable methods for agglomerating are described in U.S. Pat. Nos. 3,881,911, 3,973,948 and 4,025,734 hereinafter discussed. The use of spray drying results in a close control over the size of the agglomerates. The blending technique results in a uniform mixture of the ingredients.
An alternative method of preparing the agglomerated particles is in a fluidized bed, such as a Glatt fluidized bed granulator. According to this method, a fine spray of liquid and soluble binder is introduced into the fluidized mixture of powders. One example of a liquid and binder system is water and polyethylene glycol. The gases passing through the fluidized bed which maintain the powders to be agglomerated in suspension are heated such that the liquids in the spray are evaporated. The fine particles in the fluidized bed then become bound together as larger agglomerates with the binder which remains after the evaporation.
The agglomerates may be conveniently classified to obtain a desired particle size distribution, for example it is generally desired to have at least 80% of the particles within a range of 50 micron average particle size.
The classified agglomerates are passed through a furnace at low temperatures to decompose the binders used for agglomeration and further treated at high temperatures to strengthen them for subsequent handling.
The sintered agglomerates can be subsequently screened to yield a particle size distribution suitable for creating plasma sprayed coatings. Typically these distributions fall within two ranges, -200 +325 mesh or -270 mesh. The coarser distribution powder typically contains 10% +200 and 10% -325 material. The finer distribution powder generally has a restriction on the percentage of ultra fine particles allowable, e.g. a maximum of 20% -20 μm.
Alternatively, the agglomerated and sintered particles can also be subsequently plasma densified so as to produce fine, spherical, densified particles. The densification process comprises entraining agglomerated powders in a carrier gas and feeding the entrained particles through a high temperature reactor. The particles pass through the reactor at such a flow rate that interparticle contact and coalescence are avoided but that at least the outer surfaces of the particles are melted. After melting, the particles fall through a distance sufficient to permit solidification and cooling prior to contact with a solid surface or each other.
Because the particles are melted while entrained in a carrier gas, the solidified particles are substantially spherical, have smooth surfaces and thus excellent flowability. In addition, the solidified particles have the same general size range as the starting material. However, depending on the porosity of the starting material, they may have a smaller mean particle size, due to densification during melting. Preferably the melting during densification is to such an extent that each particle becomes prealloyed, i.e., the metals (nickel and/or cobalt and/or iron) alloy together and achieve intimate contact with the densified carbide. Some solution of the constituents in one another may also take place. A major portion and preferably substantially all of the densified powder consists essentially of particles wherein each particle has a substantially uniform composition.
The plasma densification is preferably carried out in a plasma flame reactor. Details of the principles and operation of such plasma flame reactors are well known. The temperature within the plasma flame can be adjusted between 10,000° F. and 30,000° F. The temperature which the particles experience is a function of the rate at which they are fed through the reactor. Commercially available feeding devices allow rates between approximately 1/2 and 30 pounds per hour, depending on the bulk density of the material being fed. Conditions for plasma densification are established such that the particles reach a temperature at least above the melting point of the highest melting component and preferably below the vaporization point of the lowest vaporizing component.
The melted particles must be cooled at a rate sufficient to solidify at least an outer layer of the particles prior to their contact with a solid surface o with each other in order to maintain their sphericity and particle integrity. While any of several methods may be used to achieve this result, it has been found convenient to feed the melted particles into a liquid cooled chamber containing a gaseous atmosphere. The chamber may conveniently serve as a collection vessel.
After the powders have been plasma densified they can be classified to achieve the desired particle size distribution for use in plasma spray applications. Particle size distributions similar to those for the agglomerated and sintered particles are desired.
Alternatively, the plasma densified powders can be crushed and classified to yield a powder with a finer particle size distribution, preferably one for which all the particles pass through a 270-mesh U.S. screen and at least 60 percent of the particles are less than 20 microns in average diameter. A typical particle size distribution has less than 10 percent of the particles below about 5 microns. The bulk density is from about 5.5 to about 7.0 grams/cc.
EXAMPLE 1
A sintered agglomerated powder is prepared by blending nickel and iron powder, with a particle size less than approximately 10 micron with tungsten carbide (WC) powder of the same particle size in amounts sufficient to result in a blend comprising 12% of the nickel/iron and 88% tungsten carbide. The nickel/iron powder contains about a 1 to 1 ratio of nickel to iron by weight. A slurry is prepared by combining the resulting powder blend with polyvinyl alcohol in the ratio of 98:2 respectively, with enough water to make an 50-80% solids concentration. Spray drying is carried out by pumping the slurry at low pressure through a two fluid nozzle located at the top of a commercially available spray dryer. The slurry is continually agitated throughout the spray drying run. The atomization air pressure to the nozzle is 40-60 psi. The inlet air temperature is 370° C. with an outlet temperature of 140°-150° C. The spray dried powder is slowly passed through a hydrogen furnace at 450° C. to remove the organic binder. It is then fired for approximately 7 hours at 1000° C. to strengthen the agglomerated particles. The resulting particles are screened to yield powders with a -200 +325 or a -270 +20 μ m particle size distribution. These particles can then be used as plasma spray powders.
EXAMPLE 2
The agglomerated spray dried and sintered particles of Example 1 are fed through a commercially available plasma torch into a jacketed water cooled collection tank. A mixture of 126 cubic feet per hour of argon and 70 cubic feet per hour of hydrogen is fed to the plasma torch. The torch power is about 28KVA. Nitrogen gas is fed to a powder feeder at the rate of 7 cubic feet per hour to entrain the powder which is fed through the torch. The powder produced is then screened as in Example 1. Analysis of the -270 powder indicated 15%-15 μm particles. These prealloyed powder particles can then be used as a plasma spray powder.
EXAMPLE 3
A plasma densified spray powder as produced in Example 2 is comminuted and air classified to produce a powder having the following distribution: 60-90% less than 20 μm, no more than 15% less than 5 microns.
EXAMPLE 4
A sintered agglomerate is prepared according to the process described in Example 1 by substituting a nickel/iron powder containing a one to one weight ratio of nickel to iron and about 5% by weight cobalt. Similar results are obtained.
EXAMPLE 5
The sintered agglomerate powder of Example 4 is plasma densified according to the process as set forth in Example 2. The results were similar.
EXAMPLE 6
The densified plasma powder of Example 5 is comminuted and classified as in Example 3 with similar results.
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A plasma spray powder having a substantially uniform composition consisting essentially of a metal selected from the group consisting of cobalt, nickel, iron, mixtures and alloys thereof the balance consisting essentially of tungsten and carbon in a ratio of about one mole of carbon per one mole of tungsten wherein the ratio of iron and nickel to cobalt is at least about 4 to one.
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TECHNICAL FIELD
[0001] The present invention relates to novel fluorine-containing bisphosphonate derivatives and use thereof. More particularly, the present invention relates to fluorine-containing bisphosphonic acids, fluorine-containing bisphosphonate ester derivatives and pharmaceutical compositions, lymphocyte-treating agents, antitumor immune cell therapy agents, anti viral infection immune cell therapy agents and the like, each containing said derivative as an active ingredient.
BACKGROUND ART
[0002] Bisphosphonic acids are a group of compounds having a P—C—P skeleton, and show high bone tissue penetration and high affinity for bone. In addition, when the first generation bisphosphonic acids such as etidronic acid, clodronic acid and the like are selectively incorporated into monocytic cells such as osteoclasts and the like by liquid-phase endocytosis, they are metabolically converted to ATP analogs, act antagonistically to ATP receptors and show cytotoxicity. Thus, the first generation bisphosphonic acids suppress bone resorption by inducing cell death in osteoclasts. Utilizing such property, bisphosphonic acids are applied to various bone-related diseases. To be specific, they are used as prophylactic or therapeutic drugs for diseases relating to the fragility of bone and calcium concentration variation such as osteoporosis, osteitis deformans, osteogenesis imperfecta and hypercalcemia in malignant tumor. In addition, bisphosphonic acids belonging to the second generation such as pamidronic acid, alendronic acid, ibandronic acid and the like, and bisphosphonic acids belonging to the third generation such as risedronic acid, zoledronic acid and the like contain a nitrogen atom in the side chain, and are called nitrogen-containing bisphosphonic acids. When these bisphosphonic acids are selectively incorporated into monocytic cells such as osteoclast and the like, they specifically inhibit farnesyl diphosphate synthase and show cytotoxicity. Utilizing the properties thereof, various nitrogen-containing bisphosphonic acids have been used as improving-drugs for osteoporosis and hypercalcemia in malignant tumor. Recently, moreover, it has been reported that the disease-free survival is preferentially extended when zoledronic acid is used as an adjuvant therapy drug in the endocrine therapy and chemotherapy of premenopausal estrogen sensitive early breast cancer cases and multiple myeloma (non-patent documents 1, 2). This is considered to be because nitrogen-containing bisphosphonic acid has direct cytotoxicity and/or indirect cytotoxicity via activation of immunocytes on tumor cells and shows an antitumor effect.
[0003] For example, a part of etidronic acid or clodronic acid administered to a living body enters into the cell by a fluid phase endocytosis action, is transferred to nucleoside monophosphate, and converted to a nucleoside triphosphate analog compound. A metabolite thereof is shown to antagonistically inhibit biological enzyme reaction utilizing high energy phosphate bond of nucleoside triphosphate. When the incorporating cell is osteoclast, bone resorption is suppressed, and the concentration of calcium in the plasma decreases. In the case of tumor cells, the tumor cells are injured and a direct antitumor effect is expected.
[0004] The second generation and third generation nitrogen-containing bisphosphonic acids transferred into the cell have been shown to inhibit farnesyl diphosphate synthase involved in the biosynthesis pathway of isoprenoidal metabolites such as cholesterol and the like. Such enzyme catalyzes a reaction to synthesize geranyl diphosphate from isopentenyl diphosphate and dimethylallyl diphosphate, and a reaction to synthesize farnesyl diphosphate from isopentenyl diphosphate and geranyl diphosphate. Therefore, inhibition of farnesyl diphosphate synthase is considered to shut off the metabolic pathway located downstream of geranyl diphosphate, as well as cause accumulation of isopentenyl diphosphate to be an enzyme substrate. When the biosynthesis pathway located downstream of geranyl diphosphate is shut off, isoprenoidal compounds such as cholesterol, liposoluble vitamins, bile acid, lipoprotein and the like are not biosynthesized, and the proliferation of tumor cells is considered to be suppressed.
[0005] Generally, the isopropenyl group of farnesyl diphosphate and geranylgeranyl diphosphate biosynthesized by farnesyl diphosphate synthase is transferred to, what is called, small G proteins such as Ras, Rho, Rap, Rab, Rac and the like. The small G protein having the transferred isopropenyl group is translocated to a cellular membrane, which is an inherent action site of small G protein, since the isopropenyl group functions as a cellular membrane anchor, and exhibits important physiological functions such as cell proliferation, adhesion and the like. However, when nitrogen-containing bisphosphonic acid such as zoledronic acid and the like inhibits farnesyl diphosphate synthase, transfer of the isopropenyl group is inhibited, translocation to the membrane of small G protein is prevented, and, as a result, tumor cell proliferation is inhibited. This is one of the mechanisms that explain direct antitumor effects shown by nitrogen-containing bisphosphonic acid.
[0006] When farnesyl diphosphate synthase is further inhibited, the intracellular concentration of isopentenyl diphosphate as a substrate thereof increases. The increase in the intracellular concentration of isopentenyl diphosphate is detected by a butyrophilin 3A1 transmembrane type protein, and the change thereof is recognized by γδ T cells having a Vγ2Vδ2 T cell receptor (non-patent documents 3, 4). As a result, the γδ T cells are degranulated to release perforin and granzyme B, which induces apoptosis of tumor cells and virus infected cells. It is shown that nitrogen-containing bisphosphonic acid indirectly and efficiently damage tumor cells and virus-infected cells via activation of immunocyte.
[0007] The direct and indirect cytotoxicity by the nitrogen-containing bisphosphonic acids as mentioned above depends on the degree of incorporation into the cells to be injured, and the degree of inhibition of farnesyl diphosphate synthase. However, since bisphosphonic acids clinically applicable at present have all been synthesized for the purpose of improving bone-related disease, synthesis and screening of the compounds was performed using the affinity to bone, which is the action site of osteoclast, and cytotoxicity to osteoclast as indices. However, in the development of medicaments against tumor and virus infection, high bone penetration is conversely a factor that decreases reachability to tumor cells and virus infected cells.
[0008] Therefore, when direct improvement of cytotoxicity is desired, a decrease in the bone penetration needs to be one goal. On the other hand, when improvement of activation of γδ T cell as an immunity effector is desired, it is necessary to develop drugs by using, as indices, uptake into monocyte cells to be antigen presenting cells and γδ T cells activation potency. Thus, for compound screening without using suppression of bone resorption as an index, systematic synthesis of bisphosphonic acid having a basic skeleton different from that of conventional bisphosphonic acid is necessary.
[0009] About 30% of the low molecular medicaments currently on the market have fluorine in the basic skeleton. The reason for the superiority of medicaments due to the presence of a fluorine atom has not been completely elucidated. Until now, however, in the developmental stage of bisphosphonic acid, the fluorine-containing bisphosphonic acid is only one in which the hydroxyl group bonded to C in the P—C—P skeleton of risedronic acid is substituted by fluorine. This is because introduction of a fluorine atom is synthetically difficult in bisphosphonic acids. Therefore, it is an important research progress in the development of a medicament of bisphosphonic acid to explore a synthetic pathway of a series of fluorine-containing bisphosphonate derivatives, synthesize them systematically and study their physiological activities.
DOCUMENT LIST
Non-Patent Documents
[0000]
non-patent document 1: N. Engl. J. Med., 360(7):679-691 Feb. 12, 2009
non-patent document 2: Lancet 376: 1989-1999 2010
non-patent document 3: N. Engl. J. Med., 340(9):737-738 Mar. 4, 1999
non-patent document 4: J. Immunol. 191:1029-1042 2013
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0014] The problem of the present invention is to provide a novel fluorine-containing bisphosphonate derivative capable of efficiently inducing proliferation of peripheral blood γδ T cells that express Vγ2Vδ2 T cell receptor having superior cytotoxicity against tumor cells and virus infected cells, immunizing tumor cells and virus infected cells, and inducing cytotoxicity by γδ T cells.
Means of Solving the Problems
[0015] The present inventors have conducted intensive studies in an attempt to solve the above-mentioned problem, and found that a series of fluorine-containing bisphosphonic acid having a basic skeleton P—C(F)—P immunize monocytes and can induce proliferation of γδ T cells, and said compound group immunizes tumor cells and virus infected cells and can promote sensitivity of γδ T cells to cytotoxicity, which resulted in the completion of the present invention. To be specific, a series of fluorine-containing bisphosphonic acid in which an alkylamine side chain is added, a series of fluorine-containing bisphosphonic acids in which an amino group substituted by a heterocyclic group or a heterocyclic group containing a nitrogen atom is added, and a series of fluorine-containing bisphosphonate derivatives in which the acid moiety is esterified by an alkoxymethyl group such as pivaloyloxymethyl (POM) group, n-butanoyloxymethyl (BuOM) group and the like were synthesized, and the γδ T cell proliferation-inducing ability and tumor cell and virus infected cell-sensitizing ability of such novel compounds were verified. That is, the present invention is as shown below.
[0000] [1] A compound represented by the following formula (I):
[0000]
[0000] wherein Cy is a phenyl group or a heterocyclic group, Y is a hydrogen atom, an alkyl group, a halogen atom, an alkyl halide group, a hydroxyl group, an aryl group optionally substituted by a halogen atom or an alkoxy group, or an aralkyloxy group, F is a fluorine atom, P is a phosphorus atom, R is a hydrogen atom or an alkyl group, R 1 and R 2 are the same or different from each other and each is a hydrogen atom or an alkylcarbonyloxyalkyl group, j is a number 0 or 1, m is a number 0 or 1, and n is an integer of 1-6, provided that a compound wherein Cy is a 3-pyridyl group, m is 1, n is 1, Y is a hydrogen atom, and R 1 and R 2 are hydrogen atoms is excluded, or a pharmaceutically acceptable salt thereof.
[2] The compound of the above-mentioned [1], wherein, in the formula (I), Cy is a phenyl group, or a pharmaceutically acceptable salt thereof.
[3] The compound of the above-mentioned [1], wherein, in the formula (I), Cy is a 5- to 10-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom, or a pharmaceutically acceptable salt thereof.
[4] The compound of the above-mentioned [1], wherein, in the formula (I), Cy is a 5- or 6-membered heterocyclic group containing 1 or 2 atoms selected from a nitrogen atom and a sulfur atom, or a pharmaceutically acceptable salt thereof.
[5] The compound of the above-mentioned [1], wherein, in the formula (I), Cy is an imidazolyl group, a thiazolyl group, a pyridyl group, a pyrimidyl group, or a 7-azaindolyl group, or a pharmaceutically acceptable salt thereof.
[6] The compound of any of the above-mentioned [1]-[5], wherein, in the formula (I), Y is a hydrogen atom, a C 1-3 alkyl group, a halogen atom, an alkyl halide group or a phenyl group, and R 1 and R 2 are the same or different and each is a hydrogen atom or a C 2-7 alkylcarbonyloxy-C 1-3 alkyl group, or a pharmaceutically acceptable salt thereof.
[7] The compound of the above-mentioned [1], wherein, in the formula (I), j is 1, Cy is an imidazolyl group, Y is a hydrogen atom or halogen atom, and R 1 and R 2 are the same or different and each is a hydrogen atom or a C 2-7 alkylcarbonyloxy-C 1-3 alkyl group, or a pharmaceutically acceptable salt thereof.
[8] The compound of the above-mentioned [1], wherein, in the formula (I), j is 0, Y is a hydrogen atom or a C 1-3 alkyl group, and R 1 and R 2 are the same or different and each is a hydrogen atom or a C 2-7 alkylcarbonyloxy-C 1-3 alkyl group, or a pharmaceutically acceptable salt thereof.
[9] The compound of the above-mentioned [1], wherein, in the formula (I), j is 0, Y is a hydrogen atom, R is a hydrogen atom, and R 1 and R 2 are each a hydrogen atom, or a pharmaceutically acceptable salt thereof.
[10] The compound of the above-mentioned [1], wherein, in the formula (I), j is 0, Y is a C 1-3 alkyl group, R is a C 1-6 alkyl group, and R 1 and R 2 are each a hydrogen atom, or a pharmaceutically acceptable salt thereof.
[11] The compound of the above-mentioned [1], wherein, in the formula (I), j is 1, Cy is an imidazolyl group, Y is a hydrogen atom, and R 1 and R 2 are the same or different and each is a hydrogen atom or pivaloyloxymethyl (POM) group, or a pharmaceutically acceptable salt thereof.
[12] Any one of compounds represented by the following formulas, or a pharmaceutically acceptable salt thereof:
[0000]
[0000] [13] A pharmaceutical composition comprising the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof as an active ingredient.
[14] The pharmaceutical composition of the above-mentioned [13], which is an anti-tumor cell agent.
[15] The pharmaceutical composition of the above-mentioned [13], which is an anti-virus-infected cell agent.
[16] The pharmaceutical composition of the above-mentioned [13], which is a lymphocyte-treating agent.
[17] A method of treating a lymphocyte in a living body, comprising administering an effective amount of the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof to the body.
[18] A method of proliferating and/or inducing a γδ T cell, comprising administering an effective amount of the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof to a living body.
[19] A method of suppressing proliferation of a tumor cell, comprising administering an effective amount of the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof to a living body.
[20] A method of treating cancer, comprising administering an effective amount of the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof to a living body.
[21] A method of proliferating and/or inducing a γδ T cell, comprising reacting ex vivo the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof with a sample containing γδ T cells.
[22] A method of suppressing proliferation of a tumor cell, comprising a step of reacting the compound of any of the above-mentioned [1]-[12], or a pharmaceutically acceptable salt thereof with a sample containing γδ T cells collected from a living body, and a step of returning the γδ T cells to the living body.
[0016] In the present specification, a compound represented by the above-mentioned formula (I) is to be also referred to as the compound of the present invention, or the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention.
Effect of the Invention
[0017] When the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is reacted with peripheral blood mononuclear cells, and cultured together with interleukin-2 (IL-2) for 11 days, not less than 90% of the total cells become Vδ2 positive γδ T cells. The Vδ2 positive γδ T cells induced to proliferate show a cell-injuring activity on various tumor cells and virus infected cells. Furthermore, when tumor cells and virus infected cells are reacted with the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention, the recognition ability of Vδ2 positive γδ T cells is enhanced and the cells become more prone to cytotoxicity. That is, tumor cells and virus infected cells are immunized, and easily injured by Vδ2 positive γδ T cells. Utilizing this property, a novel immunotherapy of cancer and virus infection disease becomes possible.
[0018] When the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is reacted with peripheral blood mononuclear cells, it is selectively incorporated into monocytes having high liquid phase endocytosis ability. The fluorine-containing bisphosphonic acid directly inhibits farnesyl diphosphate synthase, and the fluorine-containing bisphosphonate derivative undergoes hydrolysis of the ester, is converted to bisphosphonic acid and inhibits farnesyl diphosphate synthase. Due to the inhibitory action, isopentenyl diphosphate, which is a metabolite located directly upstream of the enzyme, is intracellularly accumulated. Isopentenyl diphosphate binds to an intracellular region of the butyrophilin 3A1 molecule present in the cellular membrane, and changes the conformation of the extracellular region or changes the degree of polymerization. The change is recognized by Vδ2 positive γδ T cells, and proliferation stimulation is produced. When a cell proliferation factor such as IL-2, IL-15 and the like acts thereon, γδ T cells proliferate markedly. The proliferated γδ T cells show high tumor cell toxicity, and high virus infected cell toxicity.
[0019] When the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is reacted with tumor cells and virus infected cells, these medicaments are incorporated into the cells, and a phenomenon similar to the changes in the monocytes occurs. That is, the fluorine-containing bisphosphonic acid directly inhibits farnesyl diphosphate synthase, and the fluorine-containing bisphosphonate ester derivative undergoes hydrolysis of the ester, is converted to bisphosphonic acid and inhibits farnesyl diphosphate synthase. Due to the inhibitory action, isopentenyl diphosphate, which is a metabolite located directly upstream of the enzyme, is intracellularly accumulated. Isopentenyl diphosphate binds to an intracellular region of the butyrophilin 3A1 molecule present in the cellular membrane, and changes the conformation of the extracellular region or changes the degree of polymerization. The change is recognized by Vδ2 positive γδ T cells, and tumor cells and virus infected cells are efficiently injured.
[0020] Utilizing these actions of the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention, a novel immunotherapy of cancer and virus infection can be established. This therapy roughly includes two methods. One is an adoptive immunotherapy, and the other is a direct administration method.
[0021] In adoptive immunotherapy, mononuclear cells are purified from the peripheral blood of cancer patients or virus infection patients, the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is added, IL-2 is further added, and the cells are cultured for 11 days, whereby not less than 90% of the total cells become Vδ2 positive γδ T cells and the proliferation rate becomes not less than 1000-fold. This cell standard product is washed with PBS and intravenously administered to patients. In this case, when the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is administered before administration the cell, cancer cells or virus infected cells are immunized and the sensitivity to γδ T cells increases.
[0022] In the direct administration method, the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is intravenously administered to cancer patients or virus infection patients. In this case, a part of the compound is incorporated into the monocyte by liquid phase endocytosis, the fluorine-containing bisphosphonic acid directly inhibits farnesyl diphosphate synthase, and the fluorine-containing bisphosphonate derivative undergoes hydrolysis of the ester, is converted to bisphosphonic acid and inhibits farnesyl diphosphate synthase. Due to the inhibitory action, isopentenyl diphosphate, which is a metabolite located directly upstream of the enzyme, is intracellularly accumulated, binds to an intracellular region of the butyrophilin 3A1 molecule present in the cellular membrane, and changes the conformation of the extracellular region or changes the degree of polymerization. The change is recognized by Vδ2 positive γδ T cells, and proliferation stimulation occurs. On the other hand, the remaining compound is incorporated into the tumor cells or virus infected cells, induces an action similar to that in the monocyte and promotes sensitivity to γδ T cells. In this way, proliferated γδ T cells efficiently injure tumor cells or virus infected cells and induce antitumor activity and/or antivirus activity.
[0023] As mentioned above, the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention induces proliferation of γδ T cell, which is one kind of immunocyte, and promotes sensitivity of tumor cells and/or virus infected cells to γδ T cells, and therefore, it is utilizable as a low molecule medicament for an antitumor immune cell therapy and an anti viral infection immune therapy.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 shows specific examples of the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention. The numbers indicated in the parentheses in the structural formulas show compound numbers. (1) A compound in which a hydroxyl group bonded to a methylene carbon atom substituted by two phosphorus atoms of pamidronic acid is substituted by a fluorine atom (PAMF). (2) A compound in which a hydroxyl group bonded to a methylene carbon atom substituted by two phosphorus atoms of ibandronic acid is substituted by a fluorine atom (IBAF). (3) A compound in which a hydroxyl group bonded to a methylene carbon atom substituted by two phosphorus atoms of alendronic acid is substituted by a fluorine atom (ALEF). (4) A compound in which a hydroxyl group bonded to a methylene carbon atom substituted by two phosphorus atoms of zoledronic acid is substituted by a fluorine atom (ZOLF). (5) A compound in which a hydroxyl group bonded to a methylene carbon atom substituted by two phosphorus atoms of zoledronic acid is substituted by a fluorine atom, and four OH bonded to the phosphorus atom are substituted by POM groups (ZOLF-POM).
[0025] FIG. 2 shows the results of FACS analysis of peripheral blood mononuclear cells of adult T cell leukemia patient (1) which were stained with phycoerythrin (PE)-labeled anti-human CD3 antibody and fluorescein isothiocyanate (FITC)-labeled anti-human Vδ2 antibody (left Figure). The results of FACS analysis of peripheral blood mononuclear cells of adult T cell leukemia patient (1) which were reacted with ZOLF-POM, cultured for 11 days together with IL-2, and stained with PE-labeled anti-human CD3 antibody and FITC labeled anti-human Vδ2 antibody (right Figure).
[0026] FIG. 3 shows the results of FACS analysis of peripheral blood mononuclear cells of adult T cell leukemia patient (2) which were stained with PE-labeled anti-human CD3 antibody and FITC-labeled anti-human Vδ2 antibody (left Figure). The results of FACS analysis of peripheral blood mononuclear cells of adult T cell leukemia patient (2) which were reacted with ZOLF-POM, cultured for 11 days together with IL-2, and stained with PE-labeled anti-human CD3 antibody and FITC labeled anti-human Vδ2 antibody (right Figure).
[0027] FIG. 4 shows the results of FACS analysis of peripheral blood mononuclear cells of adult T cell leukemia patient (3) which were stained with PE-labeled anti-human CD3 antibody and FITC-labeled anti-human Vδ2 antibody (left Figure). The results of FACS analysis of peripheral blood mononuclear cells of adult T cell leukemia patient (3) which were reacted with ZOLF-POM, cultured for 11 days together with IL-2, and stained with PE-labeled anti-human CD3 antibody and FITC labeled anti-human Vδ2 antibody (right Figure).
[0028] FIG. 5 shows the results of FACS analysis of peripheral blood mononuclear cells of lung cancer patient (1) which were stained with PE-labeled anti-human CD3 antibody and FITC-labeled anti-human Vδ2 antibody (left Figure). The results of FACS analysis of peripheral blood mononuclear cells of lung cancer patient (1) which were reacted with ZOLF-POM, cultured for 11 days together with IL-2, and stained with PE-labeled anti-human CD3 antibody and FITC labeled anti-human Vδ2 antibody (right Figure).
[0029] FIG. 6 shows the results of FACS analysis of peripheral blood mononuclear cells of lung cancer patient (2) which were stained with PE-labeled anti-human CD3 antibody and FITC-labeled anti-human Vδ2 antibody (left Figure). The results of FACS analysis of peripheral blood mononuclear cells of lung cancer patient (2) which were reacted with ZOLF-POM, cultured for 11 days together with IL-2, and stained with PE-labeled anti-human CD3 antibody and FITC labeled anti-human Vδ2 antibody (right Figure).
[0030] FIG. 7 shows when U937 (human histiocytic tumor cell) was reacted with PAMF, ALEF, ZOLF and ZOLF-POM at 10 0 -10 6 nM, Vδ2 positive γδ T cells derived from normal adult (1) were added, the cells were stained with PE-labeled anti-human CD107a antibody and FITC-labeled anti-human Vδ2 antibody and analyzed by FACS, and the proportion of CD107a positive cells in Vδ2 positive γδ T cells was determined. The proportion showed cytotoxicity and the compound concentration dependency thereof is summarized in the Figure.
[0031] FIG. 8 shows when U937 (human histiocytic tumor cell) was reacted with ZOLF-POM at 0 μM, 1.25 μM, 2.5 μM or 5 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (1) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0032] FIG. 9 shows when U937 (human histiocytic tumor cell) was reacted with ZOLF at 0 μM, 100 μM, 300 μM or 1000 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (1) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0033] FIG. 10 shows when U937 (human histiocytic tumor cell) was reacted with ALEF at 0 μM, 300 μM, 1000 μM or 3000 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (1) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0034] FIG. 11 shows when U937 (human histiocytic tumor cell) was reacted with PAMF at 0 μM, 300 μM, 1000 μM or 3000 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (1) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0035] FIG. 12 shows when U937 (human histiocytic tumor cell) was reacted with IBAF at 0 μM, 300 μM, 1000 μM or 3000 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (1) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0036] FIG. 13 shows when U937 (human histiocytic tumor cell) was reacted with ZOLF at 0 μM, 100 μM, 300 μM or 1000 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (2) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0037] FIG. 14 shows when U937 (human histiocytic tumor cell) was reacted with a medium (upper panel), ZOLF 500 μM (middle panel), or ZOLF-POM 5 μM (lower panel), a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (3) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0038] FIG. 15 shows when U937 (human histiocytic tumor cell) was reacted with a medium (upper panel), ZOLF 500 μM (middle panel), or ZOLF-POM 5 μM (lower panel), a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (4) were added. In this case, the proportion of U937 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0039] FIG. 16 shows when human monocytic tumor cells P31/FUJ were reacted with a medium (upper panel), ZOLF 500 μM (middle panel), or ZOLF-POM 5 μM (lower panel), a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (3) were added. In this case, the proportion of P31/FUJ cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0040] FIG. 17 shows when adult T cell leukemia cell line HCT-5 was reacted with a medium (upper panel), ZOLF 1 mM (middle panel), or ZOLF-POM 1 μM (lower panel), a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (4) were added. In this case, the proportion of HCT-5 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0041] FIG. 18 shows when adult T cell leukemia cell line HCT-4 was reacted with a medium (upper panel), ZOLF-POM 1 μM (middle panel), or ZOLF-POM 10 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (4) were added. In this case, the proportion of HCT-4 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0042] FIG. 19 shows when human lung cancer cell line PC9 was reacted with ZOLF-POM at 0 μM, 1.25 μM, 2.5 μM or 5 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from lung cancer patient (1) were added. In this case, the proportion of PC9 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
[0043] FIG. 20 shows when human bladder cancer cell line EJ-1 was reacted with ZOLF-POM at 0 μM, 1.25 μM, 2.5 μM or 5 μM, a chelating agent was added, the cells were washed, and Vδ2 positive γδ T cells derived from normal adult (1) were added. In this case, the proportion of EJ-1 cells injured by Vδ2 positive γδ T cells was taken as a specific cytotoxicity ratio, and effector cell/target cell ratio (E/T ratio) dependency is summarized in the Figure.
DESCRIPTION OF EMBODIMENTS
[0044] One embodiment of the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative to be used in the present invention is represented by the following formula (I):
[0000]
[0000] wherein Cy is a phenyl group or a heterocyclic group, Y is a hydrogen atom, an alkyl group, a halogen atom, an alkyl halide group, a hydroxyl group, an aryl group optionally substituted by a halogen atom or an alkoxy group, or an aralkyloxy group, F is a fluorine atom, P is a phosphorus atom, R is a hydrogen atom or an alkyl group, R 1 and R 2 are the same or different from each other and each is a hydrogen atom or an alkylcarbonyloxyalkyl group, j is a number 0 or 1, m is a number 0 or 1, and n is an integer of 1-6, provided that a compound wherein Cy is a 3-pyridyl group, m is 1, n is 1, Y is a hydrogen atom, and R 1 and R 2 are hydrogen atoms is excluded.
[0045] Cy is a phenyl group or a heterocyclic group, to which at least Y is bonded. The heterocyclic group is a 4- to 15-membered monocyclic heterocyclic group or condensed polycyclic heterocyclic group containing, as a ring-constituting atom besides carbon atom, 1-4 hetero atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the heterocyclic group include furyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, triazinyl, quinolyl, isoquinolyl, quinazolyl, quinoxalyl, benzofuryl, benzothienyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, benzotriazole, indolyl, indazolyl, pyrrolopyrazinyl, imidazopyridinyl, imidazopyrazinyl, pyrazolopyridinyl, pyazolothienyl, pyrazolotriazinyl, oxetanyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, hexamethyleniminyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, oxazolinyl, thiazolinyl, imidazolinyl, dioxolanyl, dihydrooxadiazolyl, pyranyl, tetrahydropyranyl, thiopyranyl, tetrahydrothiopyranyl, tetrahydrofuryl, pyrazolidinyl, pyrazolinyl, tetrahydropyrimidinyl, dihydroindolyl, dihydroisoindolyl, dihydrobenzofuranyl, dihydrobenzodioxinyl, dihydrobenzodioxepinyl, tetrahydrobenzofuranyl, chromenyl, dihydroquinolinyl, tetrahydroquinolinyl, dihydroisoquinolinyl, tetrahydroisoquinolinyl, dihydrophthalazinyl, 7-azaindolyl and the like.
[0046] Preferably, the above-mentioned heterocyclic group is a 5- to 10-membered heterocyclic group containing 1-3 hetero atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom, more preferably a 5- or 6-membered heterocyclic group containing 1 or 2 hetero atoms selected from a nitrogen atom and a sulfur atom. Such heterocyclic group is specifically preferably imidazolyl, thiazolyl, pyridyl, pyrimidyl or 7-azaindolyl, more preferably imidazolyl or pyrimidyl, particularly preferably imidazolyl group.
[0047] In the above-mentioned heterocyclic group, Y is bonded at a substitutable position. Y is a hydrogen atom, an alkyl group (e.g., C 1-10 alkyl group such as methyl, ethyl, hexyl, octyl and the like), a halogen atom, (e.g., chlorine atom, fluorine atom, bromine atom), an alkyl halide group (e.g., C 1-3 alkyl group (e.g., methyl, ethyl, propyl) substituted by 1 to 3 halogen atoms (as defined above), a hydroxyl group, an aryl group, or an aralkyloxy group. As used herein, the aforementioned aryl group is optionally substituted by a halogen atom (as defined above) or an alkoxy group (e.g., C 1-3 alkoxy group such as methoxy, ethoxy, propoxy and the like). Preferably, Y is a hydrogen atom, a C 1-3 alkyl group (as defined above), a halogen atom, an alkyl halide group, an unsubstituted aryl group, more preferably, a hydrogen atom, a methyl group, a halogen atom, a trifluoromethyl group or a phenyl group, most preferably, a hydrogen atom or a bromine atom.
[0048] The aryl group encompasses a monocyclic aryl group and a condensed polycyclic aryl group, and specifically, phenyl, biphenyl, naphthyl, anthryl, phenanthryl and acenaphthylenyl can be mentioned. It is preferably a C 6-18 aryl group, more preferably a C 6-8 aryl group, particularly preferably a phenyl group.
[0049] The aralkyloxy group is preferably a C 7-18 aralkyloxy group, specifically benzyloxy, phenethyloxy and the like, with preference given to benzyloxy.
[0050] R 1 and R 1 are the same or different from each other and each is a hydrogen atom or an alkylcarbonyloxyalkyl group, and at least one of R c and R 2 is an alkylcarbonyloxyalkyl group. Preferably, both of R 1 and R 2 are alkylcarbonyloxyalkyl groups. Examples of the alkylcarbonyloxyalkyl group include a C 2-7 alkylcarbonyloxy-C 1-3 alkyl group, preferably, C 3-4 alkylcarbonyloxy-methyl, particularly preferably, pivaloyloxymethyl or n-butanoyloxymethyl.
[0051] j is 0 or 1. m is 0 or 1, preferably 1. In the case wherein Cy is secondary amine such as pyrrolyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, hexamethyleniminyl, oxazolidinyl, thiazolidinyl, imidazolidinyl and the like, m is 0, Cy is bonded to —(CH 2 ) n — group at the nitrogen atom. n is an integer of 1-6, preferably 1-3, particularly preferably 1.
[0052] The fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention can be efficiently produced by 3 synthesis steps when, for example, a fluorine atom is introduced into bisphosphonic acid (or a derivative thereof). First, (a) a reactive group such as an amino group and the like of bisphosphonic acid to be the starting material is protected, (b) a fluorine atom is introduced by a fluorinating agent, and (c) the protecting group introduced in step a is removed. Examples of the fluorinating agent to be used in step b include N-fluorosulfonimides such as N-fluorophenylsulfonimide, N-fluorotoluenesulfonimide, N-fluoromethanesulfonimide, N-fluorotrifluoromethanesulfonimide and the like, N-fluoropyridinium salts such as N-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate, N-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate and the like, difluoroxenon, fluorine gas and the like. N-fluorosulfonimides are preferable in view of easy availability, easy handling, yield and the like.
[0053] Alternatively, when bisphosphonic acid (or a derivative thereof) into which a fluorine atom is introduced is obtainable, the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention can also be produced by using the compound as a starting material and introducing a desired substituent. The reagent to be used, reaction conditions and the like can be selected and determined by a known method or by appropriately modifying or altering the method according to the kind of the starting material and substituent to be introduced.
[0054] The fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention can be specifically synthesized according to the synthesis procedure of the below-mentioned Examples.
[0055] The fluorine-containing bisphosphonic acid and fluorine-containing bisphosphonate derivative in the present invention may be pharmaceutically acceptable salts. In addition, when the fluorine-containing bisphosphonic acid and fluorine-containing bisphosphonate derivative of the present invention contain an isomer (e.g., optical isomer, geometric isomer and tautomer) and the like, the present invention encompasses such isomers and also encompasses solvate, hydrate and various shapes of crystals.
[0056] In the present invention, as a pharmaceutically acceptable salt, general salts pharmacologically and pharmaceutically acceptable salts can be mentioned. Specific examples of such salt include the following.
[0057] Examples of basic addition salt include alkali metal salts such as sodium salt, potassium salt and the like; alkaline earth metal salts such as calcium salt, magnesium salt and the like; ammonium salt; trimethylamine salt, triethylamine salt; aliphaticamine salts such as dicyclohexylamine salt, ethanolamine salt, diethanolamine salt, triethanolamine salt, procaine salt and the like; aralkylamine salts such as N,N-dibenzylethylenediamine and the like; heterocycle aromatic amine salts such as pyridine salt, picoline salt, quinoline salt, isoquinoline salt and the like; quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, methyltrioctylammonium salt, tetrabutylammonium salt and the like; basic amino acid salts such as arginine salt, lysine salt and the like; and the like.
[0058] Examples of acid addition salt include inorganic acid salts such as hydrochloride, sulfate, nitrate, phosphate, carbonate, hydrogencarbonate, perchlorate and the like; organic acid salts such as acetate, propionate, lactate, maleate, fumarate, tartrate, malate, citrate, ascorbate and the like; sulfonates such as methanesulfonate, isethionate, benzenesulfonate, p-toluenesulfonate and the like; acidic amino acid salts such as aspartate, glutamate and the like; and the like.
[0059] The novel fluorine-containing bisphosphonic acid and fluorine-containing bisphosphonate derivative of the present invention have a farnesyl diphosphate synthase inhibitory activity. As a result, it suppresses production of isoprenoid metabolites such as cholesterol, liposoluble vitamin, lipoprotein and the like, which are essential for cell survival and exhibits superior direct tumor damaging effect and virus-infected cell cytotoxicity effect. Therefore, the present invention provides direct or indirect antitumor drugs and antiviral agents containing the fluorine-containing bisphosphonic acid and/or a fluorine-containing bisphosphonate derivative as an active ingredient.
[0060] The antitumor and antiviral agent of the present invention can be used by administering to the living body, and preferably administered to mammals (human, mouse, rat, hamster, rabbit, cat, dog, bovine, sheep, monkey etc.).
[0061] The novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention specifically stimulates and proliferates and/or induces Vδ2 positive γδ T cells present in the blood such as peripheral blood in the living body, or lymph fluid, as well as can induce or potentiate an antitumor action of these cells. Therefore, the present invention provides lymphocyte-treating agent containing the fluorine-containing bisphosphonic acid and/or a fluorine-containing bisphosphonate derivative as an active ingredient.
[0062] As an antitumor action of the γδ T cells, recognition of a molecule expressing in cancer cells, for example, MICA/B and IPP (isopentenyl pyrophosphate) via a T cell receptor thereof and injury of the cell by γδ T cells can be mentioned. Furthermore, enhancement of antitumor activity by the action of cytokines such as TNF-α, INF-γ and the like produced by γδ T cells can be mentioned.
[0063] The lymphocyte-treating agent of the present invention has an action to proliferate and/or induce γδ T cells in vivo and ex vivo. Therefore, the lymphocyte-treating agent of the present invention can be used by treating a sample containing γδ T cells collected from a living body, or directly administering to a living body. Here, the living body means mammals (human, mouse, rat, hamster, rabbit, cat, dog, bovine, sheep, monkey etc.), and human is particularly preferable.
[0064] The present invention also includes a method of suppressing proliferation of tumor cells, comprising a step of proliferating and/or inducing γδ T cells by reacting the lymphocyte-treating agent of the present invention on a sample containing γδ T cells collected from a living body, and a step of returning the γδ T cells to the living body.
[0065] As a sample containing γδ T cells collected from a living body, blood such as peripheral blood and lymph fluid can be recited as examples. As a target of the lymphocyte-treating agent of the present invention, peripheral blood is preferable, and it is more preferable to use a mononuclear cell fraction separated from the peripheral blood by a specific gravity centrifugation method.
[0066] It is possible to stimulate γδ T cells in a sample with the lymphocyte-treating agent of the present invention by culturing the lymphocyte-treating agent and the sample according to a conventional method. It is possible to induce and/or proliferate γδ T cells by culturing in the presence of a fluorine-containing bisphosphonic acid and/or a fluorine-containing bisphosphonate derivative in a trace amount of 100 pM-100 μM, preferably 100 pM-20 μM, further preferably 100 pM-5 μM.
[0067] Since the fluorine-containing bisphosphonic acid and a fluorine-containing bisphosphonate derivative as the active ingredient in the lymphocyte-treating agent of the present invention has a bisphosphonic acid skeleton, it shows resistance to alkaliphosphatase as compared to conventional pyrrophosphoric acid lymphocyte-treating agents (Biology Trace Element Research, 104, 131-140 (2005)). Therefore, as a culture medium of γδ T cells to induce and/or proliferate γδ T cells, one containing a serum can be used and, for example, human AB serum, fetal bovine serum and the like can be used. Since a medium containing a serum can be used, γδ T cells can be advantageously provided in an amount sufficient for use in a cancer treatment, conveniently and in a short time.
[0068] As a constitution embodiment for use of the lymphocyte-treating agent of the present invention ex vivo for proliferating and/or inducing γδ T cells, the fluorine-containing bisphosphonic acid and/or a fluorine-containing bisphosphonate derivative itself as the active ingredient may be used alone. In addition, it can also be produced as a solution of ethanol, DMSO and the like. Where necessary, other additive can also be added simultaneously. When the lymphocyte-treating agent is reacted with a sample, interleukin-2 (IL-2), interleukin-7 (IL-7), interleukin-15 (IL-15), interleukin-18 (IL-18), and the like may also be added as an aid factor at a concentration of 0.1-150 IU/mL, preferably 1-100 IU/mL or 0.11-1000 ng/mL. Specific induction and/or proliferation of the γδ T cells becomes remarkable by the addition of these.
[0069] Induction and/or proliferation of specific γδ T cells by the lymphocyte-treating agent can be evaluated by measuring, after culturing, the IFN-γ amount and/or TNF-α amount produced in the culture supernatant. For example, when the TNF-α production amount is higher than that at the time of start of culture, γδ T cells can be judged to have been induced. The IFN-γ amount and/or TNF-α amount can be performed using a conventionally-known method by using an anti-IFN-γ antibody, an anti-TNF-α antibody and the like.
[0070] The γδ T cells treated with the lymphocyte-treating agent of the present invention as mentioned above can be used by administration as a medicament to a patient. For example, a mononuclear cell fraction derived from a patient having a tumor is treated with the lymphocyte-treating agent of the present invention, and a mononuclear cell fraction found to show proliferation and/or induction of γδ T cells is administered as peripheral blood and the like to allow for exhibition of an antitumor activity. As an administration method, methods such as topical injection, intravenous injection, transdermal absorption and the like.
[0071] When the antitumor drug, antiviral agent and lymphocyte-treating agent of the present invention are used as pharmaceutical products, they are generally mixed with pharmaceutically acceptable carrier, excipient, diluent, filler, disintegrant, stabilizer, preservative, buffering agent, aromatic, colorant, sweetening agent, thickener, corrigent, solubilizing agents, and other additive known per se, specifically, water, vegetable oil, alcohol (e.g., ethanol, benzyl alcohol etc.), polyethylene glycol, glyceroltriacetate, gelatin, hydrocarbonate (e.g., lactose, starch etc.), magnesium stearate, talc, lanolin, petrolatum and the like, and a tablet, pill, powder, granule, suppository, injection, eye drop, liquid, capsule, troche, aerosol, elixir, suspension, emulsion, syrup and the like are formed by conventional methods, and they can be administered systemically or topically, orally or parenterally.
[0072] While the dose varies depending on the age, body weight, symptom, treatment effect, administration method and the like, it is generally 0.001 mg/kg-1000 mg/kg, preferably 0.01 mg/kg-100 mg/kg, per one time in the amount of active ingredient, for an adult, which is administered once to several times per day, orally or in the form of injection such as intravenous injection and the like.
[0073] The present invention encompasses direct and indirect antitumor drug and antiviral agent, and shows a treatment effect on benign and malignant tumor, and virus infected cells. In addition, the lymphocyte-treating agent of the present invention is useful for the prophylaxis and/or treatment of tumor. Examples of the tumor target include malignant tumors such as brain tumor (malignant astrocytoma, glioma having oligodendroglial tumor component etc.), esophagus cancer, gastric cancer, liver cancer, pancreatic cancer, large intestine cancer (colorectal cancer, rectal cancer etc.), urinary bladder cancer, lung cancer (non-small cell lung cancer, small cell lung cancer, primary and metastatic squamous cell carcinoma etc.), renal cancer, breast cancer, ovarian cancer, prostate cancer, skin cancer, neuroblastoma, sarcoma, bone and soft tissue tumor, bone tumor, osteosarcoma, testis tumor, extragonadal tumor, orchis tumor, uterine cancer (uterus cervix cancer, uterine body cancer etc.), head and neck tumor (maxilla cancer, laryngeal cancer, pharyngeal cancer, cancer of the tongue, mouth cavity cancer etc.), multiple myeloma, malignant lymphoma (reticulum cell sarcoma, lymphosarcoma, Hodgkin's disease etc.), polycythemia vera, leukemia (acute myeloid leukemia, chronic myeloid leukemia, acute lymphocytic leukemia, chronic lymphocytic leukemia etc.), thyroid cancer, renal pelvis cancer, ureter tumor, bladder tumor, gall bladder cancer, cholangiocarcinoma, choriocarcinoma, malignant melanoma, pediatric tumor (Ewing sarcoma family, Wilms' tumor, rhabdomyosarcoma, blood vessel sarcoma, testicular embryonal carcinoma, neuroblastoma, retinoblastoma, hepatoblastoma, nephroblastoma etc.) and the like and the like. As viral infectious disease to be the target, viral infectious disease such as HTLV-1 infections, HIV infections, influenza disease, herpes disease and the like, and the like can be mentioned. In the present invention, application to urinary bladder cancer, renal cancer, lung cancer, breast cancer, hematologic tumor such as leukemia and the like, and HTLV-1 infections is preferable.
EXAMPLES
[0074] The production method of the fluorine-containing bisphosphonic acid and a fluorine-containing bisphosphonate derivative of the present invention is specifically explained below, and shown below. The production method of the compound of the present invention is not limited to those specifically explained below.
[0075] Unless specifically indicated, all reactions were performed under air atmosphere. Unless specifically indicated, various reagents used were commercially available products.
(Measurement Method and Marking)
[0076] 1 H NMR, 13 C NMR and 19 F NMR spectra were measured by JNM-AL-400 spectrometer ( 1 H NMR at 400 MHz, 13 C NMR at 100 MHz) and Varian-500PS spectrometer ( 1 H NMR at 500 MHz, 13 C NMR at 125 MHz, 19 F NMR at 470 MHz) (JEOL Ltd., Akishima, Tokyo, Japan) in CDCl 3 or D 2 O solution. 1 H NMR chemical shift refers to tetramethylsilane (TMS) (0.00 ppm) and 13 C NMR chemical shift refers to CDCl 3 (77.0 ppm) and 19 F NMR chemical shift refers to CFCl 3 . The chemical shift is shown in one-millionth (ppm).
[0077] The multiplicity of the peak is abbreviated as follows. s, singlet; d, doublet; dt, doublet of triplets; ddd, doublet of doublet of doublets; dtt, doublet of triplet of triplets; t, triplet; tt, triplet of triplets; q, quartet; m, multiplet; br, broad; pent, pentet
[0078] Mass spectrum and high resolution mass spectrum were measured by JEOL IMS-T100TD (JEOL Ltd.).
[0079] Thin layer chromatography (TLC) was performed on a pre-coated plate (0.25 mm, silica gel plate 60F 245 , Merck Millipore, Mass.).
[0080] Column chromatography was performed on a silica gel plate (Kanto Chemical Co., Inc.).
LIST OF ABBREVIATIONS
[0081] Me: methyl,
Et: ethyl,
iPr: isopropyl,
Boc: t-butoxycarbonyl,
Boc 2 O: di-tert-butyl dicarbonate,
Et 3 N: triethylamine,
CH 2 Cl 2 : dichloromethane,
quant.: quantitatively obtained,
NFSI: N-fluorobenzenesulfonimide,
[0082] n-BuLi: n-butyllithium,
THF: tetrahydrofuran,
HCl: hydrochloric acid,
NaH: sodium hydride,
15-crown-5-ether: 15-crown-5-ether,
MeOH: methanol,
Ms: methanesulfonyl,
MsCl: methanesulfonyl chloride,
K 2 CO 3 : potassium carbonate,
DMF: N,N-dimethylformamide,
[0083] KH: potassium hydride,
18-crown-6-ether: 18-crown-6-ether,
select fluor: 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroboric acid)
Example 1
Synthesis of 3-amino-1-fluoro-propylidene-1,1-bisphosphonic acid (PAMF)
[0084]
(1) tert-butyl(3,3-bis(diethoxyphosphoryl)propyl)carbamate
[0085]
[0086] Tetraethyl-3-aminopropylidene-1,1-bisphosphonate [1] (460 mg, 1.5 mmol) dissolved in dichloromethane (20 mL) was reacted with Boc 2 O (334 μL, 1.5 mmol) and triethylamine (205 μL, 1.5 mmol) at room temperature. The reaction mixture was stirred for 9 hr, the solvent was removed under reduced pressure, and the solution was concentrated. As a result, colorless oily tert-butyl(3,3-bis(diethoxyphosphoryl)propyl)carbamate (575 mg, yield 99%) was obtained. [1] K. Ogawa, T. Mukai, Y. Arano, H. Hanaoka, K. Hashimot, H. Nishimura, H. Saji, J. Label. Compd Radiopharm. 2004, 47, 753-761.
[0087] 1 H NMR (500 MHz, CDCl 3 ) δ 1.35 (t, J=7.1 Hz, 6H), 1.53 (s, 9H), 2.06-2.15 (m, 2H), 2.40 (tt, J=6.4, 23.9 Hz, 2H), 3.30-3.37 (m, 2H), 4.17-4.22 (m, 8H), 5.06 (br. s, NH);
[0088] 13 C NMR (125 MHz, CDCl 3 ) δ 16.3-16.3 (m), 27.3, 28.3, 62.6-62.7 (m), 85.1, 146.6;
[0089] HRMS (ESI) m/z Calcd for C 16 H 35 NNaO 8 P 2 [M] + 454.1736, found 454.1696.
(2) tert-butyl(3,3-bis(diethoxyphosphoryl)-3-fluoropropyl)carbamate
[0090]
[0091] To tert-butyl(3,3-bis(diethoxyphosphoryl)propyl)carbamate (50 mg, 0.13 mmol) dissolved in THF (2.0 mL) was added dropwise n-BuLi (90 μL, 1.6 M hexane solution, 0.14 mmol) at −78° C. under an argon atmosphere. After stirring for 10 min, N-fluorophenylsulfonimide (45 mg, 0.14 mmol) was added to the carbanion solution. The reaction mixture was allowed to reach room temperature over 1 hr. After stirring for 7 hr, the reaction was discontinued with saturated ammonium chloride (10 mL). The reaction product was extracted from the aqueous phase with ethyl acetate (2×10 mL), and the obtained organic phases were mixed. This was dehydrated over magnesium sulfate, and concentrated under reduced pressure. The reaction product was passed through a silica gel column by using acetone/n-hexane=1/1 solvent system. However, since the object product could not be obtained with high purity, 28 mg of a crude product containing tert-butyl(3,3-bis(diethoxyphosphoryl)-3-fluoropropyl)carbamate as the main component was used without further purification for the next reaction.
[0092] 1 H NMR (400 MHz, CDCl 3 ) δ 1.36 (t, J=8.8 Hz, 12H), 1.42 (s, 9H), 2.33-2.43 (m, 2H), 3.45-3.48 (m, 2H), 4.22-4.31 (m, 8H), 5.18 (br. s, NH).
[0093] HRMS (ESI) m/z Calcd for C 16 H 34 FNNaO 8 P 2 [M] + 472.1641, found 472.1646.
(3) 3-amino-1-fluoro-propylidene-1,1-bisphosphonic acid
[0094]
[0095] tert-Butyl(3,3-bis(diethoxyphosphoryl)-3-fluoropropyl)carbamate (28 mg, 0.06 mmol) was dissolved in 1 mL of 6N hydrochloric acid, and the mixture was heated under reflux for 7 hr. The solvent was removed under reduced pressure and the reaction mixture was concentrated. The residue was recrystallized from water/methanol to give a yellow solid (14 mg, yield 45%).
[0096] 1 H NMR (500 MHz, D 2 O) δ 2.38-2.51 (m, 2H), 3.28-3.34 (m, 2H);
[0097] 19 F NMR (470 MHz, D 2 O) δ −183.4 (tt, J=23.1, 69.2 Hz);
[0098] HRMS (ESI) m/z Calcd for C 3 H 9 FNO 6 P 2 [M] − 235.9889, found 235.9852.
Example 2
Synthesis of 1-fluoro-3-(methyl(pentyl)amino)propylidene-1,1-bisphosphonic acid (IBAF)
[0099]
(1) tetraisopropylmonofluoromethylenediphosphonate [2]
[0100]
[0101] Tetraisopropyl methylenediphosphonate (2.5 g, 7.3 mmol) dissolved in 20 mL of DMF was cooled on ice to 0° C. NaH (386 mg, 60% in mineral oil, 16.6 mmol) dissolved in 20 mL of DMF was placed in a different flask, and cooled for 5 min at 0° C. This NaH solution was added dropwise to tetraisopropyl methylenediphosphonate. The reaction mixture was stirred at 0° C. for 10 min, and allowed to warm to room temperature. After stirring for 1 hr at room temperature, selectfluor (5.7 g, 16.6 mmol) dissolved in DMF was added, and the reaction mixture was stirred for 6 hr at room temperature. This was diluted with 50 mL of dichloromethane, and 50 mL of saturated ammonium chloride solution was added to discontinue the reaction. The aqueous phase was extracted with dichloromethane (2×50 mL) and the obtained organic phase was dried over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and purified by silica gel column (eluent: gradient of ethyl acetate/n-hexane=1/2 to ethyl acetate 100%) to give monofluoro bisphosphonate (746 mg, yield 22%) and difluorobisphosphonic acid (615 mg, yield 28%). [2] V. Jo Davisson, Darrell R. Davis, Vyas M. Dixit, C. Dale Poulter, J. Org. Chem. 1987, 52, 1794-1801.
(2) tetraisopropyl-1-fluoro-3-hydroxypropylidene-1,1-bisphosphonate
[0102]
[0103] To a suspension of NaH (96 mg, 60%, 2.4 mmol) in THF (15 mL) prepared under an argon atmosphere was added at 0° C. tetraisopropylmonofluoromethylenediphosphonate (724 mg, 2.0 mmol) dissolved in 5 mL of THF. After stirring for 30 min, 2-(2-iodoethoxy)tetrahydro-2H-pyran (615 mg, 2.4 mmol) and 15-crown-5-ether (88 mg, 0.4 mmol) dissolved in 2 mL of THF was added. The reaction mixture was stirred at room temperature for 24 hr, and the reaction was discontinued with saturated ammonium chloride solution. A compound was extracted from the aqueous phase with ethyl acetate (2×50 mL), and the obtained organic phases were mixed, dehydrated over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. A crude product of tetraisopropyl-1-fluoro-3-((tetrahydro-2H-pyran-2-yl)oxy)propylidene-1,1-bisphosphonate was treated with 2 mL of 1N hydrogen chloride methanol solution, and the mixture was stirred for 10 min. The reaction mixture was concentrated under reduced pressure and purified by silica gel column (eluate: acetone/n-hexane=1/1) to give tetraisopropyl-1-fluoro-3-hydroxypropylidene-1,1-bisphosphonate as a colorless oil (198 mg, yield 24%).
[0104] 1 H NMR (500 MHz, CDCl 3 ) δ 1.37-1.38 (m, 24H), 2.42 (dtt, J=5.4, 15.2, 27.5 Hz, 2H), 3.88 (t, J=5.1 Hz, 2H), 4.11 (br. s, OH), 4.89-4.90 (m, 4H);
[0105] 13 C NMR (125 MHz, CDCl 3 ) δ 23.7-23.8 (m), 24.2-24.3 (m), 36.8 (d, J=19.2 Hz), 73.1 (t, J=3.7 Hz), 73.2 (t, J=3.5 Hz);
[0106] 19 F NMR (470 MHz, CDCl 3 ) 5-193.8 (tt, J=22.7, 78.0 Hz);
[0107] HRMS (ESI) m/z Calcd for C 15 H 33 FN 2 NaO 7 P 2 [M] + 429.1583, found 429.1543.
(3) 2,2-bis(diisopropyloxyphosphoryl)2-fluoroethylmethanesulfonate
[0108]
[0109] To tetraisopropyl-1-fluoro-3-hydroxypropylidene-1,1-bisphosphonate (190 mg, 0.47 mmol) dissolved in 5 mL of dichloromethane were added triethylamine (78 μL, 0.56 mmol) and methanesulfonyl chloride (43 μL, 0.56 mmol) at room temperature. The reaction mixture was stirred for 7 hr, and extracted with ethyl acetate (2×50 mL). The obtained organic phase was washed with water. Then, it was washed with salt water, dehydrated over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure and purified by silica gel column (solvent: acetone/n-hexane=1/1) to give 2,2-bis(diisopropyloxyphosphoryl)2-fluoroethylmethanesulfonate (209 mg, yield 92%) as a yellow oil.
[0110] 1 H NMR (500 MHz, CDCl 3 ) δ 1.36-1.38 (m, 24H), 2.53-2.66 (m, 2H), 3.01 (s, 3H), 4.54 (t, J=7.8 Hz, 2H), 4.82-4.91 (m, 4H);
[0111] 13 C NMR (125 MHz, CDCl 3 ) δ 23.7 (dt, J=2.8, 12.9 Hz), 24.2 (d, J=28.6 Hz), 32.9 (d, J=20.1 Hz), 37.3, 65.3 (q, J=6.9 Hz), 73.2 (t, J=3.7 Hz), 73.5 (t, J=3.7 Hz);
[0112] 19 F NMR (470 MHz, CDCl 3 ) 5-195.0 (tt, J=23.1, 75.1 Hz);
[0113] HRMS (ESI) m/z Calcd for C 16 H 35 FNaO 9 P 2 S [M] + 507.1359, found 507.1353.
(4) tetraisopropyl-1-fluoro-3-(methyl(pentyl)amino)propylidene-1,1-bisphosphonate
[0114]
[0115] To 2,2-bis(diisopropyloxyphosphoryl)2-fluoroethylmethanesulfonate (150 mg, 0.31 mmol) dissolved in 2.5 mL of DMF was added a solution of potassium carbonate (129 mg, 0.93 mmol) and N-hexylmethylamine (63 mg, 0.62 mmol). The reaction mixture was stirred at 80° C. for 19 hr, and water was added to discontinue the reaction. A compound was extracted from the aqueous phase with ethyl acetate (2×50 mL), and the obtained organic phase was washed with salt water, dehydrated over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (solvent: acetone/n-hexane=1/1) to give tetraisopropyl-1-fluoro-3-(methyl(pentyl)amino)propylidene-1,1-bisphosphonate (31 mg, yield 21%) as a colorless oily substance.
[0116] 1 H NMR (500 MHz, CDCl 3 ) δ 0.90 (t, J=7.4 Hz, 3H), 1.27-1.39 (m, 28H), 1.44-1.52 (m, 2H), 2.23-2.40 (m, 7H), 2.72-2.78 (m, 2H), 4.83-4.94 (m, 4H);
[0117] 13 C NMR (125 MHz, CDCl 3 ) δ 14.0, 22.6, 23.7 (dt, J=3.0, 18.0 Hz), 24.3, (dt, J=1.4, 32.6 Hz), 27.0, 29.7, 30.3 (d, J=19.1 Hz), 42.0, 50.9 (q, J=6.2 Hz), 57.3, 72.6 (t, J=3.5 Hz), 72.9 (t, J=3.7 Hz);
[0118] 19 F NMR (470 MHz, CDCl 3 ) 5-193.6 (tt, J=23.4, 76.2 Hz);
[0119] HRMS (ESI) m/z Calcd for C 21 H 46 FNNaO 6 P 2 [M] + 512.2682, found 512.2686.
(5) 1-fluoro-3-(methyl(pentyl)amino)propylidene-1,1-bisphosphonic acid
[0120]
[0121] Tetraisopropyl-1-fluoro-3-(methyl(pentyl)amino)propylidene-1,1-bisphosphonate (30 mg, 0.06 mmol) was dissolved in 1 mL of 6N hydrochloric acid, and heated under reflux for 7 hr. The reaction mixture was concentrated under reduced pressure to give 1-fluoro-3-(methyl(pentyl)amino)propylidene-1,1-bisphosphonic acid (20 mg, yield 99%) as a viscous oil.
[0122] 1 H NMR (500 MHz, D 2 O) δ 0.79 (t, J=7.1 Hz, 3H), 1.21-1.29 (m, 4H), 1.57-1.72 (m, 2H), 2.42-2.53 (m, 2H), 2.79 (s, 3H), 2.99-3.04 (m, 1H), 3.11-3.17 (m, 1H), 3.26-3.33 (m, 1H), 3.46 (m, 1H);
[0123] 13 C NMR (125 MHz, D 2 O) δ 12.9, 21.4, 23.1, 27.3 (d, J=19.9 Hz), 27.7, 39.4, 51.5-51.7 (m), 56.3;
[0124] 19 F NMR (470 MHz, D 2 O) δ −189.5 (tt, J=21.6, 69.9 Hz);
[0125] HRMS (ESI) m/z Calcd for C 9 H 21 FNNaO 6 P 2 [M] − 320.0828, found 320.0843.
Example 3
Synthesis of 4-amino-1-fluoro-butylidene-1,1-bisphosphonic acid (ALEF)
[0126]
(1) tert-butyl(4,4-bis(diethoxyphosphoryl)butyl)carbamate
[0127]
[0128] To tetraethyl-4-aminobutylidene-1,1-bisphosphonate (345 mg, 1.0 mmol) dissolved in 10 mL of dichloromethane were added Boc 2 O (218 μL, 1.0 mmol) and Et 3 N (139 μL, 1.0 mmol) at room temperature. The reaction mixture was stirred for 20 hr, the solvent was removed under reduced pressure, and the solution was concentrated. The crude product was purified by silica gel column chromatography using acetone as a solvent to give tert-butyl(4,4-bis(diethoxyphosphoryl)butyl)carbamate (267 mg, yield 60%) as a colorless oil.
[0129] 1 H NMR (500 MHz, CDCl 3 ) δ 1.29 (t, J=7.1 Hz, 12H), 1.38 (s, 9H), 1.71 (pent, J=7.1 Hz, 2H), 1.85-1.96 (m, 2H), 2.24 (tt, J=5.9, 23.9 Hz, 2H), 3.02-3.13 (m, 2H), 4.08-4.16 (m, 8H), 4.76 (br. s, NH);
[0130] 13 C NMR (125 MHz, CDCl 3 ) δ 16.2 (d, J=2.8 Hz), 16.9 (d, J=2.5 Hz), 22.6 (t, J=5.1 Hz), 28.3, 28.9 (m), 30.1 (t, J=132.6 Hz), 39.7, 62.4 (d, J=6.5 Hz), 62.5 (d, J=6.7 Hz), 78.8, 155.8;
[0131] HRMS (ESI) m/z Calcd for C 17 H 37 NNaO 8 P 2 [M] + 468.1892, found 468.1868.
(2) tert-butyl(4,4-bis(diethoxyphosphoryl)-4-fluorobutyl)carbamate
[0132]
[0133] To tert-butyl(4,4-bis(diethoxyphosphoryl)butyl)carbamate (220 mg, 0.49 mmol) dissolved in 12 mL of THF was added dropwise n-BuLi (338 μL, 1.6 M hexane solution, 0.54 mmol) at −78° C. under an argon atmosphere. After stirring for 10 min, N-fluorophenylsulfonimide was added to carbanion solution and the mixture was allowed to warm to room temperature over 1 hr. After stirring for 12 hr, the reaction was discontinued by adding 10 mL of ammonium chloride solution. A compound was extracted from the aqueous phase with ethyl acetate (2×10 mL), and the organic phase was blended, dehydrated over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure and crudely purified by silica gel column chromatography (solvent: acetone/ethyl acetate=1/1). The crude product containing tert-butyl(4,4-bis(diethoxyphosphoryl)-4-fluorobutyl)carbamate as the main component was directly used in the next synthesis reaction (184 mg, yield <82%).
[0134] 1 H NMR (500 MHz, CDCl 3 ) δ 1.36 (t, J=7.1 Hz, 12H), 1.43 (s, 9H), 1.82-1.88 (m, 2H), 2.12-2.26 (m, 2H), 3.09-3.20 (m, 2H), 4.20-4.33 (m, 8H), 4.62 (br. s, NH); HRMS (ESI) m/z Calcd for C 17 H 36 FNNaO 8 P 2 [M] + 486.1798, found 486.1811.
(3) 4-amino-1-fluoro-butylidene-1,1-bisphosphonic acid
[0135]
[0136] tert-Butyl (4,4-bis(diethoxyphosphoryl)-4-fluorobutyl)carbamate (100 mg, 0.22 mmol) was dissolved in 2 mL of 6N hydrochloric acid, and heated under reflux for 15 hr. The reaction mixture was concentrated under reduced pressure, whereby the solvent was removed. The residue was recrystallized from water/methanol to give 4-amino-1-fluoro-butylidene-1,1-bisphosphonic acid (15 mg, yield 74%) as a white solid.
[0137] 1 H NMR (500 MHz, D 2 O) δ 1.93-2.04 (m, 2H), 2.08-2.23 (m, 2H), 2.95-3.05 (m, 2H);
[0138] 13 C NMR (125 MHz, D 2 O) δ 21.7 (q, J=6.0 Hz), 29.3 (d, J=19.6 Hz), 39.5;
[0139] 19 F NMR (470 MHz, D 2 O) δ −189.5 (tt, J=23.8, 72.5 Hz);
[0140] HRMS (ESI) m/z Calcd for C 9 H 19 FNO 8 P 2 [M] − 250.0046, found 250.0069.
Example 4
Synthesis of 1-fluoro-(2-imidazoyl-1-ethylidene)-1,1-bisphosphonic acid (ZOLF)
[0141]
[0142] Tetrakisisopropyl-1-fluoro-(2-imidazoyl-1-ethylidene)-1,1-bisphosphonate (58 mg, 0.15 mmol) was dissolved in 1 mL of 6N hydrochloric acid, and heated under reflux for 12 hr. The reaction mixture was concentrated under reduced pressure, whereby the solvent was removed. The residue was recrystallized from water/methanol to give 1-fluoro-(2-imidazoyl-1-ethylidene)-1,1-bisphosphonic acid (42 mg, yield 99%) as a white solid.
[0143] 1 H NMR (500 MHz, D 2 O) δ 4.72-4.81 (m, 2H), 7.28 (s, 1H), 7.37 (s, 1H), 8.62 (s, 1H);
[0144] 13 C NMR (125 MHz, D 2 O) δ 51.2 (br. d, J=18.5 Hz), 118.7, 123.6, 135.9;
[0145] 19 F NMR (470 MHz, D 2 O) δ −189.8 (tt, J=25.7, 67.9 Hz, 1F);
[0146] HRMS (ESI) m/z Calcd for C 5 H 8 FN 2 O 6 P 2 [M] − 272.9842, found 272.9807.
Example 5
Synthesis of tetrakispivaloyloxymethyl-1-fluoro-2-(1H-imidazoyl-1-ethylidene)-1,1-bisphosphonate (ZOLF-POM)
[0147]
[0148] To potassium hydride (21 mg, 30%, 0.16 mmol) suspended in 2 mL of THF was added imidazole (11 mg, 0.16 mmol) at 0° C. under an argon atmosphere. After stirring at 0° C. for 1 hr, the mixture was stirred at room temperature for 30 min. This was cooled to 0° C., and 1.5 mL of a solution of tetrakispivaloyloxymethylvinylidene-1,1-bisphosphonate (100 mg, 0.16 mmol) in THF was added. This was stirred for 30 min, and 1.5 mL of a solution of 18-crown-6-ether (8.2 mg, 0.03 mmol) in THF was added. The reaction mixture was stirred for 15 min and selectfluor (82 mg, 0.23 mmol) was added. The reaction mixture was stirred for 17 hr, and the reaction was discontinued with 5 mL of aqueous ammonium chloride solution. A compound was extracted from the aqueous phase with ethyl acetate (2×10 mL), and the organic phase was mixed, dehydrated over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: acetone/n-hexane=l/1 to acetone/methanol=10/1). As a result, tetrakispivaloyloxymethyl-1-fluoro-2-(1H-imidazoyl-1-ethylidene)-1,1-bisphosphonate was obtained (30 mg, yield 26%).
[0149] 1 H NMR (500 MHz, CDCl 3 ) δ 1.23 (s, 36H), 4.67 (ddd, J=9.1, 10.3, 25.9 Hz, 2H), 5.60-5.71 (m, 8H), 6.96 (s, 1H), 7.02 (s, 1H), 7.51 (s, 1H);
[0150] 13 C NMR (125 MHz, CDCl 3 ) δ 26.8, 26.8, 38.7, 28.7, 48.1 (m), 82.8 (dt, J=3.2, 70.2 Hz), 120.7 (d, J=1.6 Hz), 129.2, 138.5 (d, J=1.2 Hz), 176.5, 176.6;
[0151] 19 F NMR (470 MHz, CDCl 3 ) δ −191.6 (tt, J=26.0, 71.8 Hz);
[0152] HRMS (ESI) m/z Calcd for C 29 H 49 FN 2 NaO 14 P 2 [M] + 753.2541, found 753.2502.
[0153] Methods using the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention as a lymphocyte-treating agent are specifically explained in Experimental Examples 1-5. The lymphocyte treatment method using the compound of the present invention is not limited to those specifically explained in the following.
[0154] The peripheral blood derived from each patient and used in the Experimental Examples was obtained from the patients hospitalized in the Nagasaki University Hospital and approved by the Nagasaki University Hospital clinical Research Ethics Committee.
Experimental Example 1 (FIG. 2 )
[0155] Heparin blood samples (peripheral blood 10 mL) were collected from adult T cell leukemia patients (1), and diluted with 10 mL of PBS. This was overlaid on 20 mL of Ficoll-Paque and subjected to density gradient centrifugation at 600×g for 30 min at room temperature. The layer directly above Ficoll-Paque was recovered, and washed 3 times with PBS to give peripheral blood mononuclear cells. The cells were suspended in 7 mL of Yssel medium, 1 mL therefrom was stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the left side in FIG. 2 , Vδ2 positive γδ T cells accounted for 0.75% of lymphocyte gate. The peripheral blood mononuclear cells suspended in Yssel medium were reacted with ZOLF-POM (1 μM), cultured for 11 days together with IL-2, stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the right side in FIG. 2 , Vδ2 positive γδ T cells accounted for 91.48% of lymphocyte gate. This shows that Vδ2 positive γδ T cells with high purity can be easily prepared in a large amount in 11 days from the peripheral blood mononuclear cells of adult T cell leukemia patients by using ZOLF-POM.
Experimental Example 2 (FIG. 3 )
[0156] Heparin blood samples (peripheral blood 10 mL) were collected from adult T cell leukemia patients (2), and diluted with 10 mL of PBS. This was overlaid on 20 mL of Ficoll-Paque and subjected to density gradient centrifugation at 600×g for 30 min at room temperature. The layer directly above Ficoll-Paque was recovered, and washed 3 times with PBS to give peripheral blood mononuclear cells. The cells were suspended in 7 mL of Yssel medium, 1 mL therefrom was stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the left side in FIG. 3 , Vδ2 positive γδ T cells accounted for 1.58% of lymphocyte gate. The peripheral blood mononuclear cells suspended in Yssel medium were reacted with ZOLF-POM (1 μM), cultured for 11 days together with IL-2, stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the right side in FIG. 3 , Vδ2 positive γδ T cells accounted for 96.83% of lymphocyte gate. This shows that Vδ2 positive γδ T cells with high purity can be easily prepared in a large amount in 11 days from the peripheral blood mononuclear cells of adult T cell leukemia patients by using ZOLF-POM.
Experimental Example 3 (FIG. 4 )
[0157] Heparin blood samples (peripheral blood 10 mL) were collected from adult T cell leukemia patients (3), and diluted with 10 mL of PBS. This was overlaid on 20 mL of Ficoll-Paque and subjected to density gradient centrifugation at 600×g for 30 min at room temperature. The layer directly above Ficoll-Paque was recovered, and washed 3 times with PBS to give peripheral blood mononuclear cells. The cells were suspended in 7 mL of Yssel medium, 1 mL therefrom was stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the left side in FIG. 4 , Vδ2 positive γδ T cells accounted for 0.49% of lymphocyte gate. The peripheral blood mononuclear cells suspended in Yssel medium were reacted with ZOLF-POM (1 μM), cultured for 11 days together with IL-2, stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the right side in FIG. 4 , Vδ2 positive γδ T cells accounted for 98.29% of lymphocyte gate. This shows that Vδ2 positive γδ T cells with high purity can be easily prepared in a large amount in 11 days from the peripheral blood mononuclear cells of adult T cell leukemia patients by using ZOLF-POM.
Experimental Example 4 (FIG. 5 )
[0158] Heparin blood samples (peripheral blood 10 mL) were collected from lung cancer patients (1), and diluted with 10 ml of PBS. This was overlaid on 20 mL of Ficoll-Paque and subjected to density gradient centrifugation at 600×g for 30 min at room temperature. The layer directly above Ficoll-Paque was recovered, and washed 3 times with PBS to give peripheral blood mononuclear cells. The cells were suspended in 7 mL of Yssel medium, 1 mL therefrom was stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the left side in FIG. 5 , Vδ2 positive γδ T cells accounted for 4.14% of lymphocyte gate. The peripheral blood mononuclear cells suspended in Yssel medium were reacted with ZOLF-POM (1 μM), cultured for 11 days together with IL-2, stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the right side in FIG. 5 , Vδ2 positive γδ T cells accounted for 98.59% of lymphocyte gate. This shows that Vδ2 positive γδ T cells with high purity can be easily prepared in a large amount in 11 days from the peripheral blood mononuclear cells of lung cancer patients by using ZOLF-POM.
Experimental Example 5 (FIG. 6 )
[0159] Heparin blood samples (peripheral blood 10 mL) were collected from lung cancer patients (2), and diluted with 10 mL of PBS. This was overlaid on 20 mL of Ficoll-Paque and subjected to density gradient centrifugation at 600×g for 30 min at room temperature. The layer directly above Ficoll-Paque was recovered, and washed 3 times with PBS to give peripheral blood mononuclear cells. The cells were suspended in 7 mL of Yssel medium, 1 mL therefrom was stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the left side in FIG. 6 , Vδ2 positive γδ T cells accounted for 1.95% of lymphocyte gate. The peripheral blood mononuclear cells suspended in Yssel medium were reacted with ZOLF-POM (1 μM), cultured for 11 days together with IL-2, stained with PE-labeled anti-human CD3 monoclonal antibody and FITC-labeled anti-human Vδ2 monoclonal antibody, and analyzed by flow cytometer. As a result, as shown in the panel on the right side in FIG. 6 , Vδ2 positive γδ T cells accounted for 95.72% of lymphocyte gate. This shows that Vδ2 positive γδ T cells with high purity can be easily prepared in a large amount in 11 days from the peripheral blood mononuclear cells of lung cancer patients by using ZOLF-POM.
[0160] Methods using the fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention as an antitumor immunostimulating agent are specifically explained in Experimental Examples 6-19. An antitumor immunostimulation method using the compound of the present invention is not limited to those specifically explained in the following.
[0161] In the Experimental Examples, the following tumor cell lines were used as the target of the detection of tumor cytotoxicity assay of Vδ2 positive γδ T cells. The number after the name of the cell indicates the source of supply.
[Source of Supply]
(1) Health Science Research Resources Bank
[0162] (2) supplied by Dr. Tatsufumi Nakamura, Nagasaki University
(3) supplied by Dr. Yoichi Nakamura, Nagasaki University monocyte tumor-derived U937 cells (U937)(1) monocyte tumor-derived P31/FUJ cells (P31/FUJ)(1) HCT-4 cells derived from HTLV-1 infected patients (HCT-4)(2) HCT-5 cells derived from HTLV-1 infected patients (HCT-5)(2) lung cancer-derived PC9 cells (PC9) (3) urinary bladder cancer-derived EJ-1 cells (EJ-1)(1)
Experimental Example 6 (FIG. 7 )
[0163] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 2×10 5 /200 μL, and seeded by 200 μL in a 96 well round bottom plate. The plate was centrifuged at 600×g for 2 min, and the supernatant was removed. A dilution series of 100 nM, 1 μM, 10 μM, 100 μM, 1000 μM was prepared for PAMF, ALEF, ZOLF, and a dilution series of 1 nM, 10 nM, 100 nM, 1 μM, 10 μM was prepared for ZOLF-POM. The compound solutions of the dilution series were added by 200 μL to the cell pellets after removal of the supernatant and incubated at 37° C. for 2 hr. The cells were washed 3 times with RPMI1640 medium, and 50 μL of Vδ2 positive γδ T cells derived from normal adult (1) and having a cell concentration of 2×10 5 /50 μL was added. Furthermore, PE-labeled anti-human CD107a monoclonal antibody (5 μL) was added, and the mixture was incubated at 37° C. for 2 hr. Thereto was added FITC-labeled anti-human Vδ2 monoclonal antibody (2 μL), and the mixture was incubated on ice for 20 min. This was washed 3 times with 2% FCS-added PBS, and suspended in 200 μL of 2% FCS-added PBS. This was analyzed by flow cytometer, the proportion of CD107a positive fractions in the Vδ2 positive cells was calculated, and the compound concentration dependency was summarized in the graph of FIG. 7 . As a result, a compound concentration that induces maximum CD107a expression was several hundred μM for PAMF, ALEF, ZOLF, whereas about 100 nM for ZOLF-POM. From the foregoing, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with fluorine-containing bisphosphonic acid and a fluorine-containing bisphosphonate derivative.
Experimental Example 7 (FIG. 8 )
[0164] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 1.25 μM, 2.5 μM, 5 μM was prepared for ZOLF-POM. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 8 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 1.25 μM ZOLF-POM.
Experimental Example 8 (FIG. 9 )
[0165] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 100 μM, 300 μM, 1000 μM was prepared for ZOLF. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 9 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 300 μM ZOLF.
Experimental Example 9 (FIG. 10 )
[0166] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 300 μM, 1000 μM, 3000 μM was prepared for ALEF. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 10 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 300 μM ALEF.
Experimental Example 10 (FIG. 11 )
[0167] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 300 μM, 1000 μM, 3000 μM was prepared for PAMF. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 11 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 300 μM PAMF.
Experimental Example 11 (FIG. 12 )
[0168] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 300 μM, 1000 μM, 3000 μM was prepared for IBAF. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 12 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 300 μM IBAF.
Experimental Example 12 (FIG. 13 )
[0169] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 100 μM, 300 μM, 1000 μM was prepared for ZOLF. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (2) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 13 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 300 μM ZOLF.
Experimental Example 13 (FIG. 14 )
[0170] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. The medium, ZOLF 500 μM solution or ZOLF-POM 5 μM solution was added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (3) were reacted at an effector cell/target cell ratio of 0.625:1, 1.25:1, 2.5:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 14 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 500 μM ZOLF or 5 μM ZOLF-POM.
Experimental Example 14 (FIG. 15 )
[0171] Human histiocytic tumor cell line U937 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. The medium, ZOLF 500 μM solution or ZOLF-POM 5 μM solution was added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (4) were reacted at an effector cell/target cell ratio of 0.625:1, 1.25:1, 2.5:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 15 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human histiocytic tumor cell line U937 with at least 500 μM ZOLF or 5 μM ZOLF-POM.
Experimental Example 15 (FIG. 16 )
[0172] Human monocyte tumor cell line P31/FUJ cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. The medium, ZOLF 500 μM solution or ZOLF-POM 5 μM solution was added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (3) were reacted at an effector cell/target cell ratio of 0.625:1, 1.25:1, 2.5:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 16 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human monocyte tumor cell line P3l/FUJ with at least 500 μM ZOLF or 5 μM ZOLF-POM.
Experimental Example 16 (FIG. 17 )
[0173] Adult T cell leukemia cell line HCT-5 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. The medium, ZOLF 1 mM solution or ZOLF-POM 1 μM solution was added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from adult T cell leukemia patients (4) were reacted at an effector cell/target cell ratio of 1.25:1, 2.5:1, 5:1, 10:1, 20:1, 40:1, 80:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 17 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting adult T cell leukemia cell line HCT-5 with at least 1 mM ZOLF or 1 μM ZOLF-POM.
Experimental Example 17 (FIG. 18 )
[0174] Adult T cell leukemia cell line HCT-4 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. The medium, ZOLF-POM 1 μM solution or ZOLF-POM 10 μM solution was added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from adult T cell leukemia patients (4) were reacted at an effector cell/target cell ratio of 1.25:1, 2.5:1, 5:1, 10:1, 20:1, 40:1, 80:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 18 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting adult T cell leukemia cell line HCT-4 with at least 1 μM ZOLF-POM.
Experimental Example 18 (FIG. 19 )
[0175] Human lung cancer cell line PC9 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 1.25 μM, 2.5 μM, 5 μM was prepared for ZOLF-POM. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from lung cancer patients (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 19 . From the results, it was clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human lung cancer cell line PC9 with at least 1.25 μM ZOLF-POM.
Experimental Example 19 (FIG. 20 )
[0176] Human bladder cancer cell line EJ-1 cells were suspended in RPMI1640 medium at a cell concentration of 1×10 6 /mL, and dispensed by 1 mL to a 15 mL conical tube. This was centrifuged at 600×g for 5 min, and the supernatant was removed. A dilution series of 0 μM, 1.25 μM, 2.5 μM, 5 μM was prepared for ZOLF-POM. The compound solutions of the dilution series were added by 1 mL to the cell pellets after removal of the supernatant and incubated at 37° C. for 1 hr 45 min. Thereto was added 10 mM lanthanoid metal chelating agent by 2.5 μL, and the mixture was further incubated for 15 min. These conical tubes were centrifuged at 600×g for 5 min, and the cell pellets were washed 3 times with RPMI1640 medium. Then, the cell pellets were suspended in 5 mL of RPMI1640 medium, 2 mL therefrom was placed in a different conical tube, and 6 mL of RPMI1640 medium was further added. The cell suspension was seeded by 100 μL in a 96 well round bottom plate. Vδ2 positive γδ T cells derived from normal adult (1) were reacted at an effector cell/target cell ratio of 0:1, 5:1, 10:1, 20:1, 40:1, and incubated for 40 min at 37° C. The plate was centrifuged at 600×g for 2 min, 25 μL of culture supernatant was taken, and diluted with 200 μL of europium-added acetate buffer. The mixture was taken by 200 μL, and time-resolved fluorescence was measured. The specific cytotoxicity rate was determined from the value of each sample, and the effector cell/target cell ratio dependency was graphically shown in FIG. 20 . From the results, it was m clarified that the sensitivity to a cytotoxicity activity of Vδ2 positive γδ T cells is promoted by reacting human bladder cancer cell line EJ-1 with at least 1.25 μM ZOLF-POM.
INDUSTRIAL APPLICABILITY
[0177] The novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention becomes a superior Vδ2 positive γδ T cell activator when it is reacted with the peripheral blood. When it is reacted with tumor cells or virus infected cells, it promotes sensitivity to a cytotoxicity action of Vδ2 positive γδ T cells, and functions as an antitumor or antiviral agent. From these findings, antitumor immunotherapy and antiviral infection treating method using the novel fluorine-containing bisphosphonic acid and/or a fluorine-containing bisphosphonate derivative of the present invention can be established. Specifically, peripheral blood mononuclear cells of cancer patients or virus infection patients are prepared, and cultured ex vivo in the presence of the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention and IL-2 to induce proliferation of Vδ2 positive γδ T cells. The cells are intravenously or topically administered to the patients, whereby immunotherapy of cancer and virus infection, which utilizes Vδ2 positive γδ T cells, becomes possible. In addition, immunotherapy of cancer and virus infection, which utilizes Vδ2 positive γδ T cells, becomes possible by directly administering the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention to cancer patients or virus infection patients. In this case, the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is incorporated into monocyte cells, and the fluorine-containing bisphosphonic acid directly inhibits farnesyl diphosphate synthase, and the fluorine-containing bisphosphonate derivative undergoes hydrolysis of the ester, is converted to fluorine-containing bisphosphonic acid and inhibits farnesyl diphosphate synthase. Due to the inhibitory action, isopentenyl diphosphate, which is a metabolite located directly upstream of the enzyme, is intracellularly accumulated. Isopentenyl diphosphate binds to an intracellular region of the butyrophilin 3A1 molecule present in the cellular membrane, and changes the conformation of the extracellular region or changes the degree of polymerization. The change is recognized by Vδ2 positive γδ T cells, and proliferation stimulation is produced. The proliferated γδ T cells show high tumor cytotoxicity, and high virus infected cell toxicity. On the other hand, the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention is incorporated into tumor cells and virus infected cells, during which a phenomenon similar to the changes in the monocytes occurs. That is, the fluorine-containing bisphosphonic acid directly inhibits farnesyl diphosphate synthase, and the fluorine-containing bisphosphonate derivative undergoes hydrolysis of the ester, is converted to the form of an acid and inhibits farnesyl diphosphate synthase. Due to the inhibitory action, isopentenyl diphosphate, which is a metabolite located directly upstream of the enzyme, is intracellularly accumulated. Isopentenyl diphosphate binds to an intracellular region of the butyrophilin 3A1 molecule present in the cellular membrane, and changes the conformation of the extracellular region or changes the degree of polymerization. The change is recognized by Vδ2 positive γδ T cells, and tumor cells and virus infected cells are efficiently injured. In this way, antitumor immunotherapy and antiinfection immunotherapy using the novel fluorine-containing bisphosphonic acid or fluorine-containing bisphosphonate derivative of the present invention become possible.
[0178] The compound of the present invention in an oil form is superior in solubility and preferably administered as a medicament.
[0179] This application is based on a patent application No. 2015-018260 filed in Japan (filing date: Feb. 2, 2015), the contents of which are incorporated in full herein.
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A series of fluorine-containing bisphosphonic acids in which an alkylamine side chain is added, a series of fluorine-containing bisphosphonic acids in which an amino group substituted by a heterocyclic group or a heterocyclic group containing a nitrogen atom is added, to the carbon atom of P—C(F)—P, and a series of fluorine-containing bisphosphonate derivatives in which the acid moiety thereof is esterified by an alkoxymethyl group such as POM group, n-butanoyloxymethyl (BuOM) group and the like, that is, the fluorine-containing bisphosphonic acid and fluorine-containing bisphosphonate derivative represented by the following formula (I):
wherein each symbol is as defined in the DESCRIPTION, can efficiently induce proliferation of peripheral blood γδ T cells that express Vγ2Vδ2 T cell receptor having superior cytotoxicity against tumor cells and virus infected cells, immunize tumor cells and virus infected cells, and can induce cytotoxicity by γδ T cells.
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FIELD OF THE INVENTION
The invention is principally in the field of magnetic resonance apparatus and relates particularly to efficient control of time sensitive functions of such apparatus.
BACKGROUND OF THE INVENTION
Many instrument applications require the creation and maintenance of a precisely timed event stream. Frequency agile radar, arbitrary radio frequency (RF) generation, pulsed magnetic field sources, time domain instrumentation such as NMR spectrometers, MRI imagers and the like, are a few examples. Such apparatus may be described in an instantaneous sense as existing in a well define “state”. The state in turn, is described by the quantitative condition of each of the independent variables of the apparatus. By way of a simple example, an RF synthesizer operating to produce a desired waveform from N frequency components may specify the frequency component(s), with corresponding values of amplitude, phase, state duration and perhaps a waveform repetition rate for 3N+2 variables to specify the state. The RF waveform may also be controllable as to shape, or time dependence with further computational burden. These parameters may repeat, repeat with changes in some parameters, repeat in a cyclic manner, etc., to produce the desired operation. A module that assembles the serial stream of states and provides the stream to the several sub-devices of the apparatus is referenced herein as a controller.
Another time sensitive function in an NMR device which is the subject of a controller operation is the management of magnetic gradients. In each of k spatial coordinates, a magnetic gradient is specified by ∂B z /∂X (k) (t), (that is, the time profile, or shape), the time for gating this quantity “on” and the duration. Again, a vector gradient pulse may be selectable in time dependence by ordering the instantaneous ordinate values, and the orientation of the resultant vector is determined from the vector sum of its components, each of which is the product of a corresponding controller.
Very early, the control function was implemented in a digital processor on an interrupt actuated basis where differing levels of priority were assigned to multiple tasks required for the operation of the apparatus. The processor, while executing some lower priority task, would receive an interrupt to activate a higher priority task, such as controlling the status of modules comprising the apparatus, e.g., an NMR instrument. In the case of an NMR instrument, RF excitation in the form of multiple RF pulses of diverse nature, magnetic field gradients, data acquisition, precise delays between various states and other operational parameters and logical values, all define the instantaneous state to be retrieved from memory for presentation to appropriate command buffer(s). The processor, in this generic prior art structure, might intersperse these higher priority functions with lower priority tasks as allowed by the interrupt structure. This presented a ponderous procedure with considerable complication in the software. Specific examples representative of such prior architecture are the NMR instruments manufactured by Varian under the name “Unity”.
In further developing prior art, a controller processor, communicating with a separate host processor, offered greatly improved synchronous properties in sequencing the states of the apparatus. A host processor performs high level operations including description of the NMR pulse sequence in terms of parameter values defining the pulse sequence at consecutive time increments (as well as conducting post acquisition operations). The current operational information is placed by the host on a bus communicating with (output) controller processor(s) that operates to establish the sequence of physical states of RF power and magnetic field gradient. This division of resources separates the synchronous operations of the RF power source, transmit/receive switch and gradient power supplies from the time non-critical operations of the host.
The prior art controller shown in FIG. 2 a derives fundamental instruction from a host computer 34 , through a bus interface 92 to a controller memory 94 . A state machine (stuffer) 96 assembles parameter values associated with selected controlled devices 101 , 102 , etc and the duration to associate with that macro-state of the apparatus defined by parameter values of all controllable devices contributing to the state of the apparatus. This triplet of data (device, parameter value, duration) is serially directed (stuffed) to the various controllable devices.
The prior art controller function of FIG. 2 a presents device select, duration and parameter values to an output bus 100 , common to the controllable devices that determine the state of the apparatus. Consequently, the rate at which the state of the system may be altered is distinctly limited because multiple parameter changes require a corresponding multiple device select instructions. Where the devices 101 , 102 , etc., retain their respective parameter values as previously set (that is, NRZ type devices), it follows that only changes to these values need be passed through the bus and ultimately, this type of controller may be regarded as a memory efficiency benchmark.
An advance in prior art controller apparatus is shown in FIG. 2 b wherein the structure is similar to that of FIG. 2 a with the exception that all controlled devices are addressed in parallel through independent control signals from the output of asynchronous-to-synchronous buffer 98 . Buffer 98 is preferably a FIFO device wherein the (internal) clocking of the buffer content is derived from a field of a buffer word and this time datum determines the persistence time, or duration of the state. A device such as FIFO 98 , or the equivalent provides for conversion of the asynchronous event stream to implementation of a synchronous sequence of physical states. The FIFO has a width (the FIFO word) sufficient to define the system state instantaneously. The FIFO also has a depth, that is, a forward store of consecutive states including therein, the duration of the corresponding state. It is a major function of the processor 96 to write states to the FIFO at such rate to avoid an underflow condition and similarly to avoid a FIFO overflow condition. The FIFO status depends upon the state duration that is specified within the FIFO word and thus remains independent of the activity of processor 96 . Such self clocked FIFO buffers are the subject of U.S. Pat. Nos. 4,191,919 and 4,375,676, commonly assigned herewith. The speed limiting aspect of separately addressing each controlled device is therefore eliminated. The buffer 98 must now accommodate a substantially wider buffer word in order to convey to each device, its parameter value(s), but the state duration is directly controlled from the buffer output. A more subtle limitation is imposed on the memory 94 . Because all controlled devices are set to desired parameter values, the memory 94 must accommodate the entire definition of each of the successive states of the apparatus. For magnetic resonance systems, the event stream for a measurement may require of the order of 10 8 words to be written from buffer 98 . This word stream passes through memory 94 , imposing a significant requirement on memory size and speed. In spite of this memory limitation, prior art of this type represents a speed benchmark.
A further advance in prior art replaces the state machine stuffer 96 with an intelligent processor 97 as shown in FIG. 2 c . Data to create the necessary stream of state definitions from stored data, computation or a combination thereof is treated by processor 97 and the fully assembled state description is presented to the FIFO 98 . It is important to recognize that processor 97 attends to several functions: unloading of buffered data from the bus, reassembly of the state with possibly required computation (including masking and updating the state where only state changes are transmitted on the bus and saving the now updated state for reference in forming the next state), and managing the output to the FIFO 98 to assure the operation is neither too soon nor too late. The computational load and the data management burden each lead to extreme situations which strain both memory capacity and transfer rate as applied to prior art systems. Exemplary prior art are the NMR instruments manufactured by Chemagnetics under the name “Infinity”.
A modern fourier transform NMR instrument executes a complex retinue of instructions affecting the instantaneous RF and magnetic attributes of a sensitive volume within a magnetic field. The sensitive volume may contain a substance examined for analytical study, or an object, the internal volume of which is imaged through exploitation of magnetic resonance phenomena. For example, various measurement techniques commonly require precise control of RF phase, RF pulse shape and RF amplitude and precise cycling of phase over different phase angles as applied to the content of the sensitive volume of the instrument. Many measurement techniques require application of magnetic gradient pulses to the sensitive volume, with similar requirements to phase, shape, direction and amplitude. The gradients may be independent in magnetic component and spatial dependence requiring independent sets of control apparatus. The instantaneous specification of these parameters expresses the output state of the controller. The sequence of states defines the preparation of the magnetic resonance measurement. Acquisition of spectral data represents another instrumental state commencing with precise relative timing.
A realistic specification for the functional requirements of a modern NMR instrument include the precision required for the parameters describing a state, required gating instructions and the relevant time intervals and data rates. Table I summarizes desirable precision for an RF controller and table II represents a similar summary for a vector controller as employed for typical NMR apparatus.
TABLE I
Parameter
#. bits
amplitude
16
phase
16
attenuator
8
gates
8
state duration
26
multiplexer
16
TABLE II
Parameter
# bits
amplitude X
16
amplitude Y
16
amplitude Z
16
state duration
26
It could be observed that an arbitrary controller characterized by extremely fast clocking could satisfy the requirement of aligning instrumental states on a precise time scale. The practical limit for the apparatus is not the limit of what might be achieved, but rather the requirements of the instrumental function. The physical phenomena to be observed (NMR spectra or images) are manifest in the first instance as line widths, chemical shifts, J coupling and the like, typically represented in approximately 5 MHz of bandwidth. MRI conveys spatial distributions with emphasis on spatial resolution and dynamic range, typically consuming 2 to 5 Mhz bandwidth. Assuming a 20 MHz bandwidth requirement, there is suggested a fundamental unit of time alignment for instrumental states of the apparatus of, say, 50 ns. As table I illustrates, the description of a state might require 70 bits. At a fundamental state duration of 50 ns, the system must supply states at the transfer rate of 1400 Mbits/sec. Although contemporary processors operate at such clocking frequencies, it is necessary to observe that the hypothetical 1400 Mbits/sec is a transfer rate. The sequential states of the NMR apparatus must be created (computed or derived from memory) and revised (scaling, phase cycling, vector rotation, etc) and these creation and revision operations are instrumentally and/or computationally intensive with resulting limits on the rate of physical state evolution controlling the apparatus.
A representative contemporary commercially available NMR system is the Varian INOVA® featuring a minimum time resolved state duration of 100 ns. For this system, two synchronized RF modules transfer a total of 60 bits suggesting a transfer rate of about 600 MHz whereas the operational rate for the control processor is 160 MHz. This rate disparity or gap is accommodated by very large buffers (which also present limitations for such use).
Another example of prior art is a waveform controller/synthesizer described in U.S. Pat. No. 4,707,797.
As pointed out above, a progression of many billions of well define instrumental states may be required for NMR measurements of only moderate complexity. In the limit of a large gap between a sustained state evolution rate and the control processor transfer rate, extremely massive buffering becomes economically impractical to narrow that gap. The design philosophy problem may be summarized with the observation that any high speed processor driven instrument system may be regarded as having a finite write rate, Ω, and a finite read (or evolution) rate, ρ. For the earliest prior art in an NMR application, the demand upon instrumental process rate was minimal. As the demand for higher resonance frequencies and greater complexity in the prescription of the instantaneous state increased, various schemes were implemented to narrow that excess of the state evolution rate over the rate at which state data is presented to hardware. The creation of the state sequence and formatting of those states to output devices represents a considerable computational burden and measures which reduce that burden are desirable. It should be recognized that in addition to the recognizable computational burden there is a time consuming formatting task necessary to reduce computed parameters to elements of a state descriptor. The excess of the read rate over the write rate may be accommodated by a buffer stage with accompanying requirements that become onerous as the aforesaid gap increases. The RF and vector controllers of the present invention may be viewed as specific measures interspersed between the state sequence generating processor and those output devices to which the state is written. Reduction of the aforesaid rate gap should be recognized as enabling a maximum sustained rate of device instructions processed to approach a maximum (hardware defined) write rate to external devices.
SUMMARY OF THE INVENTION
The controller of the present invention narrows the above described gap in implementing two major strategies. First, the controller architecture retains elements of the state in latched registers that retain their content until rewritten to different content. This reduces the bulk transfer rate burden when the form of the state sequence is reduced to specification of the changes in the contemporaneous state over the preceding state. Second, concurrently with transactions updating other latched registers defining the state description, a computational layer of the controller executes common mathematical operations, specialized for the corresponding fields of the status bits in parallel. These computations are implemented with application specific integrated circuits, executing in parallel within a clock cycle, thereby introducing no rate limiting step(s). Further, this strategy eliminates the need for extensive data packing. As a result, the aforesaid gap is either eliminated, or reduced for manageability through high speed FIFO buffering of modest proportion.
The present invention is directed to a novel controller architecture for control of an NMR instrument wherein the structure allocates certain computational activity within a long sequence of states to occur within a controller possessing both a computational layer and a latched register layer. These layers receive information from a data bus. A latched register retains content unless and until overwritten; thus the prior datum for the corresponding register is preserved if not subject to change. Content of these registers comprise all parameters essential to description of the state including the state duration. Consequently, only changes in status elements, including state duration, need be transmitted on the bus. Certain elements of the state description are derived by computation from parameters of the state description. These operands may or may not exhibit changes between consecutive states. Computational operations are typically addition (for example, adjustment of RF phase), multiplication (such as the scaling of the ordinate of a standard pulse shape) and matrix multiplication (to realize desired rotations of a magnetic gradient vector for NMR measurements). Concurrently active independent RF channels incorporate respective controllers of the invention and magnetic gradient operations are directed through a separate gradient controller.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 represents a magnetic resonance apparatus incorporating a controller according to the present invention.
FIG. 2 a shows one prior art controller arrangement.
FIG. 2 b shows another prior art arrangement.
FIG. 2 c shows yet another prior art arrangement.
FIG. 3 illustrates a dual level register based controller of the present invention FIG. 4 shows another register based controller of the present invention.
FIG. 5 is another embodiment comprising additional functionality in the register layer.
FIG. 6 schematically describes an embodiment of the inventive controller for vector control.
While the invention is susceptible to various modifications and alternative forms, the above figures are presented by way of example and/or for assistance to understanding the structure or phenomena. It should be understood, however, that the description herein of the specific embodiments is not intended to limit the invention to the particular forms disclosed, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined in the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
The representative physical context of the invention is an NMR apparatus that includes a number of devices to be controlled in synchrony. An idealized illustration is shown in FIG. 1 . A magnet 10 having bore 11 provides a main magnetic field along the axis of the bore. In order to control the magnetic field with precision in time and direction for selected measurements requiring magnetic field gradients, there are provided magnetic field gradient coils (not shown). These are driven by gradient power supplies 16 , 18 and 20 , respectively. Additionally, other shimming coils (not shown) and power supplies (not shown) may be required for compensating residual undesired spatial inhomogeneity in the basic magnetic field. An object for analysis (hereafter “sample”) is placed within the magnetic field in bore 11 and the sample is subject to irradiation by RF power, such that the RF magnetic field is aligned in a desired orthogonal relationship with the magnetic field in the interior of bore 11 . This is accomplished through one or more transmitter coil(s) 12 in the interior of bore 11 . Resonant signals are induced in a receiver coil, proximate the sample within bore 11 . The transmitter and receiver coils may be the identical structure, or separate structures.
As shown in FIG. 1 , RF power is provided from first transmitter 24 a through modulator 26 a , and is amplified by an amplifier 31 a and then directed via transmit/receive (T/R) isolator 27 to the probe 12 that includes a first RF transmitter coil 12 ′ located within the bore 11 . The transmitter 24 a may be modulated in amplitude or frequency or phase or combinations thereof, either upon generation or by a modulator 26 a . The conceptual grouping of transmitter 24 a , modulator 24 a , amplifier 31 a , T/R isolator 27 and the receiver is conventionally called the “observe channel”. Additional components (transmitter 24 b /modulator 26 b /amplifier 31 b ) forming the “decoupler channel”) are often employed to independently manipulate different gyromagnetic resonators coupled to the species under investigation, e.g., 13 C or 1 H. These independent spin manipulations are conveniently supported by multiple coils or a multi-resonant coil. Transmit and receive functions are clearly not concurrently active in the observe channel. The identical observe coil 12 within the probe may be employed for both excitation and acquisition if so desired. Thus, the T/R isolator 27 is provided to separate the receiver from the transmitter 24 a . In the case of separate transmitter and receiver coils, element 27 will perform a similar isolation function to control receiver operation.
The modulators 26 a,b (or the equivalent) are responsive to controller 38 a,b including pulse programmer(s) 29 to provide RF pulses of desired frequency, amplitude, duration and phase relative to the RF carrier at precise pre-selected time intervals for application to corresponding channels. The pulse programmer may have hardware and/or software attributes. The pulse programmer also controls the gradient power supplies 16 , 18 and 20 , if such gradients are required. These gradient power supplies may impose gradient pulses or maintain selected static gradients in the respective gradient coils if so desired. Each such gradient is specified by gradient amplitude, e.g., +/−∂B z /∂y, duration, time of initiation.
The transient nuclear resonance waveform processed by receiver 28 is ordinarily resolved in phase quadrature through phase detector 30 . The phase resolved time domain signals from phase detector 30 are presented to Fourier transformer 32 for transformation to the frequency domain in accordance with specific requirements of the processing. Conversion of the analog resonance signal to digital form is commonly carried out on the phase resolved signals through analog to digital converter (ADC) structures which may be regarded as a component of phase detector 30 for convenience.
It is understood that Fourier transformer 32 may, in practice, act upon a stored (in storage unit of processor 34 ) representation of the phase resolved data. This reflects the common practice of averaging a number of time domain phase resolved waveforms to enhance the signal-to-noise ratio. The transformation function is then applied to the resultant averaged waveform. Display device 36 operates on the acquired data to present the distribution for inspection. In an NMR apparatus, master controller 38 , most often comprising one or more digital processors, controls and correlates the time critical operations, such as the performance of pulse sequences in the observe channel, the decoupler channel and the several gradients. Master controller 38 may be regarded as a plurality of distinct functional controllers (RF observe channel, RF decoupler channel and magnetic gradient, for example), each of which ordinarily operates to produce states synchronous with a common time base for maintaining synchrony with resonant spin systems. Overall operation of the entire apparatus within host processor 34 includes input 37 from operating personnel, non-time critical calculation and output for further processing or display.
Turning now to FIG. 3 , there is shown a block diagram representative of a preferred embodiment of a controller of the present invention. The central features of the controller are evident in the register layer 100 and the computation/logic layer 104 . The register layer comprises a plurality of latched registers 102 a , 102 b , . . . 102 k . Each of these registers retain a digital (or logical) parameter effecting the output state of the controller. The content of each of the latched registers of register layer 100 is retained in the respective register until overwritten by processor 96 . The register layer is further distinguished as comprising two species of latched register in accord with the destination of the register content. In the symbolic description of FIG. 3 , registers 102 i . . . 102 k contain values for direct transfer to the asynchronous buffer 98 . Registers 102 a . . . 102 d communicate with corresponding computational cells, such as 106 s and 106 a representing a computational layer 106 . Typical computational operations include scaling (integer multiplication) an instantaneous amplitude to transform a normalized pulse shape to a desired scale; and addition, such as when accumulating phase from phase increments. Computational cells 106 s and 106 a are realized in known fashion from specialized high speed logic circuits such as field programmable arrays (FPGAs) and such cell includes a latched result register to retain the computed result. Such latched mathematical result register is in correspondence to arguments of the calculation as presented from the relevant latched registers 102 a , . . . etc.
Note that the processor 96 exhibits an output rate p to the register layer 100 and the register layer exhibits a certain theoretical maximum write rate Ω to the asynchronous buffer 98 , which may be limited by the presence of a (partially) intervening computational layer 104 . Data from non-computational registers 102 j , 102 k and computational results from cells 106 s and 106 a are gated to write to the asynchronous buffer 98 by a common signal which is derived from the slowest computation, or alternatively from a logical AND of DATA READY levels available from registers of register layer 104 and computational cells of computational layer 106 . Such gating arrangements are well known to practitioners of the art.
Plural RF controllers coexist in some apparatus that require different RF channels that are concurrently active, whether or not these channels are independent. An example of this requirement is found where proton and C 13 spins are separately and concurrently manipulated, as is common in a wide variety of experiments
It has been noted above that it was known practice in prior art to reduce traffic on the system bus by description of the state sequence only through the changes therein to appear in the controlled output. In such prior art architecture the prior state was reconstituted in the controller from a stored image and the changes effected and re-stored and concurrently transferred to the asynchronous buffer. The present invention avoids such operations in the controller processor because the prior state is preserved in the corresponding set of latched registers 102 a . . . 102 k . In this way, the compression achieved by the state differential sequence description is perfected in the present invention.
The organization of the controller of FIG. 3 reduces the burden on processor 96 to the function of managing the inflow of data (comprising changed parameters of consecutive state pairs) from the bus interface and the outflow of updated state parameters into the asynchronous buffer. This is a time sensitive function because of the need to perform these manipulations within a range of operational speed that is neither too rapid (overrunning the asynchronous buffer 98 ) nor too slow (allowing underflow of asynchronous buffer 98 ).
A description of controller operation is a conventional RF controller. Such controller processor accepts the download of the program, which it will execute during the full course of the (NMR) experiment. The controller program to be executed in a particular RF channel contemplates a sequence of pulses of selected shape and frequency content, having specified phase properties, amplitude and pulse width, delays between pulses, and receiver gating. Assume a phase cycling procedure where the phase may be cycled in a selected manner, the length of the interval from receiver gated ON to receiver gated OFF may be set, and the number of repetitions determined. Phase cycling requires a phase increment to be initialized in the phase addend register, for example, and the cycling corresponds to creation of a corresponding looping regime within the controller. The appropriate controller program is composed at the host processor and delivered through the bus interface 92 for initialization by the intrinsic program loading facility of the processor 96 . Now consider the present invention: the advantage of latched registers 102 a . . . removes the unchanged state variables from any equivalent prior art software loop wherein masking of state descriptor words is carried out with consequent economy for the present invention in both transfer rate, computational burden and the like. Within the core of the interface (between the bus and the FIFO) the computational layer 104 removes computational burden altogether from the processor while executing these operations at a point in time adjacent to FIFO servicing operations.
Another embodiment is the simplified controller of FIG. 4 . This embodiment differs from the embodiment of FIG. 3 in that there is no mathematical layer and the advantage gained is that of the latched register layer alone. For NMR applications this is not a preferred arrangement inasmuch as computational operations on state variables offers a major advantage in operational efficiency. The advantages of the latched register structure alone are sufficient for a wide range of applications requiring lengthy sequences of synchronous states.
In another embodiment, an incremental register layer 106 comprises capability for modification of the arguments provided to the computational layer 104 in a prescribed sequential manner from a single datum in the data stream transmitted over the bus 92 . It should be readily appreciated that this capability contributes great additional compression in the data stream and thereby further narrows the gap between the achievable write-rate from the host computer and the required read-rate of the various output devices that implement and record the NMR phenomena. FIG. 5 shows a logical schematic of the incremental register layer 106 . A representative register 106 i ′ accommodates a subfield 140 corresponding to an argument to be presented to the computational layer 104 , another subfield 142 is treated as an increment (decrement) to the argument 140 while the remaining subfield 144 is a repetition count for adjusting the argument. Within layer 106 ′, the argument value 140 and the increment 142 are supplied to adder 302 and the resulting adjusted value argument is restored to the latched register 106 i ′ while also being presented to the computational layer under control of the latch 300 . The latch 301 presents the entire register layer 106 to the computational layer 104 , together with a data ready gate. This embodiment enables a single instruction to the controller to create a sub-sequence of numerous states in accord with the content of the repetition field 144 .
Another application of the inventive controller architecture is also to be found in vector manipulation. Vector control in high speed processes requires control of magnitude (scaling), rotations and time dependence. For magnetic resonance apparatus the manipulation of a magnetic gradient vector underlies many methods of magnetic resonance imaging (and to a lesser extent, certain spectroscopic measurements). For example a 3D image might impose a resultant magnetic gradient vector of different orientations at different times. Components of the gradient vector G are typically ∂B z /∂B x , ∂B z /∂B y , ∂B z /∂B z and these are furnished by room temperature coil windings where z is the direction of the polarizing field. The alignment of the resultant gradient vector is rotated in correspondence with the functional aspect of gradient formation. One typical class of 3D imaging sequences imposes a slice selection gradient during the RF excitation pulse resulting in excitation of nuclear spins in a selected 2D thickness of the sample forming a plane having a desired orientation. All components may be energized in corresponding magnitudes to yield the desired orientation. Mutually orthogonal phase encoding and readout gradients are similarly energized at requisite times to identify the magnetic resonance response of a pixel or line of the image. The process is repetitive in building the image incrementally by cycling through values of the slice selection, phase encode and readout gradients yielding a free induction decay waveform for each such triplet of gradient directions and intensities. The magnetic gradient resultant is thus subject to a triply cyclic program of discrete rotational increments for such imaging. The mathematical prescription of (3 dimensional) spatial rotation of the resultant gradient is prescribed by a rotation matrix R where R is a 3×3 array and the gradient controller effectuates the rotated vector G′ from matrix operators,
G′=G ( R )
Vector rotation (and scaling) requires operations for matrix multiplication, as for example
G
′
(
X
,
Y
,
Z
)
=
(
R
11
R
12
R
13
R
21
R
22
R
23
R
31
R
32
R
33
)
(
G
X
G
Y
G
Z
)
FIG. 6 describes the organization of functional operations required for a computational layer 204 to perform the rotational aspects of the above operations described above. For simplicity, vectors X, Y, and Z may be regarded as the unrotated components of G. The inputs α 1 , α 2 , and α 3 represent the triads of coefficients for each of the three rows of the rotation matrix. The quantities “Scale 1 ”, “Scale 2 ”, and “Scale 3 ” are the scaling factors to be applied to each of the three rotated components to establish the vector magnitude. It is clear that each vector component requires four multiplications and two additions to be implemented in a computational layer. FIG. 3 should be regarded as the framework within which FIG. 6 performs the manipulations for vector control through such a computational layer 204 (analogous to computational layer 104 for the RF controller).
The matrix multiplication is carried out in the computational layer 204 from vector components and array elements residing in the latched register layer (analogous to RF controller register layer 102 ). Recall that not all of these quantities change across state transitions. A gradient vector in three dimensional space, subject to rotations and scaling therefore requires control for each of three gradient basis vectors, all of which must maintain excellent mutual synchrony to produce the desired instantaneous resultant vector.
The guiding architecture for the software/firmware for operating the apparatus is founded on three observations. First, consider the central requirement for the execution of very long sequences of distinct states. Each state is prescribed by a number of parameters and in most applications, the difference between adjacent states is usually to be found in a one or two parameters, perhaps three, rarely more than three. The entire sequence of states is representative as a succession of changes beginning with an initial, or default state. Thus it is only necessary to describe the sequence by the difference of adjacent states including the state durations and such procedure is perfected by retention of state parameters within latched registers of the controller, as above described, in such manner as to obviate reconstituting the entire prior state. A vast economy is achieved in both memory and process steps for establishing each state in this manner.
The major requirement for these controllers is maintenance of precise synchrony. This necessitates both high speed attributes for the hardware driven, efficient data structures and the means for efficiently transforming a state description into a physical state. The controller herein described includes an asynchronous device. More particularly, it incorporates asynchronous-to synchronous conversion, while the self-clocked FIFO structure(s) provide hardware realization of a synchronous train of events from a sequence of prescribed digital states. There remains an intermediate problem in assuring that asynchronous software operations of loading/updating do not overrun/underrun the rate of FIFO output. This task is a greater focus of the controller processor herein by reduction of other computational burden through the computational layer of the controller and reduction in data transfer through retention of unchanging data in latched registers of the controller.
The asymptotic behavior of actual sustained rate performance of any such controller may be appreciated by recognizing that there is a hardware defined maximum rate for accepting input datums by the FIFO. Assume a FIFO accommodating a sequence of L states and that this maximum FIFO read rate is identical to the maximum FIFO output or write rate. If state descriptors are supplied to such a FIFO of depth L states, at the maximum FIFO read rate, a synchronous state description is achieved at the FIFO input and the sustained rate equals the maximum FIFO read rate for an indefinite number of n*L states. As a practical matter, the act of supplying the state descriptor includes the essential computations, data transfer and controller operations discussed herein (and separately, the FIFO clocks out individual states for significant durations). For purposes of discussion, assume the processing of an individual state requires an additional unit λ of clock time (on the average) for each set of L states, the system and controller “above” the FIFO falls behind the FIFO read rate (which we may regard as a characteristic maximum rate) by an incremental amount, or rate gap. However on these suppositions the theoretical maximum number of states accommodated in sustained synchronicity simply becomes L (L−λ). The present invention serves to reduce the number of operations required above the FIFO, with the result that the construct designated λ is greatly reduced as is the gap between sustained (asynchronous) rate of states presented to the FIFO and the maximum hardware defined state acceptance rate, for a given length state sequence. An alternative view of this is to consider the average duration T d per state in a very long sequence and an average processing time per state T p (including all relevant computation, data transfer and controller processes). It may be shown that the number of states N accommodated before underflow of the FIFO is
N=L (1 +T p /( T p −T d ))
As the time gap T p −T d is reduced (a goal of this invention), the quantity N/L increases and increased FIFO depth becomes a less stringent requirement for preservation of long synchronous state sequences.
One will appreciate that quantitative evaluation of hardware built according to the invention depends significantly upon the nature of the state variations forming the sequence. It has been observed that for relatively simple NMR state sequences involving phase and scale manipulations, an RF controller following the present invention has been observed to support a factor of two increase in sustained rate of state sequence presentation compared to prior art. The (vector) magnetic gradient controller exhibits capability for an order of magnitude increase in such sustained rate over prior art for comparable state sequences.
Although this invention has been described with reference to particular embodiments and examples, other modifications and variations will occur to those skilled in the art in view of the above teachings. It should be understood that, within the scope of the appended claims, this invention may be practiced otherwise than as specifically described.
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A controller for apparatus assuming a sequence of precisely synchronized states in accordance with a lengthy event stream is realized in an architecture comprising a register layer comprising a plurality of latched registers for receiving event descriptors and parameters from a bus and a computational/logical layer for operations on/among certain of said parameters for presentation to external operational devices. An RF controller controlling frequency, pulse width, amplitude with precise timing for magnetic resonance applications is one example and a magnetic gradient controller controlling vector magnitude and orientation is another.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to chemical recycling.
More particularly, the present invention relates to means for obtaining energy from waste products by the pyrolysic process using exhaust gas from an internal combustion engine or turbine.
2. Description of the Prior Art
Numerous innovations for chemical recycling have been provided in the prior art that are adapted to be used. Even though these innovations may be suitable for the specific individual purposes to which they address, they would not be suitable for the purposes of the present invention as heretofore described.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an apparatus for obtaining energy from waste products avoids the disadvantages of the prior art.
More particularly, it is an object of the present invention to provide an apparatus for obtaining energy from waste products that utilizes waste and heat from exhaust gases to obtain mechanical energy and chemical by-products, such as benzene and naphathaline, in addition to the metal collected. The exhaust gas produced by the use of the present invention is safe and will not poison the environment in which it functions.
In keeping with these objects, and with others which will become apparent hereinafter, one feature of the present invention resides, briefly stated, in an apparatus using fluid from a cooling system of an internal combustion engine for obtaining energy from waste products, and comprising an upper tank for receiving the waste products, a heating system for heating the upper tank by using the fluid from the cooling system of the internal combustion engine, so that the waste products are heated and wherein a reactor is provided for excepting the heated waste products.
When the apparatus is designed in accordance with the present invention, energy is obtained from the waste products.
In accordance with another feature of the present invention, it further comprises a control valve for regulating the amount of waste entering the reactor.
Another feature of the present invention is that the reactor functions as a pipe heat exchanger.
Yet another feature of the present invention is that it further comprises an electric resistance heater that provides the extra heat necessary to start a exothermic chemical reaction.
Still another feature of the present invention is that it further comprises a lower tank where the liquid and solid hydrocarbons are disposed.
Yet still another feature of the present invention is that the reactor is directly connected to the internal combustion engine without the need for connecting pipes so that no energy is wasted between the internal combustion engine and the reactor.
Still yet another feature of the present invention is that it further comprises a bolt, an exhaust pipe having a beginning, a high velocity exhaust gas, and a high temperature point so that the high temperature point is achieved by installing the bolt through the exhaust pipe at its beginning and having the high velocity exhaust ga hit the bolt and give the bolt energy that yields the high temperature point.
The novel features which are considered characteristic for the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of the specific embodiments when read in connection with the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic drawing showing the principle of operation of the carburetor engine used in the present invention;
FIGS. 2, 2A, and 2B show the reactor type pipe heat exchanger of the present invention;
FIGS. 3 and 3B show the high temperature point of the present invention;
FIGS. 4, 4A, and 4B show the reactor type spiral pipe heat exchanger of the present invention;
FIGS. 5, 5A, and 5B show the reactor type plate-pipe heat exchanger of the present invention;
FIG. 6 is a schematic drawing showing the principle of operation of the diesel engine of the present invention; and
FIG. 7 shows the distribution of temperature in the reactor and the upper tank.
LIST OF REFERENCE NUMERALS UTILIZED IN THE DRAWING
10 - engine
12 - reactor
14 - electro-resistance heater
16 - automatic electro-resistance heater switch of the electro-resistance heater switch 14
18 - sensor for the reactor temperature gauge
20 - lower tank
22 - draining valve of the lower tank 20
24 - fluid hydrocarbons in the lower tank 20
26 - solid hydrocarbons in the lower tank 20
28 - suction valve
30 - exhaust valve
32 - control valve
34 - heating jacket for the exhaust gas
36 - heating jacket for the fluid from the cooling system
38 - waste in the upper tank 40
40 - upper tank
42 - fluid from the cooling system
44 - safety valve
46 - filler/flap valve
48 - first gas hydrocarbon filter
50 - second gas hydrocarbon filter
52 - cooler
54 - gas hydrocarbon valve
56 - flow-meter for the gas hydrocarbons
58 - carburetor
60 - flow-meter for fluid fuel
62 - fluid fuel valve
64 - gauge for the exhaust gas analyzer meter
66 - automatic control system
68 - exhaust gas
70 - heating pipe in the reactor 40
72 - gas hydrocarbons
74 - fluid fuel
76 - to the servomechanism that adjusts the RPMs
78 - to angle of advance
80 - to the servomechanism of the control valve
82 - engine shown in FIG. 2
84 - pipes shown in FIGS. 2, 2A, and 2B
86 - reactor shown in FIGS. 2, 2A, and 2B
88 - exhaust gas pipe shown in FIGS. 3 and 3B
90 - bolt
92 - high temperature point shown in FIGS. 3 and 3B
94 - engine shown in FIG. 4
96 - pipes shown in FIG. 4
98 - reactor shown in FIGS. 4, 4A and 4B
100 - engine shown in FIG. 5
102 - pipes shown in FIGS. 4A, 4B, 5, 5A, and 5B
104 - reactor shown in FIGS. 5, 5A, and 5B
106 - steel rod shown in FIG. 5B
108 - high temperature point shown in FIG. 5B
110 - engine shown in FIG. 6
112 - suction valve
114 - exhaust valve
116 - exhaust gas pipe
118 - reactor shown in FIG. 6
120 - heating jacket of the exhaust gas
122 - upper tank shown in FIG. 6
124 - first gas hydrocarbon filter shown in FIG. 6
126 - second gas hydrocarbons filter shown in FIG. 6
128 - cooler shown in FIG. 6
130 - gas hydrocarbons shown in FIG. 6
132 - throttle shown in FIG. 6
134 - lower tank shown in FIG. 6
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The automatic control system 66 of the present invention regulates the purity of the exhaust gas 68, the temperature of the reaction, and the amount of obtainable gas hydrocarbons 130.
The degree of purity of the exhaust gas 68 is controlled by the amount of liquid fuel 74, and the quality of the hydrocarbon gas fuel 72.
The air-fuel mixture of the carburetor 58 is correct. If the engine 10, 82, 94, 100, or 110 has too rich a mixture the automatic control system (ACS) 66 will lower first the liquid fuel intake and next it will lower the amount of gas hydrocarbons 130.
If the engine 10, 82, 94, 100, or 110 has too lean a mixture, the ACS will increase first the amount of gas hydrocarbons 130 and next the amount of the liquid fuel.
The temperature of the reaction is controlled by changing the amount of wastes in the reactor 12, 86, 98, 104, or 118 changing the revolution per minute of the engine 10, turning the electrical resistance heater 14 on or off, and change the angle of advance 78 of the distributor of the ignition system.
The correct temperature of the reaction should be 700° C. If the temperature is too low, the ACS will lower the amount of the waste in the reactor 12, 86, 98, 104 or 118 increase the revolutions per minute of the engine 10, 10, 82, 94, 100, or 110 turn on the electrical resistance heater 14, and lower the angle of advance 78 of the distributor of the ignition system.
If the temperature is too high, the ACS turns off the electrical resistance heater 14, increases the amount of waste in the reactor 12, 86, 98, 104 or 118 and lowers the revolutions per minute of the engine 10, 82, 94, 100, or 110. The angle of distributor advance is not changed.
The ratio of hydrocarbons to air are kept correct. If there is too little gas hydrocarbons 130, the ACS 66 will increase the temperature of the reaction. If there is too much gas hydrocarbons 130, the ACS 66 will decrease the temperature of the reaction.
The automatic control system 66 of the present invention, as shown in the FIGS. 1 through 7, include a sensor 18 for the reactor temperature gauge, a gauge 64 for the exhaust gas analyzer meter, a flow-meter 56 for the gas hydrocarbons, a flow meter 60 for the fluid fuel, and a sensor for the safety valve 44.
Additionally, a control valve 32, gas hydrocarbons valve 54, fluid fuel valve 62, automatic electro resistance heater switch 16, angle of advance regulator, and a servomechanism to adjust the RPMs.
EXAMPLE OF THE DISPOSITION OF TEMPERATURE IN THE REACTOR 12 AND THE UPPER TANK 40, AS SHOWN IN FIG. 7
700° C. at the high temperature point,
100° C. at the top of the reactor 12,
800° C. at the bottom of the heating jacket 36 with fluid, and
40° C. at the top of the heating jacket 36 with fluid.
EXAMPLE OF THE ENERGY DISTRIBUTION OF THE CHEMICAL REACTION OF THE PRESENT INVENTION
Q 1 - heat gained by the exhaust gas,
Q 2 - heat gained by the chemical reaction,
Q 3 - heat gained by the fluid from the cooling system of the engine,
Q 4 - heat lost by the exhaust gas,
Q 5 - heat lost by the fluid from the cooling system of the engine,
Q 6 - heat lost by the hydrocarbons, and
Q 7 - lost waste heat.
where Q 1 +Q 2 +Q 3 =Q 4 +Q 5 +Q 6 +Q 7
EXAMPLE OF THE MASS BALANCE OF THE CHEMICAL REACTION OF THE PRESENT INVENTION
m 1 - garbage mass,
m 2 - gas hydrocarbons mass,
m 3 - fluid hydrocarbons mass,
m 4 - solid hydrocarbons mass, and
m 5 - ash mass.
where: m 1 =m 2 +m 3 +m 4 +m 5
The present invention depends upon obtaining from the waste, hydrocarbons of gas, fluid, and solid by the use of the pyrolysis process. The waste used must contain carbon and hydrogen, together with plastic, rubber, wood, straw, leaves, or cloth.
The waste is cut into small pieces and is then placed into the upper tank 40. The upper tank 40 is heated by the fluid from the cooling system 42 of the internal combustion engine 10. The waste drops down into the reactor 12 through the control valve 32 with the reactor 12 being a pipe heat exchanger. In the that comes from the internal combustion engine 10 or turbine, and the waste, is counter current. The exhaust 68 comes from an internal combustion engine 10 or turbine.
The temperature during the pyrolysis process, is dependent upon the chemical constitution of the waste. The pyrolysis process functions better at a high temperature point, that is in the range of 300° to 700°.
The additional electric resistance heater 14 provides extra heat necessary to start the exothermic chemical reaction. The heated gas hydrocarbons from the pyrolysis process return to the upper tank 40 where they are filtered and cooled. The gas comes from the internal combustion engine 10, 82, 94, 100, or 110 and is utilized as the fuel for the internal combustion engine 10, 82, 94, 100, or 110 or turbine. The process is a closed cycle and the liquid 24 and the solid hydrocarbons 26 are disposed in the lower tank 20.
The manner in which the reactor 12, 86, 98, 104 or 118 is connected to the engine 10, 82, 94, 100, or 110 is as follows. If one were to take the engine , 82, 94, 100, or 110, in which the intake manifold (not shown) and the exhaust manifold (not shown) are on opposite sides of the engine 10, 82, 94, 100, or 110, one may take the exhaust manifold (not shown) out and connect the reactor 12 directly to the engine 10, 82, 94, 100, or 110 without the need for connecting pipers, as shown in FIG. 1, FIG. 2, FIG. 4, FIG. 5, and FIG. 6. This direct connection does not waste any energy between the engine 10, 82, 94, 100, or 110 and the reactor 12, 86, 98, 104 or 118.
As shown in FIG. 1, FIG. 3, FIG. 3B, FIG. 5B, FIG. 6 and FIG. 7, the high temperature point 92 is achieved by installing a bar or bolt 90 through the exhaust gas pipe adjacent the reactor so that the exhaust gas, with its high velocity hits the bar or bolt 90 and gives the bar or bolt 90 energy that yields the high temperature point 92.
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 constructions differing from the type described above.
While the invention has been illustrated and described as embodied in means for obtaining energy from waste products by the pyrolysic process using exhaust gas from an internal combustion engine or turbine, it is not intended to be limited to the details shown, since it will be understood that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art 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.
What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims.
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Apparatus for obtaining energy from waste products is disclosed. The apparatus includes an upper tank for receiving waste products, a heating system for heating the upper tank by fluid from the cooling system of the combustion engine, and a reactor for excepting the heated waste for further processing.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Continuation in Part of U.S. patent application Ser. No. 12/799,879 filed May 4, 2010 entitled “Anti-Reversible Power Spring Apparatus and Method”. The Applicants hereby claim the benefit of the non-provisional application under 35 U.S.C. §120. The entire content of the non-provisional application is incorporated herein by this reference.
FIELD OF THE INVENTION
This invention relates to shade systems and mechanisms and methods for assisting in the movement of the shade system. In particular, in accordance with one embodiment, the invention relates, in a shade system with a bracket supporting a shade storage roll, to a modular anti-reversible power spring apparatus including a biasing member and a housing with a receiver end and a connector end where the housing encloses the biasing member and the receiver end and the connector end contain the biasing member within the housing. A connector device is connected with the housing and a receiver device is connected with the housing where the connector is connectable with a receiver and where the receiver is connectable with a connector.
BACKGROUND OF THE INVENTION
A difficulty arises with the operation of shades for windows, doors and the like. In particular, shade systems include shade rolls to which the shade is attached. The shade is rolled onto the shade roll and dispensed from the roll and taken up by the roll as required. A major difficulty is caused by the requirements to keep the shade system small enough to not be obtrusive and to fit in the window or door space while still enabling the easy operation and movement of the shade. Motors are utilized to assist the movement of the shade but the weight of the shade can require very large, noisy and expensive motors.
Prior art devices abound that provide assistance to motors and to the operation of shade systems. In particular, roll type shades, curtains, and doors can be counterbalanced as has been known in the art. In Erpenbeck, U.S. Pat. No. 4,009,745, a window shade support roller having an improved spring motor construction and method of manufacture includes a spring retaining structure which holds a driving spring and a spear structure having an integral spear. The spear structure and the spring retaining structure cooperate together, and with a ball, to form a ball clutch mechanism. The spring retaining structure has ball-receiving recesses with canting floors which simplify assembly. Assembly steps include inserting balls into the spring retaining structure, inserting the spear structure into the spring retaining structure, inserting a dowel into the spear structure, positioning a spring around the dowel, and inserting one end of such spring between portions of the spring retaining structure, which uniquely capture and retain the end without other securement, for torsional winding of the spring. However this device must be mounted horizontally so gravity can move the balls in the channel of the ratchet surface arrangement. If the device is mounted vertically, such that there is no force from gravity the balls will not move in the channel.
In U.S. Pat. Nos. 6,283,192 and 6,957,683 to Toti, a spring drive system for window covers is disclosed which includes a so-called flat spring drive and the combination whose elements are selected from a group which includes (1) a band transmission which provides varying ratio power transfer as the cover is opened and closed; (2) a gear system selected from various gear sets which provide frictional holding force and fixed power transfer ratios; and (3) a gear transmission which provides fixed ratio power transfer as the cover is opened or closed. The combination permits the spring drive force at the cover to be tailored to the weight and/or compression characteristics of the window cover such as a horizontal slat or pleated or box blind as the cover is opened and closed. This art discusses the use of multiple drums with flat type springs but does not address the issue of possible back winding the spring.
In U.S. Pat. No. 6,648,050 to Toti, a spring drive system useful for window covers is disclosed, which comprises one or more coil spring drives or flat spring drives and the combination whose elements are selected from one or more of a group which includes (1) a band or cord transmission which provides varying ratio power transfer as the cover is opened and closed; (2) gear means comprising various gear sets which provide frictional holding force and fixed power transfer ratios; (3) a gear transmission which provides fixed ratio power transfer as the cover is opened or closed; (4) crank mechanisms; (5) brake mechanisms; and (6) recoiler mechanisms. The combination permits the spring drive force to be tailored to the weight and/or compression characteristics of an associated window cover such as a horizontal slat or pleated or box blind as the cover is opened and closed.
In U.S. Pat. No. 6,659,156 to Wen et al., a screw transmission mechanism for a motor-driven blind is constructed to include a driving unit, and at least one cord roll-up unit controlled by the driving unit to lift/lower or tilt the slats of the motor-driven Venetian blind. Each cord roll-up unit includes an amplitude modulation set controlled by the driving unit to lift/lower the slats and bottom rail of the Venetian blind, a frequency modulation set for rotation with the amplitude modulation set to tilt the slats of the Venetian blind, and a linkage adapted to control connection between the frequency modulation set and the amplitude modulation set.
In U.S. Pat. No. 6,854,503 to Cross et al., the invention includes an unbalanced horizontal blind with a spring means to provide a lifting or retraction force for the slats of the blinds. A brake means prevents undesired movement of the slats that would otherwise result from the continuous retraction force of the spring means when the slats are set in a desired position. Controls for the release of the brake means and tilting are also provided in an embodiment of a blind of the invention. An embodiment of the invention permits the blind to be operated by a single wand that can be used to either raise the slats or tilt the slats. This eliminates the need for a loose cord or bead chain that would traditionally be used as the user interface for controlling the movement of the slats of the blind.
Despite these efforts, the art is still missing a counter balancing system that is easily adjustable such that counter balances may be added or deleted as the circumstances require and as they change. That is, all the prior art of which Applicants are aware are fixed systems or complex adjustable systems that are bulky and hard to manipulate. At best prior art systems can accommodate small adjustments but major changes in the weight of the shade to be moved require total replacement of existing counter balances.
Another missing element in the prior art is a simple system for the prevention of back winding of the counter balance springs. For example, if some element of a prior art system was changed, like a battery or batteries, and then the shade was rehung partially deployed, this can result in a reverse wind of the counter balance spring when the motor moves the shade up to the fully open position. This is not desirable since it can, and often does, damage the counter balance systems in the prior art.
The cross referenced application goes a long way to eliminating the prior art problems but others still remain. It has been determined that the cross referenced housing limits the number of biasing members by its own dimensions. That is, while the housing may contain multiple biasing members only a certain definite number may be contained in any one preconstructed housing.
Further, in order to add or delete biasing members, the entire group of biasing members and the entire housing must be removed, the housing opened, the biasing member(s) added or removed, and then the housing resealed and reinserted for operational use.
Further, there is no way provided by the prior art to add additional housings within the system and, at the same time, ensure that the additions are secure with each other and within the system.
Thus, it is an object of this invention to provide a counter balance system and method that is modular and that is easy to install and adjust. Further it is an objective of the invention to provide a counter balance system that does not back wind and can not back wind during operation of a shade system.
SUMMARY OF THE INVENTION
Accordingly, according to one embodiment in a shade system with a bracket supporting a shade storage roll, a modular anti-reversible power spring apparatus includes a biasing member and a housing with a receiver end and a connector end where the housing encloses the biasing member and together the housing, the receiver end and the connector end contain the biasing member within the housing. A connector is connected with the housing and a receiver is connected with the housing where the connector is connectable with a receiver and where the receiver is connectable with a connector.
Terms used herein are given their common and ordinary meaning as known by those of ordinary skill in the art. “Modular” is used to describe a device that includes identical or nearly identical attributes such as form and dimension, for example only, such that one may be added to and removed from another, for example only, in a simple, predicable manner. “Connector” and “receiver” describe structures that cooperate together to hold two items together. Likewise “female connector” and “male connector” describe structures designed to cooperate with each other to secure one to the other. Further, “biasing member” describes a device that can exert pressure in a system to move it or resist movement, for example only, such as a spring, for example only and not by way of limitation.
In one aspect of the invention, a second housing enclosing a second biasing member is provided and a connector on one housing connects with a receiver on the other housing such that the two housings are locked together.
In another aspect, the invention further includes a support connected with the bracket, such that the support does not move. The support is also connected with the biasing member within the housing. A first end cap and a second end cap are provided where one end cap is connected to the shade storage roll at each end of the shade storage roll and also to the support such that the first end cap and the second end cap are held stationary along with the support but the shade storage roll is free to rotate about the end caps. Further, a connector is connected with the first end cap and a receiver is connected with the second end cap where, again, the connector is connectable with a receiver and the receiver is connectable with a connector.
As used herein, the term “connectable” means “capable of being connected” and describes a structure or combination of structures that provide the ability, when combined, to result in joining together, at least temporarily, two or more separate structures.
In one aspect, the biasing member further includes a first end and a second end where the first end of the biasing member is connected with the housing and where the second end of the biasing member is connected with the support. In a further aspect, the support has a length and the housing has a length and the support is conformed in length to approximately the length of the housing.
In one aspect of the invention, the shade storage roll includes a female connector and the housing includes a male connector and the male connector is conformed to connect with the female connector and to lock the housing with the shade storage roll.
In another aspect, the connection of the second end of the biasing member with the support is such that the biasing member is held in place when the housing rotates in one direction and is released when the housing rotates in an opposite direction. In a further aspect, the support includes a groove that accepts the second end and holds the second end against movement when the storage roll is rotated in one direction but which allows passage of the second end past the groove when the storage roll is rotated in the opposite direction.
In another aspect, the biasing member is selected from a group consisting of: a spring and a coiled flat spring.
According to another embodiment of the invention, in a shade system with a bracket supporting a shade storage roll, a modular anti-reversible power spring apparatus includes a biasing member and a housing with a receiver end and a connector end where the housing encloses the biasing member and the receiver end and the connector end contain the biasing member within the housing. A connector is provided that is connected with the receiver end and a receiver is provided that is connected with the connector end where the connector is connectable with a receiver and where the receiver is connectable with a connector. A support is connected with the bracket, such that the support does not move, and where the support is also connected with the biasing member within the housing. A first end cap and a second end cap are provided where one end cap is connected to the shade storage roll at each end of the shade storage roll and to the support such that the first end cap and the second end cap are held stationary with the support and the shade storage roll is free to rotate about the end caps. And a connector is connected with the first end cap and a receiver is connected with the second end cap where the first end cap connector is conformed to connect with the connector end receiver and the second end cap receiver is conformed to connect with the receiver end connector.
In one aspect of this invention, it further includes more than one housing with a biasing member where each housing is conformed to connect with at least one additional housing.
In another aspect, the biasing member further includes a first end and a second end where the first end of the biasing member is connected with the housing and where the second end of the biasing member is connected with the support. In one aspect, the support has a length and the housing has a length and the support is conformed in length to approximately the length of the housing. In a further aspect, the shade storage roll includes a female connector and the housing includes a male connector and the male connector is conformed to connect with the female connector and to lock the housing with the shade storage roll.
In a further aspect, the connection of the second end of the biasing member with the support is such that the biasing member is held in place when the housing rotates in one direction and is released when the housing rotates in an opposite direction. In another aspect, the support includes a groove that accepts the second end and holds the second end against movement when the storage roll is rotated in one direction but which allows passage of the second end past the groove when the storage roll is rotated in the opposite direction.
According to another embodiment of the invention, in a shade system with a bracket supporting a shade storage roll, a modular anti-reversible power spring method includes the steps of:
a. providing a biasing member; a housing with a receiver end and a connector end where the housing encloses the biasing member and the receiver end and the connector end contain the biasing member within the housing; a connector connected with the housing; and a receiver connected with the housing where the connector is connectable with a receiver and where the receiver is connectable with a connector; and
b. connecting the housing with the shade storage roll.
In another aspect of this invention the method includes the steps of”
a. providing a support connected with the bracket, such that the support does not move, and also connected with the biasing member within the housing; a first end cap and a second end cap where one end cap is connected to the shade storage roll at each end of the shade storage roll and to the support such that the first end cap and the second end cap are held stationary with the support and the shade storage roll is free to rotate about the end caps; and a connector connected with the first end cap and a receiver connected with the second end cap where the first end cap connector is conformed to connect with a receiver and the second end cap receiver is conformed to connect with a connector; and
b. connecting an end cap with a housing.
In one aspect, the biasing member further includes a first end and a second end where the first end of the biasing member is connected with the housing and where the second end of the biasing member is connected with the support such that the biasing member is held in place when the housing rotates in one direction and is released when the housing rotates in an opposite direction.
In another aspect, the method includes the steps of:
a. providing more than one housing with a biasing member where each housing is conformed to connect with at least one additional housing; and
b. connecting each housing with at least one additional housing.
DESCRIPTION OF THE DRAWINGS
Other objects, features and advantages of the present invention will become more fully apparent from the following detailed description of the preferred embodiment, the appended claims and the accompanying drawings in which:
FIG. 1 is a perspective view of a shade roll and bracket assembly for the modular anti-reversible power spring apparatus of the present invention according to one embodiment;
FIG. 2 is an exploded perspective view of the invention of FIG. 1 showing three separate housings each including one biasing member;
FIG. 3 is a close up, exploded perspective view of the invention of FIGS. 1 and 2 ;
FIG. 4 is a close up, exploded perspective view of one end cap and one housing with one biasing member;
FIG. 5 is a close up, exploded perspective view of FIG. 4 from the opposite view from FIG. 4 ;
FIG. 6 is an end section view of the invention;
FIG. 7 is a side perspective view of the invention showing three housings and a support approximately the same length as the total length of the three separate housings;
FIG. 8 is a side perspective view of the invention showing two housings and a support approximately the same length as the total length of the two separate housings; and
FIG. 9 is a side perspective view of the invention showing one housing and a support approximately the same length as the total length of the one housing.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiment of the present invention is illustrated by way of example in FIGS. 1-9 . With specific reference to FIG. 1 , the preferred embodiment of the modular anti-reversible power spring apparatus 10 of the present invention includes an associated roll shade assembly 12 consisting of a shade material 14 , mounting bracket 16 , a shade storage roll 18 and at least one arbor shaft or support 20 . The shade material 14 is attached to the storage roll 18 as is known in the art. As used herein, the term “shade material” is used in its common manner to indicate a substance used to provide shade. It thus includes fabric and plastic, for example only and not by way of limitation, and any other flexible material now known or hereafter developed capable of being rolled onto and off of a storage roll.
Referring now to FIGS. 2 and 3 , the inside of the storage roll 18 , according to a preferred embodiment is hollow. It thus is capable of including within the hollow interior 22 many mechanisms such as, for example only, a motor assembly 24 , including a motor and gearbox (not shown) for example, and a power supply 26 , including batteries (not shown) for example only. The motor assembly 24 and the power supply 26 have one or more male connectors 28 , such as a spline or ridge as shown for example only, that mate with an internal longitudinal groove(s) or female connector 30 in the interior surface of the hollow interior 22 of storage roll 18 . The figures show one or two longitudinal female connectors 30 but there may be more. The effect of inserting motor assembly 24 and power supply 26 within the hollow interior 22 of storage roll 18 , by aligning the male connector 28 with the female connectors 30 , is to lock the elements together such that the motor assembly 24 and the power supply 26 , and any and all other elements connected in such a manner with storage roll 18 as will be discussed more fully hereafter, turn with the storage roll 18 .
Still referring to FIGS. 2 and 3 , in a preferred embodiment, a first end cap 32 and a second end cap 34 are provided. First end cap 32 is connected with support 20 and storage roll 18 on one end of storage roll 18 and second end cap 34 is connected with support 20 and storage roll 18 on the other end of storage roll 18 as illustrated. The connection of support 20 with mounting bracket 16 is fixed. That is, support 20 does not move with relation to bracket 16 once it is secured thereto. Likewise, support 20 is connected with first end cap 32 and second end cap 34 in a fixed relation such that once secured in place, the end caps 32 and 34 do not move either. Storage roll 18 , however, although it is supported between and by the two end caps 32 and 34 is free to move in relation to the end caps 32 and 34 . This movement may be facilitated by the use of bearings 36 at end caps 32 and 34 , for example only. In this manner, output from motor assembly 24 which is connected with storage roll 18 as described above, turns shade roll 18 about end caps 32 and 34 when power from power supply 26 is applied.
Finally, FIGS. 2 and 3 illustrate housing 38 with a receiver end 40 and a connector end 42 . Preferably, housing 38 is cylindrically shaped and similar in dimension to the inside diameter of storage roll 18 . Together, housing 38 and receiver end 40 and connector end 42 enclose biasing member 44 (see FIGS. 4 and 5 ) and retain biasing member 44 inside housing 38 . Here it should be noted that housing 38 encloses only a single biasing member 44 as will be described more fully hereafter. The figures also show that, preferably, housing 38 includes male connectors 28 that cooperate with female connectors 30 to secure housings 38 in place within storage roll 18 , as discussed above with regard to the motor assembly 24 and the power supply 26 . And, the figures show that preferably, support 20 is connected with each housing 38 as will be described more fully hereafter.
Referring now to FIG. 3 , this close up view further illustrates some of the features of the present invention such as receiver end 40 connected with housing 38 . Connector end 42 is not shown (see FIG. 4 ) but is opposite from receiver end 40 and connected with housing 38 as well.
Further, it can be seen that support 20 is conformed, according to a preferred embodiment, to pass through first end cap 34 and housings 38 and to connect with power out put shaft 46 . Again, because support 20 is fixed and does not move, and because motor assembly 24 is connected with storage roll 18 , which is allowed to move, when operated power out put shaft 46 turns storage roll 18 .
Importantly, FIG. 3 also clearly illustrates receiver 48 . Receiver 48 preferably consists of one or more keyed slots as illustrated. FIG. 4 shows connector 50 . Connector 50 preferably consists of one or more extended keys as illustrated. Connector 50 cooperates with receiver 48 to lock two separate housings together, as will be discussed more fully hereafter.
Referring now to FIGS. 4 and 5 , many of the above features are more clearly illustrated along with a clear view of the biasing member 44 . Preferably, biasing member 44 is a spring, such as a coiled, flat spring as shown. Biasing member 44 has a first end 52 and a second end 54 . The first end 52 is connected with housing 38 . Preferably, first end 52 fits within slot 56 in housing 38 and is held in that position after installation.
Second end 54 fits within groove 58 on support 20 . Importantly, second end 54 and groove 58 cooperate together to prevent movement between them when housing 38 rotates with storage roll 18 in one direction. However, second end 54 is released from groove 58 when rotated in the opposite direction as is more clearly seen from FIG. 6 and as will be discussed more fully hereafter.
Another important feature of the present invention is shown in FIGS. 4 and 5 in which second end cap 34 includes connectors 50 as described above. As a result, connectors 50 on second end cap 34 cooperate with receivers 48 on connector end 42 of housing 38 to secure housing 38 to the end cap 34 . First end cap 32 (not shown) may also include connectors 50 for the same purpose. Obviously, it is not essential to the invention which element has the connectors 50 and which has the receivers 48 but only that they are positioned so as to function as described. Nonetheless, this feature of the invention ensures that housings 38 inserted within storage roll 18 do not travel or move along the hollow interior 22 after insertion. This is a decided advantage over the prior art in that is reduces noise and vibration as Applicants have determined by testing.
FIG. 5 clearly shows connector end 42 of housing 38 with receivers 48 .
Referring now to FIG. 6 a cross section view shows storage roll 18 with female connectors 30 and housing 38 with male connectors 28 connected within female connectors 30 . Four female connectors 30 are shown in the cross section and only two male connectors 28 , which is acceptable for the purposes of the invention.
Slot 56 in housing 38 is clearly shown as is first end 52 of biasing member 44 . Also shown are second end 54 of biasing member 44 formed, for example into a rounded end and set within groove 58 of support 20 . In this position, when rotated in the direction of direction arrow 60 the second end 54 is held against movement by groove 58 in stationary support 20 and the biasing member 44 is wound up. When rotated in the direction of direction arrow 62 , the opposite direction from arrow 60 , the second end 54 ramps over the top of groove 58 and unwinds. This feature of the invention prevents reverse or back winding of the biasing member 44 .
Referring now to FIGS. 7 , 8 , and 9 it is illustrated that support 20 has a length and the length of support 20 may, according to one embodiment, be approximately the same as the combined length of the total number of housings 38 , each with a single biasing member 44 . FIG. 7 shows support 20 approximately as long as three combined housings 38 , FIG. 8 , two and FIG. 9 only one. Certainly, support 20 may be of a single length sufficient to retain multiple housings 38 covering its entire length or not. That is, fewer housings 38 are easily accommodated on a long support 20 and, as described above, held in place along the support 20 just as well without need for changing to a support 20 of a different length.
In whatever length, the important feature of the invention is that housings 38 and the single enclosed biasing member 44 may easily be added to or removed from the storage roll 18 . This is a tremendous advantage over the prior art which requires complicated removal of a large housing, if present, opening the housing, adding or removing biasing members 44 re-closing and re-installing the housing. According to the present invention, counterbalance tension as provided by the biasing members 44 may be accurately and easily adjusted to fit the needs. Further repair and replacement is just as easily accommodated.
The description of the present embodiments of the invention has been presented for purposes of illustration, but is not intended to be exhaustive or to limit the invention to the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. As such, while the present invention has been disclosed in connection with an embodiment thereof, it should be understood that other embodiments may fall within the spirit and scope of the invention as defined by the following claims.
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In a shade system with a bracket supporting a shade storage roll, an anti-reversible power spring apparatus includes a biasing member and a housing with a receiver end and a connector end where the housing encloses the biasing member and the receiver end and the connector end contain the biasing member within the housing. A connector device is connected with the housing and a receiver device is connected with the housing where the connector is connectable with a receiver and where the receiver is connectable with a connector.
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TECHNICAL FIELD
[0001] The present invention is concerned with compositions and uses of amine surfactants incorporated into crop oil concentrate (COC) adjuvants for use with various herbicides, especially glyphosate.
BACKGROUND INFORMATION
[0002] It is known in the art that surfactants are included in COCs. They function to emulsify the oil when diluted into water in the spray tank and can also be incorporated as wetters to help the spray solution spread on the target once it is applied.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] In the annexed drawings,
[0004] FIG. 1 shows a 10-day field trial using materials according to the present invention;
[0005] FIG. 2 shows a 10-day field trial using materials according to the present invention;
[0006] FIG. 3 shows a 21-day field trial using materials according to the present invention; and
[0007] FIG. 4 shows a 21-day field trial using materials according to the present invention.
SUMMARY OF THE INVENTION
[0008] The present invention is concerned with incorporation of surfactants with amine chemistries as both emulsifier and wetter. Surfactants with amine chemistries are known to maximize the efficacy of several herbicides, especially glyphosate. By using amine chemistry surfactants in COCs that are tank mixed with pesticides that benefit from the presence of amine chemistry surfactants, the surfactants in the COCs provide dual roles in the final spray solution. They will emulsify and wet the crop oil, and they will also increase the efficacy of the active ingredient.
DETAILED DESCRIPTION
[0009] The specific surfactants used include alkyl amine ethoxylates and alkyl ether amine ethoxylates. Other amine chemistry surfactants such as polyetheramine and ethylenediamine based chemistries are useful in accordance with the present invention. The aforesaid compounds have been successfully formulated in crop oil concentrates with various paraffinic oils. In addition, formulations with EXXSOL® D130 and ester solvents EXXATE® series solvents also available from Exxon are useful. A composition according to the invention can include other surfactant chemistries, other crop oils, and optionally additional formulation components known in the art.
Huntsman COC-1 Component w/w % EXXSOL ® D-130 60.0 PEL 24-3 28.0 SURFONIC ® C-2 4.5 SURFONIC ® T-10 5.5 Water 2.0
[0010] Huntsman COC-2 Component w/w % EXXSOL ® D-130 60.0 PEL 24-3 30.0 SURFONIC ® PEA-25 8.0 Water 2.0
EXXSOL® D-130 is a dearomatized hydrocarbon fluid available from ExxonMobil Chemical. PE L24-3 is a phosphate ester of SURFONIC® L24-3 surfactant available from Huntsman LLC of Austin, Tex. Any phosphate esters thereof are suitable for use in the present invention. SURFONIC® C-2 is a 2-mole ethoxylate of cocoamine available from Huntsman LLC of Austin, Tex. SURFONIC® T-10 is a 10-mole ethoxylate of Tallowamine available from Huntsman LLC of Austin, Tex. SURFONIC® PEA-25 is an alkyl polyetheramine ethoxylate available from Huntsman LLC of Austin, Tex.
[0011] Unexpected results of the invention include the fact that the efficacy of active ingredient is improved by choice of adjuvant surfactant chemistry formulated into companion crop oil concentrate. Efficacy is improved past expectations from crop oil alone.
[0012] A field trial was performed with blinded sample numbers. A protocol summary of the field trial is given below:
Evaluation of Huntsman COC's with Assure® and Roundup® Original
[0013] Objective: Evaluate the performance of Huntsman crop oil concentrates compared to Agriliance HI-PER-OIL with Assure II and Roundup Original® in Roundup Ready® soybeans.
Target Weeds Code Common Name Scientific Name IPOSS Morningglory Ipomoea spp. ABUTH Velvetleaf Abutilon theophrasti AMASS Pigweed Amaranthus spp. SIDSP Teaweed Sida spinosa SORVU Shattercane Sorghum bicolor SETFA Giant foxtail Setaria faberi ZEAMX Volunteer RR corn Zea mays Target Crop Code Crop Common Name GLXMA Roundup Ready ® soybean Glycine max
Geographic Area/Environmental Considerations and General Comments: Overhead irrigation is not required, but should be supplied if drought conditions threaten loss of data.
[0014] Insure adequate broadleaf weed distribution and density by broadcasting Roundup Ready® corn seed, morning glory, velvetleaf, pigweed and prickly sida weed seeds just before the final seedbed preparation (field cultivator and/or harrow).
[0015] Plant Roundup Ready® soybeans in 30″ rows. Traditional (30″) row width is requested to allow maximum opportunity for emergence and aggressive growth of indigenous broadleaf weeds.
[0016] Plot size is 4 rows by 30 feet. Arrange in RCB design with 4 replications. Apply treatments in 20 gal/A spray volume.
[0017] Apply experimental treatments when most broadleaf weeds are in the 3- to 6-leaf stage. At the time of application; record the stage (number of leaves), height and density (#/sq ft or sq meter) of each broadleaf weed species that is present in sufficient density and distribution for good assessment. This data should be taken from the two center row-centers of each non-treated control plot.
[0018] Assess phytotoxicity to the crop at 2, 10, and 21 days after treatment. Include a description of the injury symptom and scale used for the assessment, i.e., necrotic leaf spots assessed as percent of leaf surface afflicted, percent crop height reduction, etc.
[0019] Assess percent (%) control of each weed species at 10 and 21 days after treatment. Crop yield is not measured. Treatments to be Evaluated:
TABLE I Sample No. Name Form Type Rate Unit 1 Control 2 Assure II 0.88 EC 4 fl oz/A 3 Assure II 0.88 EC 4 fl oz/A HI-PER-OIL 0.5 % V/V 4 Assure II 0.88 EC 2 fl oz/A HI-PER-OIL 0.5 % V/V 5 Assure II 0.88 EC 4 fl oz/A Huntsman COC 1 0.5 % V/V 6 Assure II 0.88 EC 2 fl oz/A Huntsman COC 1 0.5 % V/V 7 Assure II 0.88 EC 4 fl oz/A Huntsman COC 2 0.5 % V/V 8 Assure II 0.88 EC 2 fl oz/A Huntsman COC 2 0.5 % V/V 9 Assure II 0.88 EC 4 fl oz/A Roundup Original 4 EC 16 fl oz/A 10 Assure II 0.88 EC 4 fl oz/A Roundup Original 4 EC 16 fl oz/A HI-PER-OIL 0.5 % V/V 11 Assure II 0.88 EC 2 fl oz/A Roundup Original 4 EC 8 fl oz/A HI-PER-OIL 0.5 % V/V 12 Assure II 0.88 EC 4 fl oz/A Roundup Original 4 EC 16 fl oz/A Huntsman COC 1 0.5 % V/V 13 Assure II 0.88 EC 2 fl oz/A Roundup Original 4 EC 8 fl oz/A Huntsman COC 1 0.5 % V/V 14 Assure II 0.88 EC 4 fl oz/A Roundup Original 4 EC 16 fl oz/A Huntsman COC 2 0.5 % V/V 15 Assure II 0.88 EC 2 fl oz/A Roundup ® Original 4 EC 8 fl oz/A Huntsman COC 2 0.5 % V/V
[0020] Product quantities required for listed treatments and applications in one trial:
TABLE II Amount Unit Product 44.0 ml Assure ® II 0.88 EC 51.2 ml HI-PER-OIL 51.2 ml Huntsman COC 1 51.2 ml Huntsman COC 2 88.0 ml Roundup Original ® 4 EC
Calculations based on 20 gal/A spray volume, mix size=2.565 liters.
[0021] Evaluation of Huntsman COCs with Assure and Roundup Original—continued
Protocol Spry Sheet Reps: 4; Plots: 10 by 30 feet
[0023] Spray Vol: 20 gal/ac Mix Size: 2.565 liters
TABLE III Sample No. Name Form Type Rate Unit to Measure 1 Control 2 Assure II 0.88 EC 4 fl oz/A 4.0 ml 3 Assure II 0.88 EC 4 fl oz/A 4.0 ml HI-PER-OIL 0.5 % V/V 12.8 ml 4 Assure II 0.88 EC 2 fl oz/A 2.0 ml HI-PER-OIL 0.5 % V/V 12.8 ml 5 Assure II 0.88 EC 4 fl oz/A 4.0 ml Huntsman COC 1 0.5 % V/V 12.8 ml 6 Assure II 0.88 EC 2 fl oz/A 2.0 ml Huntsman COC 1 0.5 % V/V 12.8 ml 7 Assure II 0.88 EC 4 fl oz/A 4.0 ml Huntsman COC 2 0.5 % V/V 12.8 ml 8 Assure II 0.88 EC 2 fl oz/A 2.0 ml Huntsman COC 2 0.5 % V/V 12.8 ml 9 Assure II 0.88 EC 4 fl oz/A 4.0 ml Roundup 4 EC 16 fl oz/A 16.0 ml Original 10 Assure II 0.88 EC 4 fl oz/A 4.0 ml Roundup 4 EC 16 fl oz/A 16.0 ml Original HI-PER-OIL 0.5 % V/V 12.8 ml 11 Assure II 0.88 EC 2 fl oz/A 2.0 ml Roundup 4 EC 8 fl oz/A 8.0 ml Original HI-PER-OIL 0.5 % V/V 12.8 ml 12 Assure II 0.88 EC 4 fl oz/A 4.0 ml Roundup 4 EC 16 fl oz/A 16.0 ml Original Huntsman COC 1 0.5 % V/V 12.8 ml 13 Assure II 0.88 EC 2 fl oz/A 2.0 ml Roundup 4 EC 8 fl oz/A 8.0 ml Original Huntsman COC 1 0.5 % V/V 12.8 ml 14 Assure II 0.88 EC 4 fl oz/A 4.0 ml Roundup 4 EC 16 fl oz/A 16.0 ml Original Huntsman COC 2 0.5 % V/V 12.8 ml 15 Assure II 0.88 EC 2 fl oz/A 2.0 ml Roundup 4 EC 8 fl oz/A 8.0 ml Original Huntsman COC 2 0.5 % V/V 12.8 ml
[0024] Assure II and Roundup Original® were the active ingredients tested.
TABLE IV Weed Species Studied ZEAMX = Volunteer Roundup Ready ® field corn SORVU = shattercane ( Sorghum bicolor ) IPOSS = morningglory ( Ipomoea spp.) ABUTH = velvetleaf ( Abutilon theophrasti ) AMATU = tall waterhemp ( Amaranthus tuberculatus ) SIDSP = prickly sida [a.k.a. teaweed] ( Sida spinosa )
[0025] Results of the field trial are in the attached 10-Day and 21-Day tables:
TABLE V 10 DAY Evaluation of Huntsman Surfactants with Assure on Roundup Ready Soybeans Weed Code ZEAMX SORVU IPOSS ABUTH AMATU SIDSP Crop Code GLXMA Rating Data Type PHYGEN CONTRO CONTRO CONTRO CONTRO CONTRO CONTRO Rating Unit % % % % % % % Weed Stage 7 leaf 6 leaf 9 leaf 9 leaf 9 leaf 9 leaf Trt-Eval Interval 10 DA-A 10 DA-A 10 DA-A 10 DA-A 10 DA-A 10 DA-A 10 DA-A Treatment Rate Plot Control 101 0 0 0 0 0 0 0 206 0 0 0 0 0 0 0 310 0 0 0 0 0 0 0 404 0 0 0 0 0 0 0 avg 0 0 0 0 0 0 0 Assure II 4 102 0 60 70 0 0 0 0 204 0 70 85 0 0 0 0 312 0 70 80 0 0 0 0 408 0 75 80 0 0 0 0 avg 0 69 79 0 0 0 0 Assure II 4 105 0 80 90 0 0 0 0 Huntsman 0.5 208 0 85 85 0 0 0 0 COC-1 313 0 85 90 0 0 0 0 412 0 80 85 0 0 0 0 avg 0 83 88 0 0 0 0 Assure II 2 106 0 60 80 0 0 0 0 Huntsman 0.5 207 0 80 80 0 0 0 0 COC-1 309 0 85 90 0 0 0 0 414 0 85 90 0 0 0 0 avg 0 78 85 0 0 0 0 Assure II 4 107 0 80 90 0 0 0 0 Huntsman 0.5 211 0 80 85 0 0 0 0 COC-2 308 0 85 85 0 0 0 0 415 0 80 85 0 0 0 0 avg 0 81 86 0 0 0 0 Assure II 2 108 0 70 80 0 0 0 0 Huntsman 0.5 212 0 80 90 0 0 0 0 COC-2 305 0 70 90 0 0 0 0 401 0 60 90 0 0 0 0 avg 0 70 88 0 0 0 0 Assure II 4 109 0 80 90 20 20 95 40 Roundup 16 202 0 60 90 20 20 95 70 Original ® 301 0 80 85 40 20 95 50 410 0 80 85 30 20 98 60 avg 0 75 88 28 20 96 55 Assure II 4 112 0 80 90 30 20 95 60 Roundup 16 214 0 85 85 30 30 95 40 Original ® Huntsman 0.5 311 0 80 90 20 30 95 60 406 0 75 90 25 25 95 60 avg 0 80 89 26 26 95 55 Assure II 2 113 0 80 85 20 20 95 60 Roundup 8 203 0 70 90 30 20 90 50 Original ® Huntsman 0.5 304 0 80 80 20 20 70 50 COC-1 402 0 75 90 20 20 80 30 avg 0 76 86 23 20 84 48 Assure II 4 114 0 85 90 20 20 95 50 Roundup 16 213 0 85 90 40 40 95 60 Original Huntsman 0.5 307 0 85 90 20 30 85 60 COC-2 405 0 80 90 35 30 90 60 avg 0 84 90 29 30 91 58 Assure II 2 115 0 70 90 30 20 95 40 Roundup 8 209 0 80 90 20 20 90 40 Original Huntsman 0.5 315 0 60 90 20 10 90 50 COC-2 411 0 85 85 20 20 95 50 avg 0 74 89 23 18 93 45
[0026]
TABLE VI
21 DAY
Evaluation of Huntsman Surfactants with Assure on Roundup Ready ® Soybeans
Weed Code
ZEAMX
SORVU
IPOSS
ABUTH
AMATU
SIDSP
Crop Code
GLXMA
Rating Data Type
PHYGEN
CONTRO
CONTRO
CONTRO
CONTRO
CONTRO
CONTRO
Rating Unit
%
%
%
%
%
%
%
Weed Stage
8 leaf
8 leaf
9+ leaf
9+ leaf
9+ leaf
9+ leaf
Trt-Eval Interval
21 DA-A
21 DA-A
21 DA-A
21 DA-A
21 DA-A
21 DA-A
21 DA-A
Treatment
Rate
Plot
Control
101
0
0
0
0
0
0
0
206
0
0
0
0
0
0
0
310
0
0
0
0
0
0
0
404
0
0
0
0
0
0
0
avg
0
0
0
0
0
0
0
Assure II
4
102
0
90
95
0
0
0
0
204
0
100
100
0
0
0
0
312
0
92
100
0
0
0
0
408
0
100
95
0
0
0
0
avg
0
95.5
97.5
0
0
0
0
Assure II
4
105
0
100
100
0
0
0
0
Huntsman
0.5
208
0
100
100
0
0
0
0
COC-1
313
0
100
100
0
0
0
0
412
0
100
100
0
0
0
0
avg
0
100
100
0
0
0
0
Assure II
2
106
0
100
95
0
0
0
0
Huntsman
0.5
207
0
100
100
0
0
0
0
COC-1
309
0
100
100
0
0
0
0
414
0
100
100
0
0
0
0
avg
0
100
98.75
0
0
0
0
Assure II
4
107
0
100
100
0
0
0
0
Huntsman
0.5
211
0
100
100
0
0
0
0
COC-2
308
0
100
100
0
0
0
0
415
0
100
100
0
0
0
0
avg
0
100
100
0
0
0
0
Assure II
2
108
0
99
100
0
0
0
0
Huntsman
0.5
212
0
100
100
0
0
0
0
COC-2
305
0
92
100
0
0
0
0
401
0
96
99
0
0
0
0
avg
0
96.75
99.75
0
0
0
0
Assure II
4
109
0
100
100
50
50
95
60
Roundup
16
202
0
100
100
60
50
95
60
Original ®
301
0
100
100
60
40
95
50
410
0
100
100
50
40
95
50
avg
0
100
100
55
45
95
55
Assure II
4
112
0
100
100
60
60
95
50
Roundup
16
214
0
100
100
60
60
92
50
Original ®
Huntsman
0.5
311
0
100
100
60
60
95
60
COC-1
406
0
100
100
60
60
90
60
avg
0
100
100
60
60
93
55
Assure II
2
113
0
100
100
50
50
90
50
Roundup
8
203
0
100
100
50
40
90
50
Original ®
Huntsman
0.5
304
0
100
100
40
50
85
40
COC-1
402
0
100
100
50
50
85
50
avg
0
100
100
47.5
47.5
87.5
47.5
Assure II
4
114
0
100
100
40
40
92
60
Roundup
16
213
0
100
100
60
60
95
60
Original ®
Huntsman
0.5
307
0
100
100
60
70
95
60
COC-2
405
0
100
100
65
70
85
60
avg
0
100
100
56.25
60
91.75
60
Assure II
2
115
0
100
99
50
30
95
50
Roundup
8
209
0
100
100
40
60
90
50
Original ®
Huntsman
0.5
315
0
100
100
40
40
92
60
COC-2
411
0
100
100
60
50
95
50
avg
0
100
99.75
47.5
45
93
52.5
[0027] Ten-Day Conclusions for Assure w/o glyphosate: Efficacy of Assure II at full rates was improved by using COCs COC1 and COC2 on both ZEAMX and SORVU. After cutting Assure rates in half, efficacy on both ZEAMX and SORVU using COC-1 was almost retained at the full rate with COC, and was significantly above full rate w/o COC. After cutting Assure rates in half, efficacy on ZEAMX using COC-2 was slightly lower than full rate with COC, but was still above full rate w/o COC. Efficacy on SORVU using COC-2 was retained at the full rate with COC, and was significantly above full rate w/o COC.
[0028] Ten-Day Conclusions for Assure with glyphosate: Data is not significantly different within individual weed species.
[0029] Twenty-one-Day Conclusions for Assure w/o glyphosate: Efficacy of Assure II at full rates was improved by using both COCs on both ZEAMX and SORVU. After cutting Assure rates in half, efficacy on both ZEAMX and SORVU using both COCs was almost retained at the full rate with COC, and was above the full rate w/o COC.
[0030] Twenty-one-Day Conclusions for Assure with glyphosate: On IPOSS, efficacy was slightly improved with COCs at full glyphosate rate, and only slightly less than full rate when glyphosate rate was cut in half. For ABUTH, efficacy was improved with COCs at full glyphosate rate, and equal to the full rate when glyphosate rate was cut in half. For AMATU, efficacies were not significantly different for glyphosate at full rate, glyphosate plus COCs at full rate, and COC-2 with glyphosate at half rate. Efficacy was only slightly reduced with COC-1 and glyphosate at half rate. For SIDSP, COC-2 improved efficacy over glyphosate at full rate, and matched efficacy of glyphosate at full rate w/o COC when glyphosate rate was cut in half. COC-1 matched full glyphosate efficacy at full glyphosate rate, but COC-1 efficacy at half glyphosate rate was slightly reduced.
[0031] Thus, the present invention provides blend compositions comprising: a) a first surfactant which comprises an alkoxylated amine; b) a second surfactant which comprises a phosphate ester; and c) and oil phase. The invention further comprises an emulsion which comprises a blend composition as just described, in combination with water and a herbicidally-active or pesticidal ingredient.
[0032] An amine surfactant according to the present invention is one or more materials selected from the group consisting of:
a) one or more materials represented by the structure:
in which R 1 is any C 8 -C 30 saturated, unsaturated, linear, or branched alkyl group and/or any C 8 -C 30 alkyl, alkaryl (linear or branched); R 2 is any C 2 -C 6 alkyl (linear or branched) or combinations thereof; x+y is in the range of between about 2 and 50; and Z is in the range of 0 to 10;
b) one or more materials represented by the structure:
in which R 1 is any C 2 to C 6 alkyl (linear or branched) group; R 2 is any C 2 to C 6 alkyl (linear or branched) or combinations thereof; and w+x+y+z is in the range of 4 to 50;
c) one or more materials represented by the structure:
in which R 1 is a C 8 to C 30 alkyl (saturated, unsaturated, linear or branched), and/or C 8 to C 30 alkyl, alkylaryl (linear or branched); R 2 is any C 2 to C 6 alkyl (linear or branched); and R 3 is any C 1 to C 6 alkyl (linear or branched) group;
d) one or more materials represented by the structure:
in which R 1 is a C 8 to C 30 alkyl (saturated, unsaturated, linear or branched), and/or C 8 to C 30 alkyl, alkylaryl (linear or branched); R 2 is any C 2 to C 6 alkyl (linear or branched); and R 3 is any C 2 to C 6 alkyl (linear or branched) or combinations thereof; and x+y is in the range of 2-50,
including mixtures of any of the foregoing four.
[0041] A phosphate ester surfactant according to the present invention comprises one or more materials represented by the structural formula:
in which R 1 and R 2 are each independently selected from the group consisting of H, and any C 9 to C 30 alkyl (linear, branched, saturated, unsaturated or combinations thereof) condensed with 0 to 30 moles of one or more of C 2 -C 6 alkylene oxides, and/or C 8 -C 30 alkyl, alkaryl (alkyl is linear and/or branched) condensed with 0-30 moles of one or more of C 2 to C 6 alkylene oxides and/or combination of aforementioned alkoxylated alkyl and alkyl, alkaryl, subject to the proviso that both R 1 and R 2 are not both simultaneously H.
Agriculturally-Active Materials
[0042] As used in this specification and the appended claims, the words “agriculturally active material” means any chemical substance that: 1) when applied to a given foliage that is generally regarded as undesirable adversely affects the longevity and/or reproductive capability of such foliage; or 2) when applied to a vicinity where insects dwell adversely affects the longevity and/or reproductive capability of such insects; 3) is regarded by those skilled in the art as possessing agriculturally-beneficial properties, including insecticidal, herbicidal, fungicidal, and growth-enhancing properties. Include within this definition, without limitation, are those chemical materials such as: 2,4,5-T, Acephate, Acetamiprid, Acrinathrin, Aldicarb, Amitraz, Amitrole, Arsenic and its compounds, Bendiocarb, Benfuresate, Bensulfuron methyl, Bentazone, BHC, 2,4-D Bitertanol, Butamifos, Butylate, Cadusafos, Captafol(Difolatan), Captan, Carbaryl, Chinomethionat, Chlorfenvinphos, Chlorfluazuron, Chlorimuron ethyl, Chlormequat, Chlorobenzilate, Chlorpropham, Chlorpyrifos, Chlorthalonil, Cinmethylin, Clofentezine, Copper terephthalate trihydrate, Cyanide compounds, Cyfluthrin, Cyhalothlin, Cyhexatin, Cypermethrin, Cyproconazole, Cyromazine, Daminozide, DCIP, DDT (including DDD,DDE), Deltamethrin, Demeton, Diazinon, Dicamba, Dichlofluanid, Dichlorvos, Diclomezine, Dicofol (Kelthane), Dieldrin (including Aldrin), Diethofencarb, Difenoconazole, Difenzoquat, Diflubenzuron, Dimethipin, Dimethoate, Dimethylvinphos, Edifenphos, Endrin, EPN, EPTC, Esprocarb, Ethiofencarb, Ethofenprox, Ethoprophos, Ethoxyquin, Etobenzanide, Etrimfos, Fenarimol, Fenbutatin oxide, Fenitrothion, Fenobucarb, Fenpyroximate, Fensulfothion, Fenthion, Fenvalerate, Flucythrinate, Flufenoxuron, Fluoroimide, Flusilazole, Flusulfamide, Flutolanil, Fluvalinate, Fosetyl, Fosthiazate, Glufosinate, Glyphosate, Guthion, Halfenprox, Heptachlor (including Heptachlor epoxide), Hexaflumuron, Hexythiazox, Imazalil, Imazosulfuron, Imibenconazole, Iminoctadine, Inabenfide, Inorganic bromide, Iprodione, Isophenphos, Isoprocarb, Lead & its compounds, Lenacil, Malathion, Maleic hydrazide, MCPA (including Phenothiol), Mepanipyrim, Mephenacet, Mepronil, Methamidophos, Methiocarb, Methoprene, Methoxychlor, Metolachlor, Metribuzin, Mirex, Myclobutanil, Nitenpyram, Oxamyl, Paclobutrazol, Parathion, Parathion-methyl, Pencycuron, Pendimethalin, Permethrin, Phenthoate, Phosalone (Rubitox), Phoxim, Picloram, Pirimicarb, Pirimiphos-methyl, Pretilachlor, Prohexadione, Propamocarb, Propiconazole, Prothiofos, Pyraclofos, Pyrazoxyfen, Pyrethrins, Pyridaben, Pyridate, Pyrifenox, Pyrimidifen, Pyriproxyfen, Quinalphos, Quinclorac, Sethoxydim, Silafluofen, Tebuconazole, Tebufenozide, Tebufenpyrad, Tecloftalam, Tefluthrin, Terbufos, Thenylchlor, Thiobencarb, Thiometon, Tralomethrin, Triadimenol, Tribenuron methyl, Trichlamide, Trichlorfon, Triclofos-methyl, Tricyclazole, Triflumizole, and Vamidothion.
Agricultural Adjuvants
[0043] Adjuvants are chemical materials which are often employed as a component of an formulation containing one or more agriculturally active materials and which are designed to perform specific functions, including wetting, spreading, sticking, reducing evaporation, reducing volatilization, buffering, emulsifying, dispersing, reducing spray drift, and reducing foaming. No single adjuvant can perform all these functions, but different compatible adjuvants often can be combined to perform multiple functions simultaneously; thus, adjuvants are a diverse group of chemical materials. Within the meaning of the term “Adjuvants” is included any substance added to the spray tank to modify a pesticide's performance, the physical properties of the spray mixture, or both.
[0044] Spray application is perhaps the weakest link in the chain of events a pesticide follows through its development process. Some researchers claim that up to 70 percent of the effectiveness of a pesticide depends on the effectiveness of the spray application. Selection of a proper adjuvant may reduce or even eliminate spray application problems associated with pesticide stability, solubility, incompatibility, suspension, foaming, drift, evaporation, volatilization, degradation, adherence, penetration, surface tension, and coverage, thereby improving overall pesticide efficiency and efficacy.
[0045] Surfactant adjuvants physically alter the surface tension of a spray droplet. For a pesticide to perform its function properly, a spray droplet must be able to wet the foliage and spread out evenly over a leaf. Surfactants enlarge the area of pesticide coverage, thereby increasing the pest's exposure to the chemical. Without proper wetting and spreading, spray droplets often run off or fail to adequately cover these surfaces. Such materials enhance the absorbing, emulsifying, dispersing, spreading, sticking, wetting or penetrating properties of pesticides. Surfactants are most often used with herbicides to help a pesticide spread over and penetrate the waxy outer layer of a leaf or to penetrate through the small hairs present on a leaf surface.
[0046] While surfactant adjuvants may be anionic, cationic, or non-ionic, the non-ionic surfactants are in most common usage. The “multi-purpose” non-ionic surfactants are composed of alcohols and fatty acids, have no electrical charge and are compatible with most pesticides. Certain other surfactants may be cationic (+ charge) or anionic (− charge) and are specialty adjuvants that are used in certain situations and with certain products. Anionic surfactants are mostly used with acids or salts, and are more specialized and used as dispersants and compatibility agents. Cationic surfactants are used less frequently but one group, the ethoxylated fatty amines, sometimes are used with the herbicide glyphosate.
[0047] Silicone-based surfactants are increasing in popularity due to their superior spreading ability. Some of these surfactants are a blend of non-ionic surfactants (NIS) and silicone while others are entirely a silicone. The combination of a NIS and a silicone surfactant can increase absorption into a plant so that the time between application and rainfall can be shortened. There are generally two types of organo-silicone surfactants: the polyether-silicones that are soluble in water and the alkyl-silicones that are soluble in oil. Unlike polyether-silicone types, alkyl-silicone surfactants work well with oil-based sprays, such as dormant and summer oil sprays used in insect control. Alkyl-silicone-enhanced oil sprays can maximize insecticidal activity and even allow significantly lower pesticide use rates that reduce residue levels on crops.
[0048] Sticker adjuvants increase the adhesion of solid particles to target surfaces. These adjuvants can decrease the amount of pesticide that washes off during irrigation or rain. Stickers also can reduce evaporation of the pesticide and some slow ultraviolet (UV) degradation of pesticides. Many adjuvants are formulated as spreader-stickers to make a general purpose product that includes a wetting agent and an adhesive.
[0049] Extender adjuvants function like sticker surfactants by retaining pesticides longer on the target area, slowing volatilization, and inhibiting UV degradation.
[0050] Plant penetrant surfactants have a molecular configuration that enhances penetration of some pesticides into plants. A surfactant of this type may increase penetration of a pesticide on one species of plant but not another. Systemic herbicides, auxin-type herbicides, and some translocatable fungicides can have their activity increased as a result of enhanced penetration.
[0051] Compatibility agent adjuvants are especially useful when pesticides are combined with liquid fertilizers or other pesticides, particularly when the combinations are physically or chemically incompatible, such as in cases when clumps and/or uneven distribution occurs in the spray tank. A compatibility agent may eliminate problems associated with such situations.
[0052] Buffers or pH modifier adjuvants are generally employed to prevent problems associated with alkaline hydrolysis of pesticides that are encountered when the pH of a pesticide exceeds about 7.0 by stabilizing the pH at a relatively constant level. Extreme pH levels in the spray mixture can cause some pesticides to break down prematurely. This is particularly true for the organophosphate insecticides but some herbicides can break down into inactive compounds in a matter of hours or minutes in alkaline situations (pH>7). For example, the insecticide Cygon (dimethoate) loses 50 percent of its pest control power in just 48 minutes when mixed in water of pH 9. At a pH of 6, however, it takes 12 hours for degradation to progress to that extent. On the other hand, sulfonyl urea (SU) herbicides tend to break down more rapidly where the pH is below 7. At low pHs, the herbicide 2,4-D is an uncharged molecule. At higher pH, 2,4-D tends to become more anionic or negatively charged which can affect its movement in the environment. Leaf coatings often have a high pH that can contribute to poor performance with certain herbicides. The use of a buffering or acidifying adjuvant can stabilize or lower the pH of a spray solution thereby improving the stability of the pesticide being used.
[0053] Mineral control adjuvants are used to mask the problems associated with water hardness minerals in spray water which can diminish the effectiveness of many pesticides. Mineral ions such as calcium, magnesium, salts and carbonates are commonly found in hard water. These ions can bind with the active ingredients of some pesticides, especially the salt-formulation herbicides such as Roundup™ (glyphosate), Poast™ (sethoxydim), Pursuit™ (imazethapyr), and Liberty™ (glufosinate) resulting in poor weed control. The use of water-conditioning adjuvants gives hard water minerals something to bind with other than the herbicide. In addition, some ammonium sulfate-based adjuvants can be used to offset hard water problems.
[0054] Drift retardant adjuvants improve on-target placement of pesticide spray by increasing the average droplet size, since drift is a function of droplet size with drops with diameters of 100 microns or less tending to drift away from targeted areas.
[0055] Defoaming agent adjuvants are used to control the foam or frothy head often present in some spray tanks that results from the surfactant used and the type of spray tank agitation system can often can be reduced or eliminated by adding a small amount of foam inhibitor.
[0056] Thickener adjuvants increase the viscosity of spray mixtures which afford control over drift or slow evaporation after the spray has been deposited on the target area.
[0057] Oil-based adjuvants have been gaining in popularity especially for the control of grassy weeds. There are three types of oil-based adjuvants: crop oils, crop oil concentrates (COC) and the vegetable oils. Crop Oil adjuvants are derivative of paraffin-based petroleum oil. Crop oils are generally 95-98% oil with 1 to 2% surfactant/emulsifier. Crop oils promote the penetration of a pesticide spray either through a waxy plant cuticle or through the tough chitinous shell of insects. Crop oils may also be important in helping solubilize less water-soluble herbicides such as Poast™ (sethoxydim), Fusilade™ (fluaziprop-butyl) and atrazine. Traditional crop oils are more commonly used in insect and disease control than with herbicides. Crop oil concentrates (COC) are a blend of crop oils (80-85%) and the non-ionic surfactants (15-20%). The purpose of the non-ionic surfactant in this mixture is to emulsify the oil in the spray solution and lower the surface tension of the overall spray solution. Vegetable oils work best when their lipophilic characteristics are enhanced, and one common method of achieving this is by esterification of common seed oils such as rapeseed, soybean, and cotton. The methylated seed oils (MSO) are comparable in performance to the crop oil concentrates, in that they increase penetration of the pesticide. In addition, silicone-based MSOs are also available that take advantage of the spreading ability of the silicones and the penetrating characteristics of the MSOs.
[0058] The special purpose or utility adjuvants are used to offset or correct certain conditions associated with mixing and application such as impurities in the spray solution, extreme pH levels, drift, and compatibility problems between pesticides and liquid fertilizers. These adjuvants include acidifiers, buffering agents, water conditioners, anti-foaming agents, compatibility agents, and drift control agents.
[0059] Fertilizer-based adjuvants, particularly nitrogen-based liquid fertilizers, have been frequently added to spray solutions to increase herbicide activity. Research has shown that the addition of ammonium sulfate to spray mixtures enhances herbicidal activity on a number of hard-to-kill broadleaf weeds. Fertilizers containing ammonium nitrogen have increased the effectiveness of the certain polar, weak acid herbicides such as Accent™ (nicosulfuron), Banvel™ (dicamba), Blazer™ (acifluorfen-sodium), Roundup™ (glyphosate), Basagran™ (bentazon), Poast™ (sethoxydim), Pursuit™ (imazethapyr), and 2,4-D amine. Early fertilizer-based adjuvants consisted of dry (spray-grade) ammonium sulfate (AMS) at 17 lbs per 100 gallons of spray volume (2%). Studies of these adjuvants has shown that Roundup™ uptake was most pronounced when spray water contained relatively large quantities of certain hard water ions, such as calcium, sodium, and magnesium. It is thought that the ions in the fertilizer tied up the hard water ions thereby enhancing herbicidal action.
[0060] Consideration must be given to the fact that although this invention has been described and disclosed in relation to certain preferred embodiments, obvious equivalent modifications and alterations thereof will become apparent to one of ordinary skill in this art upon reading and understanding this specification and the claims appended hereto. The present disclosure includes the subject matter defined by any combination of any one of the various claims appended hereto with any one or more of the remaining claims, including the incorporation of the features and/or limitations of any dependent claim, singly or in combination with features and/or limitations of any one or more of the other dependent claims, with features and/or limitations of any one or more of the independent claims, with the remaining dependent claims in their original text being read and applied to any independent claim so modified. This also includes combination of the features and/or limitations of one or more of the independent claims with the features and/or limitations of another independent claim to arrive at a modified independent claim, with the remaining dependent claims in their original text being read and applied to any independent claim so modified. Accordingly, the presently disclosed invention is intended to cover all such modifications and alterations, and is limited only by the scope of the claims which follow, in view of the foregoing and other contents of this specification.
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In agricultural practice it is known to use emulsifiable oils (commonly referred to a Crop Oil Concentrates, COC) as bioefficacy enhancers for pesticides, especially herbicides. Cationic surfactants are widely known to be particularly effective bio-active enhancers for herbicides, especially for glyphosate-type herbicides. The present invention includes two novel aspects: 1) While the vast majority of COCs are petroleum-based paraffinic oils or esterified seed oils, this invention embodies a new oil phase, a hydrocarbon oil such exemplified by EXXON-MOBILS D-130, which when combined with the surfactants described herein, exhibits surprising enhancement of herbicidal activity in field tests; and 2) COC's are designed to form stable emulsions in water The combination of cationic surfactants and phosphate esters in this invention not only form very stable emulsions in water, but, surprisingly, also form extremely stable emulsions in concentrated liquid fertilizers, including 32-0-0 fertilizer.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a corona wire cartridge for a corona discharger that is applied to a charger, a transcriber, and a static eliminator of an image forming apparatus.
2. Background Art
A corona discharger where high voltage is applied to an electrode having a wire shape, a corona wire, to generate corona discharging is applied to, for example, a charger, a transcriber, and a static eliminator of a printer or a copier that forms images by using an electrography process.
In the corona wire, discharging efficiency may be reduced or local discharging may occur due to oxidation coming from the discharging or deterioration coming from attachment of floating toners resulting from static electricity during the discharging, and nonuniform charging of an object to be charged (photoreceptor, intermediate transfer body, paper, and so on) incurs poor printing including nonuniform concentration of black lines, white lines, and images.
Therefore, it is necessary to regularly replace the corona wire, and a structure where the corona wire is easily replaced is proposed in, for example, JP-A-62-131274
SUMMARY OF THE INVENTION
JP-A-62-131274 discloses a corona wire cassette where corona wires are wound around a reel member having a spiral spring therein and drawn from a casing and wound into the casing.
Even though the above-mentioned configuration provides improved handling of the corona wires, it is disadvantageous in that since parts such as switch rollers or felt rings for providing the spiral spring into the reel member or guiding the corona wires from the casing are required, costs of parts and assembling are increased.
Additionally, tension is continuously applied to the corona wires in the casing due to the spring or a transverse load is applied to the corona wires due to the switch roller, causing inferior effects such as lengthening or cutting of the corona wires.
A corona wire cartridge includes: a reel around which a corona wire is wound; a reel holder that rotatably supports the reel; a casing having a receiving portion which receives the reel and the reel holder and a wire drawing opening through which the corona wire is drawn; and an elastic member that movably connects the casing to the reel holder.
According to an aspect of the invention, it is possible to provide a corona wire cassette that has reduced costs of parts and assembling due to the small number of parts.
Furthermore, it is possible to prevent corona wires from being lengthened and cut, as an unnecessary load is not applied to the corona wires.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more readily described with reference to the accompanying drawings:
FIG. 1 is a sectional elevation view illustrating an internal configuration of a corona wire cartridge.
FIG. 2 is a sectional view taken in the direction of the arrow along the line A-A of FIG. 1 .
FIG. 3 is a side view taken in the direction of the arrow B of FIG. 1 .
FIG. 4 is a side view of a reel.
FIG. 5 is a sectional view illustrating another embodiment of the invention.
FIG. 6 is a view illustrating the provision of an end of a corona wire to a corona discharger.
FIG. 7 is a view illustrating a device for determining a position of the corona wire cartridge in relation to the corona discharger.
FIG. 8 is a view schematically illustrating an image forming apparatus.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is an elevation in section illustrating an internal configuration of a corona wire cartridge, FIG. 2 is a sectional view taken in the direction of the arrow along the line A-A of FIG. 1 , FIG. 3 is a side view taken in the direction of the arrow B of FIG. 1 , and FIG. 4 is a side view of a reel.
In FIG. 1 , reference character W denotes a corona wire that has a diameter of about 0.06 mm and is formed of a tungsten wire, and reference numeral 31 denotes a reel around which the corona wire W is wound. As shown in FIG. 4 where the reel 31 is seen in the opposite direction in relation to FIG. 1 , the reel 31 has a thick portion 31 c at a circumference thereof so that a recess 31 b is formed around a reel shaft 31 a.
A radial groove 31 d extending from the recess 31 b to the circumference of the reel 31 is formed in a portion of a thick portion 31 c.
As to the reel 31 having the above-mentioned configuration, a wheel a that is provided at an end of the wire is hanged on the reel shaft 31 a so that the corona wire W is supported by the reel 31 . A portion other than the end of the wire W is drawn from the groove 31 d and wound around the circumference of the reel 31 . Meanwhile, an annular member b is provided at another end of the wire W.
Turning to FIG. 1 , the reel 31 is supported by a reel holder 32 . As shown in FIG. 2 , the reel 31 is inserted into the reel holder 32 and the reel shaft 31 a is fitted into through holes 32 a provided in the reel holder 32 , so that the reel 31 is rotatably supported by the reel holder 32 .
A receiving portion 33 a is formed in a casing 33 of the corona wire cartridge to receive the reel 31 supported by the reel holder 32 , and the reel 31 and the reel holder 32 are provided in the receiving portion 33 a like the arrangement of FIG. 1 .
The connection between the reel holder 32 and the casing 33 is performed using a spring 34 extending between a protrusion 33 b provided in the receiving portion 33 a and the reel holder 32 .
Since the reel holder 32 is always biased by the spring 34 in the direction of the arrow x, the reel 31 is also drawn in the same direction due to the reel holder 32 . For this, the reel 31 is supported by inclined sides 33 c provided in the receiving portion 33 a to stop the drawing of the reel and to regulate the position of the reel 31 in the receiving portion 33 a , so that excessive force (excessive tension) is not applied to the corona wire W.
A supporting portion 33 e is provided at a wire drawing opening 33 d of the casing 33 to support an annular member b provided at the wire W.
As shown in FIG. 6 , the annular member b which is provided at the wire W acts as a terminal hooked on a hook member 40 a that is provided in a corona discharger 40 when the wire is provided into the corona discharger. In order to provide the wire W into the corona discharger 40 , first, the annular member b is hooked on the hook member 40 a of the corona discharger.
Next, the cartridge longitudinally moves in relation to the corona discharger 40 to unwind the wire W. As shown in FIG. 7 , the position of the cartridge that moves from an end of the corona discharger 40 to another end thereof is determined by a projection 40 c that engages with a recess 33 f provided on a side of the casing 33 and an engagement hook 40 d hooked on a latch 33 g at a cartridge mounting portion 40 b provided in the corona discharger 40 .
Since the supporting portion 33 e which supports the annular member b is provided to the casing 33 to stabilize the posture of the annular member b, it is easy to hook the annular member b on the hook member 40 a of the corona discharger and the replacement of the wire W is efficiently performed.
Furthermore, since a piece 33 h having the latch 33 g is flexible, if the cartridge is to be separated from the corona discharger, an operator pushes the piece 33 h counterclockwise in FIG. 7 to unhook the latch 33 g fastened with the engagement hook 40 d of the corona discharger.
In the modification of the embodiment, as shown in FIG. 5 , a through hole 33 i may be formed in a side of the casing 33 facing the reel shaft 31 a and a groove 31 e for tools may be formed in the reel shaft 31 a.
According to the above-mentioned configuration, since the winding of the wire W around the reel 31 may be performed outside, the assembling of the cartridge is efficiently performed, and, even if the wire is loosened, the wire may be tightly wound outside.
FIG. 8 illustrates a laser beam printer on which a corona discharger equipped with the corona wire cartridge of the invention is mounted.
In FIG. 8 , reference numeral 1 denotes a laser beam printer, and a photosensitive drum 21 starts to rotate in the direction of the arrow by printing initiation signal that is transmitted from a controller 22 . The photosensitive drum 21 rotates at the speed that is identical with a printing speed of the laser beam printer 1 , and continues to rotate until the printing is stopped. If the photosensitive drum 21 rotates, high voltage is applied to the corona charger 2 including the corona discharger provided with the corona wire cartridge of the invention to uniformly charge the surface of the photosensitive drum 21 so that, for example, positive charges, are uniformly formed on the surface.
A polygonal rotating mirror 3 starts to rotate immediately after power is supplied to the laser beam printer 1 , and rotates highly precisely at a constant speed while the power is supplied. A laser beam emitted from a light source 4 that is formed of a semiconductor laser and so on reflects from the polygonal rotating mirror 3 and is radiated through an fθ lens 5 onto the photosensitive drum 21 while scanning is performed.
If letter data or figure data converted into dot images are transmitted from the controller 22 to the laser beam printer 1 as on/off signal of the laser beam, portions onto which the laser beam is and is not radiated are formed on the surface of the photosensitive drum 21 to form the so-called electrostatic latent image.
When the photosensitive drum having the electrostatic latent image reaches a portion facing a developing device 6 , a toner is supplied to the electrostatic latent image so that the positively charged toner is absorbed by static electricity, thus forming toner images at a portion from which electric charges are removed by radiation of the laser beam onto the photosensitive drum 21 .
Paper 7 that continuously extends and is received in a paper hopper 11 is transported between the photosensitive drum 21 and a transcriber 10 by using a paper transportation tractor 8 in synchronization with the arrival of the toner images of printed data formed on the upper surface of the photosensitive drum 21 to a transcription position. Furthermore, the transcriber 10 is a kind of corona discharger which is equipped with the corona wire cartridge of the invention.
The toner images formed on the photosensitive drum 21 are absorbed on the paper 7 by using the transcriber 10 that provides electric charges having the polarity opposite to that of toner images on a rear side of the paper 7 .
Therefore, the paper 7 that is provided in the paper hopper 11 is transported through the paper transportation tractor 8 , the transcriber 10 , the paper transportation tractor 9 , and a buffer plate 24 to a fixing device 12 . After the paper 7 transported to the fixing device 12 is preheated by a preheating plate 13 , the paper 7 is transported while being heated and pressed by using a nip portion formed by a pair of fixing rollers that is formed of a heating roller 14 provided with a heater lamp 25 and a pressing roller 15 to fix the toner images on the paper 7 by fusing.
The paper 7 which has been already transported by using the heating roller 14 and the pressing roller 15 is moved to a stacker table 19 by using a transportation roller 16 and accordion-folded along a roulette due to the swing of a swing fin 17 . Furthermore, the folded paper is adjusted by using rotating paddles 18 and stacked on the stacker table 19 . A portion of the photosensitive drum 21 that passes a transcription position is cleaned by using a cleaning device 20 , and then waits for the next printing.
In FIG. 8 , reference numeral 23 denotes a display screen that displays information regarding the state of the laser beam printer during the printing. The buffer plate 24 is used to compensate loosening or tightening of the paper 7 in the case of when there is a difference in paper transportation speed of the paper transportation tractor 9 and the fixing rollers 14 and 15 . Furthermore, reference numeral 26 denotes a web member that is capable of coming into contact with the surface of the heating roller 14 and being wound and is used to clean the surface of the heating roller 14 and apply a release agent on the surface of the heating roller 14 .
In the above-mentioned embodiment, a description is given of the application of the corona discharger provided with the corona wire cartridge of the invention to the charger 2 and the transcriber 10 . However, a corona static electricity remover may be provided to remove static electricity from a portion of the surface of the photosensitive drum 21 between the transcriber 10 and the cleaning device 20 , or a corona discharger for pre-electrification may be provided to perform pre-electrification of the surface of the photosensitive drum 21 between the cleaning device 20 and the charger 2 . In this connection, the invention may be applied to the corona static electricity remover and the corona discharger for pre-electrification.
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A corona wire cartridge includes: a reel around which a corona wire is wound; a reel holder that rotatably supports the reel; a casing having a receiving portion which receives the reel and the reel holder and a wire drawing opening through which the corona wire is drawn; and an elastic member that movably connects the casing to the reel holder.
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FIELD OF THE INVENTION
Embodiments of the present invention relate generally to waste management. Particularly, embodiments of the present invention relate to improved methods of handling waste products. More particularly, embodiments of the present invention relate to baling recyclables and trash.
BACKGROUND
A baler is a piece of machinery used to compress material into bales and bind the bales. There are several different types of balers commonly used. Balers are also used in the material recycling facilities, primarily for baling plastic, paper, or cardboard for transport to a recycling facility.
A baler is a piece of machinery used to compress material. Compressing takes up less space when stored, or when transported via truck or train to a recycling facility. A baler is just one step of the recycling process. They can also be used to compact other forms of waste, such as trash or even large boxes.
Balers can be portable or stationary. Older machines tend to be stationary—once they're set up, they stay there. Today, most balers are portable. Almost all modern balers use a hydraulic press. A motor powers a pump that pushes hydraulic fluid to drive cylinders. Using principles of force-multiplication, a hydraulic system can generate over 2,000 psi and impart more than 150 tons of force.
The press consists of several parts: bed where all the material is loaded; a plate rises to apply the compacting power; an engine, pump, valves, tubing and other parts of the hydraulic system, guideposts aligning the plate and making sure the compacting force is applied evenly.
While the above described baling structure may be suitable for baling paper, cardboard or other dry materials, it is generally not suitable for handling trash including moist garbage or other fluid containing refuse.
There are also available refuse compactors which are suited to the handling of liquid containing refuse and they generally solve the problem by utilizing a waterproof container into which the loose trash is compacted. It is to be noted; however, if one were to attempt to utilize a preformed carton in the baler apparatus, during the downward stroke of the compaction plate thereof, the container would be at least partially torn and crushed.
Most trash compactors compress trash in the compactor into a cube shape but when the trash is removed the trash tends to expand and unless contained in a bag or box the cube of compacted trash tends to expand and fall apart making the compacted trash hard to handle and move from the trash compactor to a waste container such as a dumpster or for shipping to a land fill.
It would be an advantage to be able to bale the compacted trash in the trash compactor before removing the compacted trash and transporting it to waste storage and thereafter to a landfill or other waste disposal facility.
A need, therefore, exists for a waste baling machine providing:
an easy way to wrap string around a bale of compacted trash in the cavity of a trash compactor without removing the bale from the trash compactor cavity before it is baled;
quick and easy baling of trash in a trash compactor;
easy access to the bale of trash and safety features to isolate the trash during compaction;
easy access entryways to the trash bales;
effortless handling of large access doors to the trash bales;
a way to pull baling string around the back and under a bale of compacted trash without undue resistance of the string between the compacted trash and the cavity walls or base; and
a storage area for the baling string and an easy way to use the string stored in the storage area.
SUMMARY OF THE INVENTION
In some embodiments, a compactor may include one or more of the following features: (a) a base, a first side panel, and a second side panel, (b) a first door for access to the compactor to place trash into the compactor for compacting, (c) a second door for access to the compactor to remove compacted trash (d) at least one door operably coupled to a counterbalance weight to provide easy movement of the at least one door to move along a track, (e) at least one continuous channel beginning in an upper portion of a back wall and traversing to a front of the base, the channel having a curved portion transitioning from the back wall to the bottom wall, (f) a machine compartment for housing string used to tie around a bale of trash in the compactor, the string surrounding the compacted trash and tied off to secure the bale of compacted trash prior to removal from the cavity of the compactor, (g) a top panel operably coupled to the first and second side panel, (h) a third door for access to the machine compartment, and (i) a second counterbalance operably coupled to the second door to provide easy movement of the second door along a second track.
In some embodiments, a refuse compactor may include one or more of the following features: (a) a base, a first side panel, and a second side panel, (b) a machine compartment, a receiving compartment, and a compaction compartment located within the compactor, (c) a first door operably coupled to a first counterbalance to allow the first door to slidably move along a first track, (d) a second door operably coupled to a second counterbalance to allow the second door to slidably move along a second track, (e) a platen operably coupled to a hydraulic pump located in the machine compartment for compacting refuse in the compaction compartment, (f) a top panel, (g) a third door providing access to the machine compartment, (h) a control box located on at least one side panel, and (i) a power control switch and operational switch located adjacent to the control box.
In some embodiments, a method of compacting refuse may include or more of the following steps: (a) inputting the refuse into a receiving compartment of a compactor where the refuse comes to rest in a compacting compartment of the compactor, (b) placing a first door over an access to the receiving compartment and a second door over an access to the compacting compartment, (c) initiating compaction of the refuse, (d) powering on the compactor, and (e) removing a refuse bale after compaction.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an embodiment of the present invention;
FIG. 2 is a side view of an embodiment of the present invention;
FIG. 3 is a exploded view of an embodiment of the present invention;
FIG. 4 is an isometric view of a front of a compactor in an embodiment of the present invention; and
FIG. 5 is a flow process diagram showing an operation in an embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following discussion is presented to enable a person skilled in the art to make and use the present teachings. Various modifications to the illustrated embodiments will be readily apparent to those skilled in the art, and the generic principles herein may be applied to other embodiments and applications without departing from the present teachings. Thus, the present teachings are not intended to be limited to embodiments shown, but are to be accorded the widest scope consistent with the principles and features disclosed herein. The following detailed description is to be read with reference to the figures, in which like elements in different figures have like reference numerals. The figures, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of the present teachings. Skilled artisans will recognize the examples provided herein have many useful alternatives and fall within the scope of the present teachings. While embodiments of the present invention are described with reference to a trash compactor it is fully contemplated embodiments of the present invention could be used for recyclables and reusable material's without departing from the spirit of the invention.
Referring first to FIG. 1 , the trash compactor cabinet of the present invention is indicated generally by numeral 10 . It includes a base plate 12 , a top panel 14 , frame 11 having a right side panel 16 , a left side panel 18 , and a rear wall 20 . These panels are joined to form a generally rectangular parallelepiped of a predetermined length, width, and height Secured in tracks 4 , 6 , and 8 on the front edge of the front portion 21 are first 22 , second 24 , and third 26 access doors. The cabinet 10 may be mounted on castors as at 28 to facilitate the repositioning of the compactor 10 .
Frame 11 can be made of two panels 16 and 18 of sheet metal which are shaped to provide a front portion 9 , a side wall 5 , and half the back wall 20 of frame 11 . The construction of frame 11 is discussed in more detail in a co-pending patent application titled “Trash Compactor Cabinet”, Ser. No. 11/949,855, filed on Dec. 4, 2007, the contents of which are herein incorporated by reference in its entirety. Front portion 9 of frame 11 has a small front facing surface for attaching doors 22 , 24 , and 26 for access to compactor 10 . Back 20 and sides 5 has a V-shaped indentation 44 for allowing a passage between back 20 and shelving in compactor 10 and to give back 20 added strength. Back 20 also has a V-shaped overlap portion 37 which connects two pieces 16 and 18 of frame 11 and adds strength to compactor 10 . Shelves can be attached to the walls in frame 11 which provide strength for frame 11 and support the mechanisms for compacting trash.
Compactor 10 can be made from pieces of sheet metal which are shaped to provide side panels 16 and 18 and rear 20 . The front of compactor 10 has doors 22 , 24 , and 26 for access to compactor 10 . Rear panel 20 has a V-shaped indentation for allowing a passage between the back wall and a shelf in compactor 10 and to give rear panel 20 added strength. Shelves and supports are attached to panels 16 , 18 , and 20 in compactor 10 which provide strength for compactor 10 and support the mechanisms for compacting trash. A base 12 and top panel 14 attached to the sheet metal pieces complete the construction of compactor 10 . Panels 16 and 18 of compactor 10 are bent into the desired shape and are lightweight, inexpensive, and strong. V-Shaped indentations 44 add strength to rear panel 20 and allow a passageway between rear panel 20 and shelves ( FIG. 3 ) inside trash compactor 10 .
With reference to FIG. 2 , a side view of an embodiment of the present invention is shown. Mounted upon right side panel 16 is control box 30 with power control switch 32 and operational switch 34 . Power control switch 32 activates or provides power to compactor 10 when an operator turns power control switch 32 from an “off” position to an “on” position. Operational switch 34 is used by an operator when it is desired to compact materials within compactor 10 . The operator would turn operation switch 34 to a “compact” position to begin the compaction process. Also shown are counterbalances 40 and 42 discussed in more detail below.
Next, with reference to FIG. 3 , it can be seen the interior of compactor 10 is effectively and functionally divided into three compartments or volumes. Specifically, the so-called machine compartment is identified by numeral 50 , trash receiving compartment 51 , and the trash compacting compartment by numeral 52 . Dividing the machine compartment 50 from the trash compacting compartment 52 is a mounting plate 54 on which is mounted a hydraulic pump 56 , a hydraulic cylinder 58 , and the various electrical and hydraulic controls for the system. Piston 60 of the hydraulic cylinder 58 passes through an opening in the mounting plate 54 and affixed to the lower end thereof is a compaction plate or platen 62 . With reference to FIG. 3 , there is further shown a cross arm 64 which is also disposed in the machinery containing compartment 50 and which is affixed at opposed ends thereof to panels 16 and 18 . The uppermost end of the cylinder 58 abuts and is fastened to a further horizontal structural member comprising the cabinet framework and the lower end thereof is suitably clamped to the cross arm 64 . Thus, when actuated, the piston 60 moves outwardly from its cylinder 58 causing the platen 62 to move downward for a predetermined distance into compaction compartment 52 .
In operation, after trash compactor 10 compresses the trash in compaction compartment 52 a cube of trash in compartment 52 could be baled so it remains in a cube and is easier to handle for transporting, storing, and disposal. In order to bale the cube of compacted trash it is necessary to surround the bale with a bailing material such as twine, rope, string, a webbing material, tape, or wire. A spool of string 70 provides string to bale the left side of the compacted trash in compartment 52 and a spool 72 provides string for the right side of the compacted trash in compartment 52 . String from spool 70 runs behind spool shelf 74 and then travels in channel 80 behind mounting plate 54 and stays in channel 80 behind platen 62 to enter compartment 52 . Similarly string from spool 72 runs behind spool shelf 74 and then travels in channel 82 behind mounting plate 54 and stays in channel 82 to go behind platen 62 to enter compartment 52 . The strings can then be placed on the back side and the bottom side of the compacted cube of trash without removing the cube of trash from the cavity.
With reference to FIG. 4 , an isometric view of a front of a compactor in an embodiment of the present invention is shown. Door 22 is most commonly shut to isolate machine compartment 50 from the operator. Should the operator need access to machine compartment 50 , perhaps to replace a spool of string 70 , the operator would simply grasp handle 100 and pull door 22 towards the operator lifting on handle 100 and sliding door 22 along roller tracks 101 along a top portion of machine compartment 50 . With door 22 open, the operator could perform duties or maintenance within machine compartment 50 as necessary. When the operator was finished, he/she could grasp handle 100 pull door 22 towards them, lowering handle 100 so door 22 once again covers machine compartment 50 .
Trash compacting compartment 52 is adjacent to trash receiving compartment 51 . Trash receiving compartment 51 provides a space for an operator to input trash and recyclables into compactor 10 . There are several ways an operator could input trash and/or recyclables into compactor 10 . An operator could slide door 24 upward along track 6 placing door 24 in an up position. Now the operator could input the trash directly into trash receiving compartment 51 allowing the materials to fall to compacting compartment 52 . Door 24 slides easily along track 6 . Very little effort is needed by the operator as door 24 is counterbalanced by weight 42 . Door 24 could also be lowered toward base 12 thus again exposing trash receiving compartment 51 . In this operation, door 24 would move in a downward direction as counterbalance 42 moved man upward direction. Whether door 24 is in a fully up or down state, the operator is able to input trash into trash receiving compartment 51 .
If necessary trash receiving compartment 51 and compaction compartment 52 can be fully exposed to an operator by sliding doors 24 and 26 along tracks 6 and 8 respectively upwards. Here once again, counterbalances 42 and 40 respectively allow the operator to apply minimal force to doors 24 and 26 to raise them. Doors 24 and 26 , and counterbalances 42 and 40 can weigh approximately the same amount. Therefore, counterbalances 42 and 40 would not tend to fall due to gravity if doors 24 and 26 weighed less than counterbalances 42 and 40 . This would also prevent doors 24 and 26 from falling due to gravity if left unattended if the weight of counterbalances 42 and 40 was less than the doors. By having the weight of doors 24 and 26 be approximately the same as the counterbalances 42 and 40 a balance can be obtained where doors 24 and 26 will remain when placed somewhere by the operator.
With door 26 in an upward position, an operator could have access to compaction compartment 52 to remove a bale of trash or recyclable material. The operator could also insert material to be compacted this way as well.
With reference to FIG. 5 , a flow process diagram showing an operation in an embodiment of the present invention is shown. In process operation 200 then, trash can be inserted into the compaction compartment 52 or receiving compartment 51 at state 202 . The operator can also ensure doors 22 is closed and doors 24 and 26 are covering receiving compartment 51 and compaction compartment 52 respectively at state 204 . When a sufficient level of trash is deposited into compaction compartment 52 , the operator turns switch 34 to actuate motor 56 causing the hydraulic piston 60 to move out from its cylinder 58 at state 206 . In doing so, compaction plate 62 traverses receiving compartment 51 and partially enters compaction compartment 52 at state 208 . The loose refuse is thereby compacted and, again, piston 60 and platen 62 can be raised to permit additional trash to be deposited. When the level of compacted trash reaches a predetermined level or weight, the operator can open the access door 26 and remove the trash bale at state 210 . More material can now be inserted into receiving compartment 51 and the process can begin all over again at state 202 .
Thus, embodiments of the WASTE BALING MACHINE are disclosed. One skilled in the art will appreciate the present teachings can be practiced with embodiments other than those disclosed. The disclosed embodiments are presented for purposes of illustration and not limitation, and the present teachings are limited only by the following claims.
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In some embodiments, a compactor for a restaurant facility may include one or more of the following features: (a) a base, a first side panel, and a second side panel, (b) a first door for access to the compactor to place trash into the compactor for compacting, (c) a second door for access to the compactor to remove compacted trash, (d) at least one door operably coupled to a counterbalance weight to provide easy movement of the at least one door to move along a track, and (e) at least one continuous channel beginning in an upper portion of a back wall and traversing to a front of the base, the channel having a curved portion transitioning from the back wall to the bottom wall.
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BACKGROUND OF THE INVENTION
This invention is directed toward the art of joints and couplings. More particularly, the invention relates to an apparatus for testing the adequacy of swaging of tubes or pipes.
The present invention is especially suited for use in testing the adequacy of pull up of ferrules of swage type tube fittings on tubes or pipes and hence the adequacy of the swaging operation and will be described with particular reference thereto. It should, however, be appreciated that the subject invention is capable of broader applications and could be used for testing the adequacy of pull up of ferrules onto cylindrical members that are used for many different purposes.
Swage type tube or pipe fittings have become widely used. These fittings generally employ one or more ferrules which encircle the tube or pipe to be coupled. As the coupling nut is advanced on the coupling body, the ferrule or ferrules are subjected to axial pressure and are forced into a tapered mouth in the coupling body thereby causing the ferrule to contract upon the tube or pipe. In this way, the ferrule is progressively deformed into a gripping and sealing engagement with the tube or pipe by a radial contraction of the ferrule due to the interaction of the coupling nut and the fitting body. Since the contraction of the ferrule upon the tube or pipe is produced by an advancement of the coupling nut along the coupling body, it is apparent that the amount of contraction of the ferrule is determined by the amount of advancement of the coupling nut.
To a considerable extent, the successful utilization of couplings of the aforementioned type depends upon a controlled constriction or swaging of the walls of the tubular member to be coupled. In fittings of this type, the optimal amount of tube wall constriction or swaging is a predetermined quantity depending upon the correct amount of linear nut advancement necessary to produce the optimum amount of swaging. If the coupling nut is not advanced far enough, the ferrules will not be contracted or collapsed sufficiently to produce the required swaging of the tube wall. An insufficient swaging results in a connection which is susceptible to leakage. On the other hand, should the coupling nut be advanced more than the prescribed amount, the annular ferrules will be overcontracted upon the tube wall causing an overswaging of the tube. Such excessive swaging may result in reducing the number of times that the fitting can be disconnected and remade. It can also cause a rupture of the tubular member wall or at least create fluid flow problems in the tubular member.
In making an effective and tight connection between a tube or pipe in this type of fitting, it is also important that the dimensional relationships between the tube or pipe and the various components of the fitting not vary appreciably from those prescribed. Deviations from the prescribed tolerances on the amount of radial contraction of the ferrules onto the tube or pipe to create a clinching grip on the tube or pipe may result in unsatisfactory connections leading to inadequate sealing and leakage.
While there have been some devices which measure the amount of swaging or tube deformation that has occurred between a cylindrical body and a fitting, none of these has been found to be fast, easy to use and precise in its readout of the adequacy of swaging. Also, none of the current measuring devices can be selectively recalibrated as desired. Further, none of the current measuring devices are provided with a master to check the accuracy of the readings provided by the measuring device.
Accordingly, it has been considered desirable to develop a new and improved device for measuring the adequacy of swaging which would overcome the foregoing difficulties and others while providing better and more advantageous overall results.
BRIEF SUMMARY OF THE INVENTION
In accordance with the present invention, a gauge for fittings of the type including a coupling nut having a threaded internal opening and adapted to encircle a cylindrical member and a ferrule positioned on the cylindrical member is provided. The gauge is used for determining the pull up of the ferrule and the deformation or swaging that the cylindrical member has undergone.
More particularly in accordance with this aspect of the invention, the gauge comprises an indicating unit having a readout means for showing whether the swaging of the cylindrical member is within tolerances. A piston is movably mounted in the indicating unit and is operatively connected to the readout means. The piston comprises a body having a bore and an external thread means on the body circumferentially of the bore to threadedly engage the threaded internal opening of the coupling nut carried on the cylindrical member. A means is provided within the piston body bore for aligning the cylindrical member with the bore and for limiting the extent of movement of the cylindrical member into the bore.
According to another aspect of the invention, a gauge is provided for determining the pull up to an outer periphery of a cylindrical pipe or tube that a ferrule has undergone and the swaging of the pipe or tube by a fitting of the type including a coupling nut having a threaded internal opening and adapted to encircle the pipe or tube and a ferrule positioned on the pipe or tube.
More particularly in accordance with this aspect of the invention, the gauge comprises an indicating unit and a base secured to the indicating unit and including a longitudinally extending bore. A piston is slidable in the base bore. The piston comprises a body having a bore and an external thread means on the body circumferentially of the bore to threadedly engage the threaded internal opening of the coupling nut which is carried on the pipe or tube. A tapered mouth is formed in the bore for aligning the pipe or tube with the bore and for limiting the extent of movement of the pipe or tube into the bore. A means is provided for limiting a sliding movement of the piston in the base bore.
According to a further aspect of the invention, a method is provided for determining the swaging that a cylindrical member has undergone by a ferrule positioned on the outer periphery of the cylindrical member.
More particularly in accordance with this aspect of the invention, the method comprises the steps of providing a swaged cylindrical member having a coupling nut with a threaded internal opening that is adapted to encircle the cylindrical member and a ferrule pulled up on the cylindrical member. An indicator unit is provided that has a readout means for indicating acceptable and unacceptable swaging as well as a base and a piston secured thereto. The piston includes a bore that is adapted to receive a portion of the cylindrical member and includes an external threaded section. The fitting coupling nut is threaded onto the piston threaded section. The swaged fitting cylindrical member is then pushed into contact with the indicator base thereby changing the readout means. The readout means of the indicator unit is thereupon viewed to see whether the swaged fitting is acceptable or unacceptable.
According to a still further aspect of the invention, a device is provided for calibrating a gauge which measures the swaging of a cylindrical member.
More particularly in accordance with this aspect of the invention, the device comprises a coupling nut having a threaded internal opening and a gauge pin extending through the coupling nut internal opening. The gauge pin comprises a first section of a first diameter and a second section of a second diameter which is larger than the first diameter. A fastener means is provided for securing the gauge pin to the coupling nut.
One advantage of the present invention is the provision of a new means for testing the adequacy of a ferrule setting or swaging operation.
Another advantage of the present invention is the provision of a gauge which enables one to determine whether a ferrule has been adequately pulled up on a cylindrical member and whether the cylindrical member has been correctly swaged.
Still another advantage of the present invention is the provision of a gauge, which checks the amount of swaging of a cylindrical member, with a means for calibrating the gauge to check the accuracy of the readings provided by the gauge.
A further advantage of the present invention is the provision of a tube or pipe swaging gauge which is so constructed that it can be modified or adjusted as necessary in order to test the adequacy of swaging of tubes or pipes of different diameters and with different types of fittings.
A still further advantage of the present invention is the provision of a gauge for testing the adequacy of swaging of a cylindrical member with a visual readout which enables one to ascertain quickly and conveniently whether the swaging of the cylindrical member is within acceptable limits.
Still other benefits and advantages of the invention will become apparent to those skilled in the art upon a reading and understanding of the following detailed specification.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take physical form in certain parts and arrangements of parts, a preferred embodiment of which will be described in detail in this specification and illustrated in the accompanying drawings which form a part hereof and wherein:
FIG. 1 is a front elevational view of a gauge according to the present invention which is shown as measuring the adequacy of swaging of a cylindrical member;
FIG. 2 is a side elevational view partially in cross-section of a portion of the gauge of FIG. 1;
FIG. 3 is an enlarged front elevational view in partial cross-section of a portion of the gauge of FIG. 1; and,
FIG. 4 is an enlarged front elevational view in partial cross-section of a portion of the gauge of FIG. 1 having a master secured thereto instead of a fitting, the master being used to check the accuracy of the readings provided by the gauge.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, wherein the showings are for purposes of illustrating a preferred embodiment of the invention only and not for purposes of limiting same, FIG. 1 shows the subject new gauge unit A that is used for testing the adequacy of swaging of one or more components of a fitting B onto a cylindrical member C. While the gauge is primarily designed for and will hereinafter be described in connection with a particular type of fitting, it will be appreciated that the overall inventive concept involved could be adapted for use with other types of fittings and other types of cylindrical bodies as well.
With reference now to FIG. 2, the gauge unit comprises a housing 10 which is generally elongated and is provided at one side with a relatively long recess 12 which houses a dial indicator 14 between a top wall 16 and a bottom wall 18. The bottom wall 18 is relatively thick and is provided with a passage 20 extending therethrough and communicating with the interior recess 12. The housing 10 is also provided with a keyway indicated generally at 24 in which is longitudinally slidable a key slide 26. At its lower end, the key slide 26 has a forwardly projecting recessed portion 28 adapted to receive a clamping element 30 which can be secured to the forwardly projecting portion by suitable fasteners 32. The clamping element 30 cooperates with the key slide to engage the lower portion of the dial indicator 14 and to carry it for vertical adjustment.
At its upper end, the key slide 26 includes a rearwardly extending lug 34 which is threaded and which is movable in an elongated seat 36 formed in the inner wall of the housing. The top wall 16 of the housing includes a recess 38 in which is received an adjustment retainer cap 40. The cap is retained in position by a pair of set screws 42 (FIG. 1) or the like. Retained in position by the adjustment retainer cap 40 is an adjustment screw 44 the lower end of which is threadedly engaged with the lug 34 of the keyway slide.
In addition, the housing is provided on the outer face of its back wall with an elongated slot 46 through which extend a pair of clamping screws 48. These screws are threadedly engaged with the key slide 26. It will be readily apparent that when the screws 48 are loosened, the dial gauge 14 may be adjusted vertically by appropriate rotation of the adjusting screw 44 and the indicator may thereafter be locked in the adjusted position by again tightening the clamping screws 48. The passage 20 is threaded and receives an adjusting thimble 54 which has an opening therethrough for receiving a plunger 56 of the dial indicator. The opening through the thimble is enlarged at the lower portion thereof for reception of a light compression spring 58. Below the lower end of the thimble 54 is received a ball 60. A set screw 62 is provided in the housing 10 for preventing movement of the ball 60 out of the passage 20.
The ball 60 has a range of movement limited outwardly by its engagement with the set screw 62 and inwardly by its engagement with a lower end of the adjusting thimble 54. It will be apparent that the thimble 54 may be adjusted independently of the key slide 26 by a simple turning motion thereof.
With reference now to FIG. 3, the housing lower end includes a flat surface 70 tapped as indicated at 72 for the reception of fasteners 74. A gauge of the type described above is available from the A. G. Davis Gauge and Engineering Company of Hazel Park, Mich.
The fasteners 74 are adapted to secure a base 80 to the gauge. The base 80 includes a flanged portion 82 having apertures 84 extending therethrough which are suitably counterbored for receipt of the fastener heads. A bore 86 extends longitudinally through a main portion 87 of the base 80. Additionally, a threaded aperture 88 extends through the wall of the base main portion and communicates with the bore 86 therein.
A piston 90 is adapted to be slidably secured in the bore 86. The piston has a body 92 which is provided at one end with an axial bore or aperture 94 extending thereinto. At the front end of the piston aperture 94 is provided an outwardly tapered mouth surface or seat 96. A slot 98 is machined into an outer periphery 100 of the piston 90. The slot 98 is so located as to communicate with the aperture 88 in the base 80. A threaded section 102 is provided on the piston outer periphery 100 circumferentially of the aperture 94 to receive a coupling nut 110 which is internally threaded as at 112.
The piston 90 is held in the base 80 through the cooperation of a threaded fastener 114 (FIG. 1) which extends through the threaded aperture 88 of the base 80. A free end of the fastener 114 extends into the slot 98 in the piston to control the range of movement that the piston can have in relation to the base. If desired the piston can move a limited amount such that in a lower position, an inner end of the piston is below the flat 25 surface 70 of the gauge body 10 (see FIG. 3) and in an upper position, the inner end of the piston is above the flat surface 70 (see FIG. 1). As the piston 90 moves, the ball 60 is moved as is the plunger 56 of the dial indicator 14. In this way, the piston is operatively connected to the dial indicator.
The nut 110 of the fitting B is of the type adapted to encircle a cylindrical member 120 such as a pipe or tube and at least one ferrule positioned on the cylindrical member. In the embodiment illustrated, the fitting includes a front ferrule 122 and a back ferrule 124. It should, however, be appreciated that the fitting B could have other configurations as well. The back ferrule is held in a captive relationship between the front ferrule and an internal annular flange 126 formed on the unthreaded end of the coupling nut 110 internal wall. When a suitable deformation operation has been performed on the ferrules, the generally tapered shape of the ferrules 122, 124 will cause a sequential inward gripping of the cylindrical member 120 as is well known in the art and as is evident from FIG. 3.
In a swage type fitting of the nature here involved, the amount of swaging or deformation of the cylindrical member 120 is very critical since too great a deformation or swaging will cause an internal obstruction in the member 120 and create fluid flow problems as well as possibly a rupture of the cylindrical member and assuredly a defective connection. On the other hand, an inadequate amount of swaging will produce an unstable or unreliable fitting and allow a leakage of fluids.
In practice, the various elements of the fitting are manufactured to extremely close tolerances and the fitting is most often used in connection with tubing which is manufactured within very close tolerances as well. The coupling assembly is generally shipped to the user in a finger tight condition and for use is slipped onto the tubing until the tube abuts against the seat of the coupling body.
Various ways and means have been used to control very accurately the amount of swaging or gripping between the coupling and the cylindrical body. One technique has been to use a fixed gauge between the forward portion of the coupling nut and the body to which the nut is meant to be coupled until further advance is arrested by the gauge. Another practice has been to rotate the coupling nut a prescribed amount. When the prescribed tolerances of all the critical elements in the fitting as well as the dimensions of the pipe are adhered to accurately, the aforementioned methods of assembly have generally proven adequate. Difficulty arises, however, if the cylindrical member is not within tolerances or if the methods of assembly are not accurately followed.
Accordingly, several swaging tools are known to the art which are meant to provide an hydraulically powered swaging of a cylindrical body.
Whichever technique of swaging is used, a need exists for ascertaining whether the swaging has been correctly performed. In other words, it would be beneficial to know whether the ferrule or ferrules have been correctly pulled up on the cylindrical member. The gauge device of the present invention can be used for this purpose. The gauge is so configured that the coupling nut of the fitting and the ferrule(s) thereof engage the piston and thereafter the cylindrical member 120 can be pushed into the gauge member, together with the piston, to ascertain whether the swaged member 120 is within tolerances.
For this purpose, the nut 110 is threaded onto the piston 90 in a finger tight manner. At this point, the front ferrule 122 engages the piston tapered mouth surface 96 to prevent the cylindrical member 120 from sliding further into the piston aperture 94. Thereafter the swaged assembly, and the piston 90, are pushed into the gauge base 80 and the dial 14 is read. A means is provided for limiting the motion of the piston 90 into the base 80.
In this connection, the nut 110 after it has been threaded onto the piston 90 is, as shown in FIG. 3, able to travel a distance 130 between confronting planar substantially parallel faces 132 of the base 80 and 134 of the nut 110. As may be seen from FIG. 1, when the nut 110 is abutting the base 80, a needle 140 of the dial indicator 14 should read within an acceptable swaging range 142 on the dial and not within an unacceptable range 144.
The geometry and dimensional interrelationship of the components are such as to insure that the inventive gauge will operate correctly when measuring all conventional swaging operations of a cylindrical body to indicate whether the swaging operation has been performed within accepted tolerances.
If desired, the gauge can be preset so that when at rest the needle 140 reads at approximately nine o'clock. The movement of a correctly swaged assembly against the gauge base will then pivot the needle approximately 450° clockwise into the zero or twelve o'clock position as is illustrated in FIG. 1. In the preferred embodiment, the gauge can be so set that the needle cannot swing back into the acceptable range 142 more than once after having rotated through the unacceptable range 144. Of course, other ways of controlling the motion of the gauge needle can also be selected. It should be recognized that the setting of the needle can be changed as desired simply by a rotation of the knob 54.
When the gauge is at rest, there is no force exerted on the piston 90 pushing it into the base 80. At this time, the spring 58 serves as a means for biasing the piston away from the housing 10, and the base 80 secured thereto, by urging the ball 60 downwardly in the bore 20 to the extent allowed by the set screw 62. The ball 60 in turn urges the piston 90 downwardly in the base 80 to the extent allowed by the slot 98 cut in the piston outer periphery.
With reference now also to FIG. 4, a master D can be utilized with the gauge A as a means for checking the accuracy of the readings provided by the gauge. The master D comprises a nut 150 having a threaded inner periphery 152 which can be threaded onto the threaded section 102 provided on the outer periphery 100 of the piston 90. Held in the nut 150 is a gauge pin 160 which includes first and second spaced sections 162, 164 that are of different diameters. The first section 162 is of a diameter which can slide into the aperture 94 in the piston 90. The second section 164 is of a somewhat larger diameter which will be restricted from continued movement into the piston aperture 94 by engagement with the tapered surface 96 as is evident from FIG. 4. In this way, the gauge pin is limited in its sliding motion into the piston 90. A pair of flanges 165, 166 can also be positioned on the gauge pin in a spaced manner for confining a seal 168 therebetween. A recessed area 170 can also be provided on the pin in a spaced manner from the flanges 166 for holding a second seal 172. An additional recess 174 can be provided on the gauge pin 160 for housing a snap ring 176 which restricts the movement of the gauge pin in one direction in relation to the nut 150. Movement of the gauge pin in the other direction in relation to the nut is prevented by an engagement of a back side of the flange 166 with an inner face 178 of the nut.
While the seal elements 168 and 172 are not always necessary, they are considered to be advantageous in order to prevent any dirt or particles from locating between the nut inner face 178 and a back side of the flange 166 when the master is used in a dirty environment. Should any dirt accumulate on the nut face 178, the measurements provided by the master would be erroneous. However, it should be appreciated that there may not be a need for such sealing elements 168, 172 when the master is utilized in a clean environment.
In use, the accuracy of readings provided by gauge is checked with the master by threading the master onto the gauge piston 90 in a finger tight manner, thereafter the master is pushed into the gauge until a face 132 of the base 80 is contacted by a face 180 of the nut, thereby eliminating the gap 130 between them, much as in FIG. 3. At this point, the needle 140 shown in FIG. 1 should read zero or twelve o'clock.
In other words, when the master nut 150 has been threaded finger tight on the gauge piston 90, the setting of the needle 140 on the dial can be much the same as with the coupling B such that the initial setting of the needle 140 is at the nine o'clock position. Thereafter, the needle 140 should swing around approximately 450° clockwise to the zero or twelve o'clock position as the master is pushed into the gauge, if the gauge is correctly calibrated. Should this not be the case, the gauge can be recalibrated as desired so that it again indicates correctly when the master is used. Thereafter, the gauge can again be used in measuring the swaging of various cylindrical members.
It should be appreciated that the gauge can be adapted for use with different tube or pipe diameters and different types of couplings, i.e. having only one ferrule, simply by a replacement of the piston 90 with a suitably sized and apertured piston having a desired tapered mouth or seat.
Generally the gauge and its master are set by its manufacturer during assembly. Normally readjustment of the gauge should not be done except when the master indicates that the gauge is reading inaccurately.
The invention has been described with reference to a preferred embodiment. Obviously, modifications and alterations will occur to others upon a reading and understanding of this specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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A gauge for fittings of the type including a coupling nut having a threaded internal opening and adapted to encircle a cylindrical member and a ferrule positioned on the cylindrical member, the gauge being used for determining the pull up of the ferrule and the swaging of the cylindrical member, includes an indicating unit having a readout for showing whether the swaging of the cylindrical member is within tolerances. A piston is movably mounted on the indicating unit and is operatively connected to the readout. The piston includes a body having a bore and an external threaded area on the body circumferentially of the bore to threadedly engage the threaded internal opening of the coupling nut carried on the cylindrical member. The piston further includes a section within the bore for aligning the cylindrical member with the bore and for limiting the extent of movement of the cylindrical member into the bore. A master is provided for calibrating the gauge. The gauge is used in a method for determining the swaging that a cylindrical member has undergone.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to the manufacture of printed circuit boards and panels that are used in the electronics industry, and more particularly, to an automatic system that feeds, laminates, unloads, stores and transfers laminated panels to subsequent systems for further processing.
2. Description of the Prior Art
Automatic laminators for securing sheets of photopolymer dry film simultaneously to the opposite sides of a succession of panels are known in the prior art. Thus, in my prior U.S. Pat. No. 4,464,221 granted on Aug. 7, 1984, there is disclosed an automatic laminator for laminating photopolymer resist dry film onto each of a succession of printed circuit boards or panels. The laminator operates with a single roll of photoresist dry film to effect single sheet wrap around lamination of each of the panels and removal of the polyethylene cover sheet that is provided for protecting and facilitating the handling of the photoresist dry film. Following such lamination, the panels are delivered to a panel stacker and arranged in an upright lean-to fashion for cooling and chemical stabilization or setting.
It has been the practice following such lamination to transfer the panels manually to a subsequent system, for example, an exposure unit, for imaging. Such manual handling of the laminated panels not only adds to the cost of manufacture but subjects the panels to risk of contamination.
There is thus a need and a demand to provide an automatically operative unit or system that not only feeds and laminates each of a succession of panels, in turn, but which also, during a post lamination period for each of the panels in succession, automatically unloads, stores and transfers the panels to a subsequent system for further processing.
By reference herein, the disclosure of my prior U.S. Pat. No. 4,464,221 is made a part hereof.
SUMMARY OF THE INVENTION
An object of the invention is to provide for use with an automatic laminator a buffer interface unit to create a holding or storage area for the laminated panels to allow them to stabilize chemically prior to imaging.
Another object of the invention is to provide such a buffer interface unit that is automatically operative to take each of the stored panels after it has chemically stabilized and translate it from a vertical to horizontal position and deliver it to the infeed portion of a subsequent system, for example, exposure equipment that is mated with it.
In accomplishing these and other objectives of the present invention, the automatic laminator of my above-mentioned prior patent has been modified slightly to accept the buffer interface unit. A first area of modification is in the laminated panel delivery section of the laminator. The delivery belts of the laminator function as they did previously. However, a second set of two additional belts are provided, also. These latter belts act as a loading stop for each panel as it exits the laminating nip and is delivered downwardly to a loading position for pick up by a waiting panel pickup or gripper bar and movement into a storage area for chemical stabilizing. Other modifications include the provision of additional solenoid valves to actuate the additional pneumatic cylinders that are required, specifically a gripper bar loading cylinder, a gripper bar transfer-to-load cylinder, and a loading position belt actuating cylinder. The programmable controller provided in the automatic laminator has an expandable IO (Input/Output) Rack to accommodate the additional circuitry that is needed to operate the buffer interface.
In an operative embodiment of the invention, the holding or storage area, which may also be termed a magazine area, normally carries 41 panels. When a panel is placed in the storage area by the gripper loading cylinders, the panel in the most advanced position in the storage area is transferred to a delivery chain and subsequently is translated from a vertical to a horizontal position and delivered on to a panel delivery or exit belt that carries the panel on to the table of an exposure unit that is mated to the buffer interface.
As those skilled in the art will understand, the buffer interface unit, including the magazine area which serves as the storage area and the delivery section that translates the panel from a vertical to a horizontal position to deliver it to the associated exposure equipment, has the potential of a stand alone system.
BRIEF DESCRIPTION OF THE DRAWINGS
Having summarized the invention, a detailed description follows with reference being made to the accompanying drawings which form part of the specification, of which:
FIG. 1 is a schematic illustration of an automatically operative unit, according to the invention, comprising an automatic laminator with an integrated buffer/interface;
FIG. 2 is a view of a gripper bar return-to-load transfer arm with a sensor switch to detect a gripper bar after return;
FIG. 3 is a view of the inside front plate of the buffer/interface showing the gripper bar return-to-load transfer arm with a first gripper bar in a pocket thereof, and showing, also, a second gripper bar in rack storage position #1 in the magazine storage area;
FIG. 4 is a rear view of a complete gripper bar and shows it as comprising a cylindrical bar having an attached centrally located shorter rectangular bar with grippers mounted on the cylindrical bar and biased into engagement with the rectangular bar for clamping the edge of a panel therebetween;
FIG. 5 is a view, on a larger scale, of a portion of a gripper bar showing a nylon gripper, an inserted urethane pad, a helical tension spring, and locating collars;
FIG. 6 is a view of the inside front plate of the buffer/interface showing the gripper bar return-to-load transfer arm with a first gripper bar positioned in a pocket thereof, and in addition, showing a second gripper bar in the grasp of a gripper bar loading cylinder holding claw or device;
FIG. 7 is a view from the delivery end of the automatically operative unit with the gripper bars shown in the same position as in FIG. 6 and showing the laminator delivery belts and the buffer/interface loading position belts;
FIG. 8 is a view from the feeder end of the unit showing the laminated panel delivery section with a limit switch for the laminator delivery belts and an actuating cylinder for the loading position belts;
FIG. 9 is an angle view from the front of the unit through a lower opening showing the laminator delivery belts and the buffer/interface loading position belts in the delivery section;
FIG. 10 is an angle view from the rear of the unit looking over the rear side frame of the delivery unit and shows a gripper bar return-to-chain transfer arm in the transfer position with a gripper bar resting in a return chain bucket;
FIG. 11 is an angle view from the front of the unit looking over the front frame of the delivery unit and shows in greater detail the transfer arm of FIG. 10 in transfer position with a gripper bar resting in the return chain bucket;
FIG. 12 is a front view of the storage magazine showing the gripper bars in the normal spacing relation thereof;
FIG. 13 is an angle view from the rear of the unit looking over the rear side frame of the delivery unit and shows the panel exit delivery belts and a gripper bar just entering the unloading area (no panel being shown);
FIG. 14 is an angle view similar to that of FIG. 13 but shows grippers on the gripper bar just engaging a gripper release device;
FIG. 15 is an angle view from the front of the delivery unit showing a gripper bar as just exiting the unload or gripper release point, and showing, in addition, pinch rolls on top of the panel exit delivery belts;
FIG. 16 is an angle view similar to that of FIG. 15 but with the gripper bar now shown in a "hold" position, and showing, also, the infeed table of an exposure unit;
FIG. 17 is a view from the left end, at an angle from above, of a magazine storage area assembly, before installation in the supporting frame of the automatically operative unit, comprising a gripper bar recycling or return chain, gripper loading cylinders, and gripper opening cylinders;
FIG. 18 is a view, from directly below, of the gripper loading cylinders and gripper opening cylinders of the assembly of FIG. 17;
FIG. 19 is a view, from the right end and at an angle from above, of a portion of the assembly of FIG. 17 showing in greater detail the gripper bar return chain and the gripper opening cylinders;
FIG. 20 is a view from the left end, at an angle from above, showing a gripper bar and the set of gripper bar opening cylinder structures in greater detail.
FIGS. 21 and 22 are views showing in greater detail the laminator delivery belts and the storage area loading positioning belts;
FIGS. 23 and 24 are views showing a sensor switch for detecting the lowering of a panel to a gripper bar loading position stop;
FIGS. 25 and 26 are angle views from the front of the buffer/interface unit, at the right side thereof and looking up at the delivery unit, showing the gripper release mechanism in greater detail; and
FIGS. 27 and 28 are additional angle views of the delivery unit from the right side of the buffer/interface unit looking over the front side of the frame.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIG. 1 there is shown an automatically operative unit, generally designated by a reference numeral 1, that comprises an automatic laminator and an associated integrated printer buffer/interface.
The automatic laminator is indicated by the numeral 10 and may be identical to the automatic laminator disclosed in my aforementioned patent except, as mentioned hereinbefore, for modification of the laminated panel delivery unit. Thus, the laminator 10 includes a CRT graphic display unit 12, a panel pick-up unit 14, a panel load-pile feed unit 16, a photoresist dry film unwind supply roll 18, and a polyethylene or polyester film take-up roll 20. The laminator 10 further includes a laminating station 22 at the left end of which a dry film cutoff knife 24 is provided. At the laminating station 22 there is further provided a pair of heated laminating rolls 26, a vacuum film feed bar 28, a left film length adjust vacuum bar 30, a left film length adjust knob 32, a right film length adjust vacuum bar 34, a right film length adjust knob 36, and intensified IR (infra red) lamps 38. Additionally, the laminator 10 includes a film loop dancer control 40, a control panel 42, a vacuum film tension bar 44, an air exhaust 46, an exhaust duct 48, and an exit delivery belt unit 50.
As may be seen by reference to FIG. 1, photoresist dry film 52 is unwound from the film supply roll 18 and drawn down over a guide roll 54. At the guide roll 54, a protective polyethylene cover 56 is separated from the dry film 52 and is directed upwardly to be wound on the take-up roll 20. The dry film 52 continues in a downward path to and around the dancer control 40. From the dancer control 40, the dry film 52 is continued upwardly and over a guide roll 58 to the left film length adjustment vacuum bar 30 from where the film 52 is shown as having been drawn or extended through the laminating station 22, terminating at the vacuum film feed bar 28. When so extended, the film 52 is in proper position to be cut by cutoff knife 24 and laminated on a panel or board 60.
In an operative embodiment, the automatic laminator 10 is contained within a housing or supporting frame, designated by reference numeral 62, which may be made of aluminum plate or other suitable material. The laminator 10 accommodates panels or boards 60 in sizes from 24"×24" (609×609 mm.) to 10"×10" (254×254 mm.) having a thickness ranging from 0.032" to 0.125" (0.81 to 3.18 mm.), and has a capacity for cycling 100 panels of 0.062" (16 mm.) per load. Typically, such panels 60 are made of copper.
The panel load-pile feed unit 16 comprises a generally reverse L-shaped member 64 that is positioned for forward and aft movement or activation on a flat surface or table 66. A transversely adjustable edge guide (not shown) is provided for accommodating panels 60 of different width. The L-shaped member 64 includes an upwardly directed backing plate 68 for supporting a load of panels 60 to be laminated. The surface of the backing plate 68 is slanted at an angle of approximately 10 degrees counterclockwise from the vertical direction, as shown in FIG. 1, so that the panels 60 will stay stably in place, as stacked, until picked up by the pick-up unit 14.
As the panels 60 are picked up by the pick-up unit 14, the member 64 is moved in incremental steps to the right to advance each of the successive panels 60 into position to be picked up.
The pick-up unit 14 comprises a plurality of vacuum cups or suckers, indicated at 70, that are carried at the ends of transverse vertically spaced pneumatic cylinder driven arms or bars (not shown). The latter arms or bars are moved alternately to the left and right. This causes the plurality of vacuum cups 70 to reach out into engagement with the surface of the immediately adjacent panel 60 in the stack in the panel load-pile feed unit 16 to bring the panel 60 with the lower edge thereof above a lamination nip indicated at 72. Immediately thereafter, in the cycle of operation, the panel pick-up unit 14 is actuated downwardly to move the panel 60 that has been picked up down into the lamination nip 72 and between the laminating rolls 26.
An IR lamp controller (not shown) controls the energization of the IR lamps 38 as required to maintain the temperature of the laminating rolls 26 at a predetermined value, typically 250° F. The response of the temperature sensing means and the lamp controller is very fast whereby the temperature of the laminating rolls 26 is maintained precisely at the desired value.
As the panel pick-up unit 14 is actuated downwardly to move the panel 60 down through the laminator nip 72 and through the lamination rolls 26, the lower edge of the panel 60 engages the photoresist dry film 52, and pulling the film 52 downwardly, folds or wraps it into engagement with the opposite sides of the panel 60. The heated lamination rolls 26 heat the film 52 and press it into tight engagement with the opposite sides of the panel 60 thereby providing a laminated structure. The laminated panel 60 is delivered to the laminator exit delivery belt unit 50. Upon release of the laminated panel 60 by the pick-up unit 14, the latter is returned to its upper position shown in FIG. 1 and the laminator 10 is restored to a condition wherein it is ready to effect the lamination of the next one of the panels 60 that are stacked in the panel load-pile unit 16.
Mated to the automatic laminator 10 is a buffer/interface unit 74. A primary function of buffer/interface unit 74 is to establish a holding area for the laminated panels 60 to enable them to become stabilized chemically prior to imaging. An ancillary purpose is to take each of the stored panels, in turn, after it has become stabilized, and translating it from a vertical to a horizontal position, to deliver it to the infeed portion of exposure or punching equipment that is mated with it.
The buffer/interface unit 74, as shown in FIG. 1, includes a plurality of panel gripper bars 80, a magazine storage area 82 having an infeed end or portion 84 and an output end or portion 86, the laminator exit delivery belt unit 50 being positioned adjacent the infeed portion 84, a delivery chain 88, a set of idler rollers 130, and a plurality of delivery or panel exit belts 92 associated with and positioned adjacent the output portion 86. Also positioned adjacent the infeed portion 84 of storage area 82 are two gripper bar loading pneumatic cylinders 90 and a plurality of return-to-load gripper bar transfer arms 96. Coupling the infeed portion 84 and output portion 86 of the storage area 82 is a gripper bar return chain 104. Positioned adjacent the output portion 86 is a plurality of gripper bar return-to-chain transfer arms 138. The buffer/interface unit 74 further includes a plurality of gripper bar opening devices or cams 132, as shown in FIGS. 13, 14 and 25-28.
As shown in FIGS. 1 and 7-9, the delivery belt unit 50 includes a first set of two spaced delivery belts 76, and in addition, a second set of two spaced delivery belts 78. The first set of delivery belts 76 function, as explained in my aforementioned prior patent, to lower each of the laminated panels 60, in succession, as it exits the nip of the laminating rolls 26. The second set of two belts 78 act as a loading position stop for each of the panels 60 and lower each of the panels to a gripper bar loading position where it is picked up by one of a plurality of gripper bars 80 and carried thereby into the magazine or storage area 82 of the buffer/interface unit 74.
In FIG. 1 three panels 60 are shown as having been put into the storage area 82 at the infeed portion 84 thereof and a single panel 60 is shown at the opposite or output end 86 of the storage area 82, the latter panel 60 being ready for transfer to the delivery chain 88 in the buffer/interface unit 74 for movement to and subsequent utilization in an imaging process.
In an operative embodiment of the invention, the storage area 82 is adapted to accommodate 41 panels at the same time. When a panel 60 is placed in the infeed end 84 of the storage area 82 by the gripper bar loading cylinders 90, the panel 60 in the storage area 82 at the output end 86 is transferred to the delivery chain 88. Subsequently, the latter panel 60 is translated from a vertical to a horizontal position and delivered on to the delivery belts 92. The delivery belts 92 carry the panel 60 and deposits it on an infeed table 94, as seen in FIG. 16, of an exposure unit that is mated to the buffer/interface unit 74.
As shown in FIGS. 2 and 3, the gripper bar transfer-to-load transfer arm 96 includes a sensor switch 98 and is provided for transferring each of a plurality of gripper bars 80 in succession to a panel pick-up or loading position. Transfer arm 96 is pivoted at an opening 101 thereof for rotation on a shaft 100, being fixedly attached thereto, and is rotatable counterclockwise approximately 90 degrees to a vertical position from the position shown in FIG. 3.
When in the position shown in FIG. 3, transfer arm 96 is in position to receive, in a pocket 102 thereof, a gripper bar 80 that has been recycled by a gripper bar return chain 104 after having transported a panel 60 to the opposite and unloading end 86 of the buffer/interface unit 74 and released the panel thereat.
Rotation of the transfer arm 96 counterclockwise 90 degrees then places the gripper bar 80 in the pocket 102 thereof in a proper attitude for gripper bar loading. FIG. 6 shows the transfer arm 96 with a first gripper bar 80 in the pocket 102 of the transfer arm 96 and a second gripper bar 80 in rack storage position #1 in the storage area 82.
Detail views of a single gripper bar 80 are shown in FIGS. 4 and 5. Each gripper bar 80, as shown, includes a cylindrical rod 106 and a rectangular bar 108 that is somewhat shorter in length than rod 106 and is suitably attached by fasteners 118 at its ends to rod 106. A plurality of nylon grippers 110 are positioned in spaced relation along the length of rod 106, by locating collars 112. Each of the nylon grippers 110 is biased by a helical spring 114 for counterclockwise rotation into engagement with a respectively associated urethane pad 116 that is inserted in rectangular bar 108.
When a gripper bar 80 is in the pocket 102 of transfer arm 96 and is in proper attitude for loading, two cylinders 90, as best seen in FIGS. 1, 17 and 18 are moved forward to pick up the gripper bar 80 by a claw-like mechanism 120 on each of the ends of the cylinders 90. As soon as such pick up or attachment is effected, a set of gripper opening pneumatic cylinders 122, as shown in FIGS. 19 and 20, is actuated to rock or rotate each of the grippers 110 against the tension of its associated spring 114 to an open position thereof to allow the gripper bar 80 to accept a panel 60.
Upon passing through and exiting the laminating rolls 26 in the laminator 10, each laminated panel 60 is moved through a path that is at a 10 degree angle, approxmately, with the vertical, onto the first set of delivery belts 76. As the belts 76 proceed downwardly, the panel 60 is stopped, at a position somewhat above the region of delivery described in my aforementioned patent, in a set of two delivery stops 124, as best seen in FIGS. 21-24, that are provided on the loading position delivery belts 78. An electrical switch 123 is carried on an electrically insulating plate 127 that bridges the stops 124. Stops 124 desirably are adjustable to accommodate different lengths of panels 60. Such adjustment is in a plane that is displaced 10 degrees from the vertical plane and is such as to position the delivered laminated panel 60 at a height that is correct for the gripper bar 80 to make a proper attachment to the panel 60 at the upper end thereof.
When the panel 60 reaches the correct position for attachment to the gripper bar 80 and contacts switch 123, the gripper bar cylinders 90 are actuated and retract to move the gripper bar 80 to the left, as seen in FIG. 1, to contact the panel. When cylinders 90 make such contact, a reed switch 127 shown in FIG. 18 is closed and the gripper opening cylinders 122 retract to allow the individually spring loaded grippers 110, as seen in FIGS. 4 and 5, to secure the panel 60 in the grip thereof, thus completing the loading operation.
At this point in the cycle of operation, the loading position belts 78 are actuated to lower the delivery stops 124 down out of the way of the lower end of the panel 60. Simultaneously, the gripper bar loading cylinders 90 are actuated to the right, as seen in FIG. 1, to place the gripper bar 80 and the just loaded panel 60 in the magazine area 82 with the ends of the cylindrical rod 106 of the gripper bar 80 resting on opposed ledges 125, as indicated in FIGS. 1, 17 and 19. Subsequently, the gripper bar attaching claws 120 are opened and the gripper bar 80 and the attached panel 60 remain in the magazine area 82 as the gripper bar loading cylinders 90 are actuated for retraction fully to the left, as seen in FIG. 1.
In accordance with the invention, the gripper bar loading cylinders 90 have three distinct positions. The position all the way to the left, as seen in FIG. 1, is the loading position. The position fully extended to the right is the unload position. A center position is the pick up position where a laminated panel 60 is attached to the gripper bar 80.
As may be seen in FIG. 12, the gripper bars 80 are closely positioned in the storage area 82, each being in contact with the one next to it. With the magazine area fully loaded, when a gripper bar 80 is loaded and placed in the infeed end 84 of the magazine storage area 82, a simultaneous action occurs at the opposite or output end 86. Upon such occurrence, the 41st gripper bar 80 at the end 86 of the storage area 82 is forced out of the magazine storage area 82 into a carrier bucket 126 on the delivery chain 88. Simultaneoulsy, also, the delivery chain 88 is actuated and moved in a counterclockwise direction, as seen in FIG. 1, whereby the just received gripper bar 80 and depending panel 60 are moved on the bucket 126 that is carried by chain 88 toward the delivery end 128 of the buffer/interface unit 74.
This action translates, that is, turns the panel 60 in a clockwise direction, as seen in FIG. 1., from the vertical position in which it has been held suspended by the gripper bar 80 in the magazine storage area 82, to a horizontal position, by way of idler rollers 130, and moves the panel 60 onto the delivery or panel exit belts 92. As the gripper bar 80 carried by chain 88 approaches and moves through the gripper bar release or opening devices 132, as seen in FIGS. 14, 25 and 26, the grippers 110 are opened and the panel 60 is thereby released and left on the delivery belts 92. Delivery belts 92 move the panel 60 between pinch rolls 142 through the delivery end 128 of unit 1 to a utilization means, for example, infeed table 94 of an associated exposure unit for imaging, as shown in FIG. 16.
FIGS. 25-28 show the several positions into which the nylon grippers 110 are adjusted as a panel 60 carried thereby, but not shown for convenience of illustration, is translated from a suspended vertical position to a horizontal position on the delivery belts 92. Thus, FIG. 28 shows the grippers 110 as they are just beginning to be turned in a clockwise direction from the vertical position as a result of the engagement of the panel 60 with the idler rollers 130. FIG. 27 shows the grippers 110 in a horizontal position. In this position, the panel 60 (not shown) is trailing behind the grippers 110 still in the grip of the grippers 110.
FIGS. 27 and 28 show the carrier bucket 126 in engagement with a cam member 148 which together with a similar cam member on the opposite side of the buffer/interface unit 74 serves to guide the carrier buckets 126 and gripper bars 80, and hence, the panel 60 down into receiving relation with the delivery belts 92.
FIGS. 25 and 26 show the grippers 110 as having been engaged by the gripper bar release devices 132, smooth cam surfaces on the bottom of the latter forcing the grippers 110 against the force of the biasing springs 114 to an open position for releasing the panel 60 on the delivery belts 92.
The gripper bar 80 movement with the delivery chain 92 continues to a position indicated at 136, above an idler roller sprocket 134, and marked with a bucket indication.
Position 136 is a hold position for the delivery chain 88. Since there are two carrier buckets 126 mounted on the delivery chain 88, this represents a 180 degree rotation of the chain 88. Such rotation brings the other bucket 126 into gripper bar and panel receiving position at the delivery loading or output portion 86 of the magazine area 82.
The empty gripper bar 80, as it is moved back to the delivery loading portion 86 on chain 88, is intercepted by the plurality of gripper bar return-to-chain transfer arms 138, as best seen in FIGS. 1, 10 and 11. Transfer arms 138 are located just inside the pockets on the lower left hand side of the delivery chain 88, as shown in FIG. 1. As the gripper bar 80 is moved down from an idler sprocket 140 on the most upper left hand position on delivery 88, as seen in FIG. 1, the transfer arms 138 remove the gripper bar 80 from the delivery buckets 126, and being rotated counterclockwise approximately 30 degrees, serve to transfer the gripper bar 80 from the delivery chain 88 to carrier buckets 144 on the gripper bar return chain 104. This action immediately starts the return chain 104 for rotation in a counterclockwise direction. Chain 104 moves or cycles through 180 degrees and transfers the gripper bar 80 to the transfer-to-load transfer arms 96, allowing the gripper bar 80 to move down along a sloping surface of arm 96 into the pocket 102 of arm 96 while the latter is rotated to the gripper bar pick up position. The sensor switch 98 that indicates the gripper bar 80 as being in the pocket 102 is shown in FIGS. 2 and 3.
As previously mentioned, the buffer/interface according to the present invention may be controlled by the programmable controller provided in the automatic laminator 10, the latter having an expandable Input/Output Rack which is capable of accommodating the additional circuitry that is needed.
Thus, in accordance with the invention, there has been provided an automatic laminator with integrated buffer/interface. The buffer/interface is operative to provide a holding area for the laminated panels for a suitable period, for example, up to fifteen minutes, in a suspended manner out of contact with each other and adjacent surfaces except for small grippers attached to an edge thereof. This holding period allows the laminated panels to stabilize chemically prior to imaging. The handling of the panels during the lamination process and also during the post lamination period is entirely automatic.
Having described the invention in detail, those skilled in the art will appreciate that modifications may be made to the invention without departing from the spirit thereof. Therefore, it is not intended that the scope of the invention be limited to the specific embodiment that is illustrated and described. Rather, it is intended for the scope of the invention to be determined by the appended claims.
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An automatic system that feeds, laminates, unloads, stores and transfers laminated panels to subsequent processing for use in the electronics industry includes an automatic laminator that operates with a single roll of photoresist dry film to effect single wrap around lamination of each of a plurality of panels in succession and removal of the polyethylene protective cover sheet, and further includes a buffer/interface unit that is operative during a post lamination period to provide a holding area for the laminated panels to allow them to chemically stabilize prior to imaging, and in addition, is operative after the panel has stabilized to translate each of the panels, in turn, from a vertical to a horizontal position and deliver it to the infeed portion of an exposure machine that is mated with it.
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BACKGROUND OF THE INVENTION
This invention relates to screening apparatus for separating fine material from coarse material, and in particular to such an apparatus in combination with a portable carrier.
Previously, it has been known to provide portable screening apparatus for separating fine materials from coarse material, wherein the portability of the apparatus is dependent upon wheels attached to the chassis of the apparatus. The wheels are generally made movable relative to the apparatus chassis from an operative position for transporting the apparatus to an inoperative position for resting the frame flush on the ground. Such a unit is shown, for example in U.S. Pat. Nos. 4,923,597; 4,256,572; 4,237,000; 4,197,194; and Des. 263,836, as well as U.K. Patent No. 2,223,963A. An apparatus, with attached wheels, is registered with the various state governments as a road vehicle and towed to the various desired locations for operation. The generally bulkiness of the apparatus makes it difficult to transport, especially since the apparatus is designed primarily as a screening apparatus rather than as a road vehicle.
An alternate to the above towed apparatus has historically been to mount or carry the screening apparatus on a trailer or truck. Since trailers and trucks are designed primarily as road vehicles, the inherent dangers of towing a screening apparatus are eliminated. However, operating the screening apparatus on a trailer or truck requires elaborate conveyors or chutes because of the mounted height of the screening apparatus. This approach has been considered unsatisfactory, because of inherent operating difficulties, as well as instability and danger from toppling. To set the screening apparatus directly on the ground, a crane is required to lift the screening apparatus from the trailer or truck to position it on the ground for screening operation.
To overcome the limitations of the prior art, applicant devised an apparatus that could both separate fine materials from coarse materials and mix two or more fine materials together. The apparatus was transportable in combination with a carrier. The apparatus was self-loading onto and off the carrier without the need for a crane.
SUMMARY OF THE INVENTION
The present invention provides a combination screening apparatus and carrier. The screening apparatus has three hydraulic leg assemblies which are adapted to lift and lower the screening apparatus off and onto a carrier. The legs are positioned and operable that a carrier may be slid directly under the screening apparatus without interference with the legs. The carrier has pivotable holding elements which engage grasping elements fixedly attached to said screening apparatus. The shape and configuration of the holding elements and grasping elements are such that the screening apparatus is self-aligning on the carrier. The carrier may be left under the screening apparatus or removed during screening operations.
These together with other objects of the invention, along with various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed hereto and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there are illustrated two preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front perspective view of a screening apparatus mounted on a carrier in accordance with the invention.
FIG. 2 is a front perspective view of the screening apparatus of FIG. 1 dismounted from the carrier with the carrier still in place beneath the screening apparatus.
FIG. 3 is a front view of the screening apparatus being lowered onto the carrier.
FIG. 4 is a conveyor side view of the invention.
FIG. 5 is a rear view of the screening apparatus being lowered onto the carrier.
FIG. 6 is a close-up view of a carrier holding element.
FIG. 7 is a top view of the invention carrier without the holding elements.
FIG. 8 is a top view of the invention carrier with the holding elements.
FIG. 9 is a close-up perspective view of a screening apparatus grasping element.
FIG. 10 is a front view of a screening apparatus grasping element.
FIG. 11 is a cross-sectional view along the line A--A of FIG. 10 of a screening apparatus grasping element in conjunction with a carrier holding element.
DETAILED DESCRIPTION OF THE INVENTION
The present invention 200 is comprised of a screening apparatus 210 in combination with a carrier 300. The screening apparatus 210 has a box-like shape with a vertical front end 211, a vertical rear end 212, a vertical tailings side 213, a vertical conveyor side 214, a top side 215 and a horizontal bottom side 216. The invention 200 longitudinal axis is coincident with an axis defined by the screening apparatus front end 211 and rear end 212.
The screening apparatus 210 includes a frame 220 for supporting a two-tiered screen assembly 221 for sifting materials. The screening apparatus 210 also includes a generally horizontal conveyer 201 installed just beneath the screen assembly 221 transverse to the invention 200 longitudinal axis. The screen assembly 221, comprising top 222 and bottom 223 screens, is sloped downwardly from the conveyer side 214 top side 215 to the tailings side 213 top side 215, and is supported at each corner by a C-shaped leaf spring (not shown) attached to the frame 220. A drive shaft (not shown) for vibrating the screen assembly 221 is driven by a hydraulic pump 231 mounted on an engine tray 230 installed on the screening apparatus front end 211. The shaft includes an off-balance counterweight (not shown) at each end to provide for eccentric rotation. The hydraulic pump 231 drives the shaft in a first rotational direction to move the materials down the screen assembly 221 in a sifting movement and in a second rotational direction to move the materials up the screen assembly 221 in a mixing movement. A crown 224 is provided in both the top and bottom screens 222, 223. The crown 224 provides a ridge which runs perpendicular to the tailings side 213. Longitudinal bars 225 for forming the crowned screens 222, 223 provide additional support to the screen assembly 221. The crowned shape of the screens 222, 223 disperses the materials more evenly on the screens. The screen assembly 221 is adjustably mounted on the frame 220 so that its slope can be adjusted. Moreover, the leaf springs are secured between side mounts on the screen assembly and mounting blocks secured to the frame 220 itself. In this way, the height of the frame 220 can be reduced while maintaining sufficient clearance below the screen assembly 221. The screening apparatus 210 is generally adapted to sift out tailings (debris and the like) and drop them out over the screening apparatus tailing side 213. The desired materials are sifted through the screen assembly 221 and deposited onto the conveyer 201 where the desired materials are moved to and dropped over the screening apparatus conveyer side 214.
The vertical tailings side 213 has a generally rectangular side-wall 280 having a front edge 281, a rear edge 282, a horizontal bottom edge 283, a horizontal top edge 284 formed just below the screening assembly conveyer 201, an outside surface 285 and an inside surface 286. The vertical conveyer side 214 has a generally rectangular side-wall 290 having a vertical front edge 291, a vertical rear edge 292, a horizontal bottom edge 293, a horizontal top edge 294 formed just below the screening assembly conveyer 201, an outside surface 295 and an inside surface 296. The side-wall inside surfaces 286, 296 are defined as those side-wall surfaces facing each other. Each side-wall 289, 290 extends forward beyond the screening apparatus front end 211 and rearward past the screening apparatus rear end 212.
This embodiment 200 of the invention also has an engine tray 230 mounted on the screening apparatus front end 211. The tray 230 has a generally rectangular shape and is positioned horizontally relative to the front end 211. The tray 230 is joined to said front end 211 and enclosed in a housing 229.
As stated above the hydraulic pump 231 is mounted on the engine tray 230. A hydraulic fluid tank 237 is mounted on the screening apparatus front end 211 above the engine tray 230. A network of hydraulic lines 238 interconnect the tank 237 and the hydraulic pump 231 with a number of hand-operated valves 239 mounted on the engine tray 230. The cables 238 then branch out from the valves 239 to their various operating terminals, i.e., hydraulic leg assemblies 204, 205, 206.
The screening apparatus 210 includes three hydraulic leg assemblies 204, 205, 206 for lifting and lowering the screening apparatus 210. One leg assembly 204 is attached to the apparatus front end 211 adjacent to the conveyer side side-wall inside surface 296. Another leg assembly 205 is attached to the apparatus front end 211 adjacent to the tailings side side-wall inside surface 286. The last leg assembly 206 is attached to the center of the screening apparatus rear end 212. Each leg assembly 204, 205, 206 has a vertical fluid cylinder 240, a piston 241 projecting downwardly from said cylinder 240, and two fluid inlet/ outlet ports 242 on each cylinder 240. The fluid inlet/outlet ports 242, i.e., operating terminals, are interconnected to the hand-operated valves 239 mounted on the engine tray 230 by hydraulic lines 238. Manipulation of the valves 239 will cause a reaction in the hydraulic leg assemblies 204, 205, 206 whereby the pistons 241 will extend outwardly or retract inwardly from the cylinders 240.
Each side-wall 280, 290 has two grasping elements 250 attached to the side-wall inside surface 286, 296, one grasping element 250 on each side-wall 280, 290 positioned between the side-wall's front edge 281, 291 and respective hydraulic leg assembly cylinder 240, a short distance up from the side-wall respective bottom edge 283, 293. The second of each grasping element 250 is attached adjacent to each side-wall's rear edge 282, 292 a short distance up from the side-wall respective bottom edge 283, 293. Each grasping element 250 has a vertical, hollow, box-like shape, with a front 251, rear 252, top 253, bottom 254 and two sides 255. The vertical axis of a grasping element 250 is from top 253 to bottom 254. The grasping element rear 252 is defined as that portion of the grasping element attached directly to the sidewall inside surface 286, 296. The grasping element front 251 is that portion of the grasping element horizontally opposite to the rear 252. The grasping element sides 255 are those two portions connecting the front 251 to the rear 252. The grasping element top 253 and bottom 254 are open. The grasping element front 251 extends vertically downward from the grasping element top 253 to a horizontal plane 256 midway along the vertical axis of the grasping element 250. The bottom 260 of each vertical side 255 extends from the grasping element bottom 254 at the grasping element rear 252 to the bottom 256 of the grasping element front 251. The grasping element 250 has a first, generally rectangular element 257 attached to the grasping element top 253 at the grasping element rear 252. The first rectangular element 257 extends into the interior 258 of the grasping element 250 toward the line 256 at the bottom of the grasping element front 251. The element 257 is attached along its sides 261 to the interior surfaces 266 of the grasping element sides 255. The grasping element 250 also has a second, generally rectangular element 263 attached to the grasping element rear 252 at the horizontal plane 256 midway along the vertical axis of the grasping element 250. The second rectangular element 257 extends into the interior 258 of the grasping element 250 up toward the top 253 of the grasping element front 251 to the undersurface 264 of the first rectangular element 257 where it is joined. The element 263 is also attached along its sides 265 to the interior surfaces 262 of the grasping element sides 255.
The carrier 300 is a trailer-type, towable device comprised of a generally rectangular frame 301 having a front 306, rear 302, two sides 303, top 304 and bottom 305. The carrier frame 301 has a V-shaped tow bar 307 attached to the frame front 306. The carrier frame longitudinal axis runs from the frame rear 302 through the frame front 306 and is parallel to the longitudinal axis of the screening apparatus 210. The carrier frame 301 has two horizontal, longitudinal beams 308, each having a forward end 309 and a rearward end 310. The longitudinal beams 308 are positioned parallel to the longitudinal axis of the carrier frame 301 and form the carrier sides 303. The longitudinal beams 308 are interconnected by two horizontal, transverse beams 311, one fixedly joined to the longitudinal beam forward ends 309 and the other fixedly joined to the longitudinal beam rearward ends 310, said transverse beams 311 forming the carrier frame front 306 and rear 302. The carrier frame 301 has two sets of axles 314 with wheels 315 attached to said carrier frame 301. The axles 314 are positioned transverse to the longitudinal axis of the carrier frame 301.
Two support beams 320 are attached to the bottom 305 of the carrier frame 301. Each support beam 320 has a top 321, a bottom 322 and two ends 323. Each support beam 320 is positioned transverse to the longitudinal axis of the carrier frame 301. The top 321 of one support beam 320 is welded to the bottom 312 of the longitudinal beams 308 near to the longitudinal beam forward ends 309. The top 321 of the other support beam 320 is welded to the bottom 312 of the longitudinal beams 308 near to the longitudinal beam rearward ends 310. Each support beam end 323 extends transversely outward past the carrier frame sides 303 an amount approximately equal to the thickness of the wheels 315, the portions of the support beams 320 extending outward past the carrier frame sides 303 being designated the support beam extension portions 324. Each support beam extension portion 324 has a vertical hole 325 formed therein near to the adjacent longitudinal beam 308.
Each longitudinal beam top 313 has a two horizontal plates 330 welded thereto, each said plate 330 extending sideways outward from the longitudinal beam top 313 over a support beam extension portion 324. Each plate 330 has a vertical hole 331 formed therein, said hole 331 being in vertical alignment with the vertical hole 325 formed in the support beam extension portion 324 directly below the plate 330.
The carrier 300 is further comprised of four elongated holding elements 340 each having two ends, a proximal end 341 and a distal end 342. Each holding element 340 also has a top 343, bottom 344 and two sides 345. Each holding element 340 has a vertical hole 346 formed therein near to its proximal end 341. Each holding element 340 is positioned between a support beam extension portion 324 and corresponding plate 330 where it is pivotally connected by means of a rod-like element 335 inserted through the plate vertical hole 331, through the holding element vertical hole 346, and through the support beam extension portion vertical hole 325. The holding element distal end 342 has a wedge-shaped protrusion 347 formed on the holding element top. The wedge-shaped protrusion 347 generally corresponds in shape to the grasping element interior 258 from the grasping element bottom 254 as modified by the rectangular elements 257 and 263.
In operation, the screening apparatus 210 rests on the ground 6, the screening apparatus tailings sidewall bottom edge 283 and conveyer side sidewall bottom edge 293 actually engaging the ground 6. The pistons 241 of the hydraulic leg assemblies 204, 205, 206 are generally retracted into the hydraulic leg assembly cylinders 240. When it is desired to move the screening apparatus 210 a carrier 300 is slid under the screening apparatus bottom side 216. The carrier holding elements 340 are initially positioned so that their longitudinal axes are parallel to the longitudinal axis of the carrier 300. The front hydraulic leg assemblies 204, 205 are activated and the leg assembly pistons 241 extended out from the cylinders 240 in a vertically downward direction thereby lifting the screening apparatus front end 211 vertically upward so that the two front grasping elements 250 are vertically higher than the carrier front holding elements 340. The front hydraulic leg assemblies 204, 205 are designed so that their pistons 241 reach the ground. The front holding elements 340 are then horizontally pivoted by hand so that their longitudinal axes are transverse to the carrier longitudinal axis. This will position the front holding element distal ends 342 vertically below the screening apparatus front grasping elements 250. The hydraulic leg assemblies 204, 205 are then activated again, withdrawing the pistons 241 into the cylinders 240 thereby causing the screening apparatus front end 211 to be lowered. The lowering action will cause the holding element wedge-shaped protrusions 347 to engage the grasping element bottoms 254 into the grasping element interiors 258 and against the rectangular elements 257 and 263. The rear hydraulic leg assembly 206 is then activated and the leg assembly piston 241 extended out from the cylinder 240 in a vertically downward direction to engage the center 326 of the rear support beam 320 thereby lifting the screening apparatus rear end 212 vertically upward so that the two rear grasping elements 250 are vertically higher than the two carrier rear holding elements 340. The rear hydraulic leg assembly 206 is shorter that the front leg assemblies 204, 205 and designed specifically so that it cannot reach the ground 6 but rather only to the carrier rear support beam 320. The rear holding elements 340 are then horizontally pivoted by hand so that their longitudinal axes are transverse to the carrier longitudinal axis. This will position the rear holding element distal ends 342 vertically below the screening apparatus rear grasping elements 250. The rear hydraulic leg assembly 206 is then activated again, withdrawing the piston 241 into the cylinder 240 thereby causing the screening apparatus rear end 212 to be lowered. The lowering action will cause the holding element wedge-shaped protrusions 347 to engage the grasping element bottoms 254 into the grasping element interiors 258 and against the rectangular elements 257 and 263. The screening apparatus 210 is thereby secured to the carrier 300 for towing. To remove the screening apparatus 210 from the carrier 300, the above procedure is reversed. The shapes of the holding element protrusions 347 and grasping element interiors 258 provide a self-aligning capability to the screening apparatus-carrier combination of the present invention. The use of three hydraulic leg assemblies rather than four, and the use of a shortened rear hydraulic leg assembly, make the screening apparatus 210 difficult to remove without the proper carrier 300, thereby reducing theft.
It is understood that the above-described embodiment is merely illustrative of the application. Other embodiments may be readily devised by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
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A combination screening apparatus and carrier. The screening apparatus has three hydraulic leg assemblies which are adapted to lift and lower the screening apparatus off and onto a carrier. The legs are positioned and operable that a carrier may be slid directly under the screening apparatus without interference with the legs. The carrier has pivotable holding elements which engage grasping elements fixedly attached to said screening apparatus. The shape and configuration of the holding elements and grasping elements are such that the screening apparatus is self-aligning on the carrier. The carrier may be left under the screening apparatus or removed during screening operations.
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FIELD OF THE INVENTION
The present invention is related to the field of targeting and is more specifically directed to Engagement Oriented Recommendation.
BACKGROUND
Online networks, such as the Internet, connect a multitude of different users to an abundance of content. Just as the users are varied, the content is similarly varied in nature and type. In particular, the Internet provides a mechanism for merchants to offer a vast amount of products and services to consumers. Internet portals provide users an entrance and guide into the vast resources of the Internet. Typically, an Internet portal provides a range of search, email, news, shopping, chat, maps, finance, entertainment, and other Internet services and content. Yahoo, the assignee of the present invention, is an example of such an Internet portal.
When a user visits certain locations on the Internet (e.g., web sites), including an Internet portal, the user enters information in the form of online activity. This information may be recorded and analyzed to determine behavioral patterns and interests of the user. In turn, these behavioral patterns and interests may be used to target the user to provide a more meaningful and rich experience on the Internet, such as an Internet portal site. For example, if interests in certain products and services of the user are determined, advertisements and other content, pertaining to those products and services, may be served to the user. A targeting system that serves highly appropriate content benefits both the content provider, who provides their message to a target audience, and a user who receives content in areas of interest to the user.
Currently, providing content through computer networks such as the Internet is widespread along with content through other mediums, such as television, radio, or print. Different online content has different objectives and appeal depending on the user toward whom the content is targeted. The value to the user of media or a particular medium will largely be based on the quality of the content provided to the user. Quality has a number of factors, including the relevance to a specific user at a specific moment in time, for instance. Hence, considering the vast amount of information available to the broad spectrum of disparate users, the delivery of quality content at any given time is not a trivial task. Moreover, content is conventionally presented by using limited resources. These resources might include inventory locations or placements for content that are distributed through a set of content properties. Maximizing use of these limited resources has certain advantages.
SUMMARY
The content provided to users may take the form of advertisements and/or recommendations for products, services, and/or additional related content. Generally, a select set of recommendations from the domain of all possible recommendation items has greater relevance to a particular user. This set of recommendations may be further ranked in order of different measures of quality. While making recommendations to users from a selected set of recommendations, the top recommendations often have a narrow scope and may only include very similar items or items that are undesirably clustered around a narrow set of topics. Presenting highly similar items to users presents the following drawbacks. First, due to a perceived amount of redundancy of recommendations from a small cluster, users have an increased tendency to become quickly “burned out” on the narrow scope of choices presented to them. Hence, interest in the same products and/or categories may become saturated. Further, the content will appear stale thereby undesirably diminishing the users' level of interest. Second, users' network experience and engagement level are limited to a narrow clustered scope, which undesirably limits cross selling, content breadth, and other opportunities for broadening user growth and level of engagement. To address these concerns, embodiments of the invention provide content and/or category-aware recommendation that balances and prioritizes among categories that are highly related, and yet, are different in various ways, such as by possessing distant semantics, and thus are more likely to involve broader or more remote topics or categories. As a result, users are introduced to greater variety of topics, and thus their engagement level is further promoted.
In some implementations, a method selects a predictor item that has a relevance to a user. The method receives a set of affinity items having affinity scores that relate the predictor item to the affinity items. The method filters the received affinity items based on the affinity scores, and selects a first set of affinity items from the filtered items. For each selected affinity item, the method calculates a difference score. The difference score indicates a difference of the affinity item from the predictor item. The method selects a first affinity item based on the difference score for the first affinity item. Preferably, content is presented to the user based on the selected first affinity item.
The filtering of some embodiments identifies affinity items having affinity scores that are greater than a threshold. In these embodiments, further calculations are selectively performed for the most relevant affinity items, thereby improving performance by reducing the amount of calculations that have lower relevance, and therefore, lesser utility. In a particular implementation, the predictor item and the affinity item are categorized in a hierarchical tree structure such as, for example, a directory tree or a category tree. In these cases, the difference score is based on a distance metric between the predictor item and the first affinity item. Preferably, the distance metric is precalculated and/or stored in a high access speed type format such as, for example, a lookup type table.
Some embodiments generally compare the difference scores for the first affinity item and a second affinity item, and select and/or recommend one or the other based on the difference scores. For cases where greater breadth of user engagement is desired, the method preferably selects the affinity item that provides a broader range of user interaction, and a reduced likelihood of clustering. In some embodiments, a total score is determined for the first affinity item and a second affinity item. The total score includes the affinity score and the difference score for the particular affinity item. Some of these embodiments select the affinity item having the higher total score after comparing the total scores for the first affinity item and the second affinity item. For some implementations, the total score further includes a weight factor applied to the difference score. The weight factor scales the difference score to the scale of the affinity score, and further adjusts the significance of the difference score in the total score. Additional embodiments include a system and/or computer readable medium having instructions for implementation and/or execution of the foregoing.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features of the invention are set forth in the appended claims. However, for purpose of explanation, several embodiments of the invention are set forth in the following figures.
FIG. 1 illustrates a relevance engine for computing affinity scores.
FIG. 2 illustrates a hierarchical tree structure for items and/or categories.
FIG. 3 illustrates a directory structure for items and/or categories.
FIG. 4 illustrates a measure of difference by using the directory structure.
FIG. 5 illustrates a table for consolidation and filtering.
FIG. 6 illustrates a table including difference and/or total scores.
FIG. 7 illustrates a table for a directory tree example.
FIG. 8 illustrates a process flow in accordance with some embodiments.
FIG. 9 illustrates a system having inventory locations and placements.
DETAILED DESCRIPTION
In the following description, numerous details are set forth for purpose of explanation. However, one of ordinary skill in the art will realize that the invention may be practiced without the use of these specific details. In other instances, well-known structures and devices are shown in block diagram form in order not to obscure the description of the invention with unnecessary detail.
Conventional targeting systems usually generate and choose recommendations by using affinity scores. The affinity scores identify and measure relationships between the chosen recommendations and predictive data. By virtue of this system, however, the highest ranked (or scored) recommendations are often undesirably too similar to each other and provide no new, or no variety of content or service. As a result, the content provided by such traditional recommendation models often undesirably causes increased user burn out rate, and/or waste of network inventory. In order to address this problem, some embodiments include novel methods and systems for including additional information into the selection of recommendations. More specifically, some embodiments determine and/or present category-sensitive recommendations. For instance, particular embodiments of the invention integrate category structures with recommendation items. These embodiments advantageously include three components: affinity scoring, categorization for affinity items, and category sensitive recommendation and/or presentation.
Affinity Score
Recommendation items are typically selected from a broad variety of content types. Items of content have various relationships including affinities between each item. The relationships are preferably identified and/or measured by a scoring system. These relationships are further represented by dividing the content items into a predictor item and affinity items for the predictor item based on the various relationships. Recommendation items are preferably selected from the pool of content items based on one or more predictor items and various relationships to several affinity items.
Preferably, affinity scores are built among the content items by an advantageous affinity algorithm. For instance, FIG. 1 illustrates a system 100 for the determination of relationships or affinities, and/or the scoring of the affinities. As shown in this figure, a predictor item (x) is input to a relevance engine 102 , which preferably outputs several affinity items and scores that describe a relationship of each affinity item to the predictor item. Some embodiments use a list format for the output of the engine 102 . However, one of ordinary skill recognizes alternatives for the output of the relevance engine 102 . A particular implementation of the system 100 uses the Yahoo Affinity Engine, provided by Yahoo Inc., of Sunnyvale, Calif. In these embodiments, the output of the engine 102 preferably has the following format, where predictor_item_x is the predictor item and affinity_item_n is one affinity item with an affinity score of score_xn:
(predictor_item_x, affinity_item_n, score_xn).
Categories and Content Items
In addition to affinity measures, some embodiments determine several categories, {C_ 1 , C_ 2 , . . . , C_n} for content and/or recommendation items, where each item is advantageously grouped with one or multiple categories. One of ordinary skill recognizes a variety of implementations for representing the relationships between categories, and/or items within the categories. For instance, one implementation of category structure is a relational hierarchy, in which categories are organized in a hierarchical tree structure. A parent category represents a broader category, or a super set, that semantically covers all of its child categories. For example, FIG. 2 illustrates a hierarchical tree structure 200 for categories including super-categories and subcategories. As shown in this figure, the super category Sports has categories such as Baseball and Basketball. Further, each of these categories has further subcategories such as major league baseball (MLB), and college or NCAA_Baseball for Baseball, while the Basketball category has NBA and ABA subcategories.
Difference Measures
As described above, each category and item within each category of FIG. 2 , has a relationship to each other category and/or item within the structure 200 , that is preferably measured by using an affinity scoring system described above in relation to FIG. 1 . Moreover, the categories and/or items within each category of FIG. 2 further include differences between each other such as, for example, semantic, categorical, and/or conceptual or associative differences. For the hierarchical tree structure 200 of FIG. 2 , one useful definition of difference between categories, subcategories, and/or items therein, is a distance metric such as, for example, the distance between two categories C_ 1 and C_ 2 . Hence, in some embodiments, a categorical distance function, C_Dist(C_i, C_j), is advantageously employed to represent a “difference” between category C_i and C_j. A larger distance metric between C_i and C_j, generally indicates more different such as, for example, more semantically different. In a particular implementation, C_Dis(C_ 1 , C_ 2 ) is the minimum number of steps that are needed to move through the category tree structure from C_ 1 to C_ 2 . Accordingly, in the Sports example:
C_Dis(MLB, NCAA_Baseball)=MLB→Baseball→NCAA_Baseball=2; and
C_Dis(MLB, NBA)=MLB→Baseball→Sports→Basketball→NBA=4.
For implementations that use distance as the difference metric, other types of category structures are also applicable if an appropriate distance function is defined for the structure. For instance, FIG. 3 illustrates a directory tree structure 300 of some embodiments. As shown in this figure, the directory structure includes a root directory /, and directories such as /Retail and /Music. Within each of these directories are sub directories, sub-sub directories, and so forth. For instance, the /Retail directory includes a sub directory for /Retail/Pet and therein a sub-sub directory for /Retail/Pet/Grooming, while the /Music directory includes a sub directory for /Music/Classic. Hereinafter, directories, sub directories, categories, and sub categories, may simply be referred to as directories, and/or categories.
As shown by FIG. 3 , the directories within the directory structure 300 have relevances to each other, such that items grouped within each directory are advantageously scored based on relevance and/or affinity, as described above. Typically, items within a directory or that are sub or super directories have higher relevance and/or affinities to each other, than items that are located within distinct directories that are located along a separate branch of sub directories, for example.
The directories illustrated by FIG. 3 have differences as well. For instance, FIG. 4 illustrates that the directory /Retail/Pet/Grooming is selected as a predictor item. Generally, a predictor item has a known relevance or importance to a user. As described above, the predictor item has relevance to each other item in the structure 400 . In relation to the predictor item, the other items in the structure 400 are referred to as affinity items. The relevance of each affinity item to the predictor item is preferably measured by using affinity scores. The predictor item, however, further has differences from each of the affinity items. Some embodiments measure such differences by using a distance metric. In a particular implementation, the distance metric is calculated by counting the number of directory traversals between the predictor item and the affinity item. Hence, in this example, the distance from /Retail/Pet/Grooming to /Retail/Pet is one, while the distance from /Retail/Pet/Grooming to /Music/Classic is five, for example (three directory traversals to the root directory, and two traversals from the root directory to the /Music/Classic directory).
Accordingly, the affinity items /Retail/Pet and /Music/Classic may have similar or equally high affinities to the predictor item /Retail/Pet/Grooming. However, these same affinity items may have very different alternative relational characteristics such as directory, category, and/or tree distance, for example. The foregoing examples describe categories and directories in various advantageous structures. One of ordinary skill recognizes, however, that the discussion herein applies equally to items of content such as within each of the categories and/or directories, as well.
Category Sensitive Recommendation for Affinity Items
Embodiments of the invention advantageously balance recommendations across a broader range of categories of affinity items by balancing selections for recommendation items associated with distinct and more diverse categories. Further, some embodiments particularly select and/or recommend items in distant categories to promote a broader level of user engagement. The foregoing is represented symbolically herein, by way of example. For a selected predictor item K, a list of affinity items, separately Aff_Item_i with affinity score AFF_Score_i, is preferably identified based on the affinity scores that relate each affinity item to the predictor item. Some embodiments use the relevance engine 102 described above in relation to FIG. 1 . Some of these embodiments further determine a difference measure for the affinity items in the list such as by using a distance metric, as described above. In an implementation, the data are advantageously compiled as follows, where Cat_i is the category of the affinity item and C_Dis_i is the distance between Cat_i and the category of the predictor item K:
(Aff_Item_ 1 , AFF_Score_ 1 , Cat_ 1 , C_Dis_ 1 )
(Aff_Item_ 2 , AFF_Score_ 2 , Cat_ 1 , C_Dis_ 1 )
(Aff_Item_ 3 , AFF_Score_ 3 , Cat_ 1 , C_Dis_ 1 )
(Aff_Item_ 4 , AFF_Score_ 4 , Cat_ 1 , C_Dis_ 1 ) . . .
(Aff_Item_m, AFF_Score_m, Cat_ 1 , C_Dis_ 1 )
(Aff_Item_n, AFF_Score_n, Cat_ 2 , C_Dis_ 2 )
(Aff_Item_p, AFF_Score_p, Cat_ 2 , C_Dis_ 2 )
(Aff_Item_q, AFF_Score_q, Cat_ 1 , C_Dis_ 1 )
(Aff_Item_r, AFF_Score_r, Cat_ 3 , C_Dis_ 3 ) . . .
Conventionally, when recommendations are made solely based on affinity scores, several drawbacks often occur. For instance, in some cases, the top scoring affinity items may cluster. That is, all the items that are likely selected for recommendation belong to the same category, or a small group of categories and subcategories, while there are other relevant and desirable items for recommendation that are associated with other categories. Traditionally, these desirable items and/or categories may never be selected for recommendation. The foregoing clustering problem is further addressed below by way of examples.
Some embodiments distribute selections for recommendation inventory among a broader range of categories that appear in the list of relevant affinity items. For example, inventory for presentation of content is a limited resource. In an exemplary case, on each page view, a maximum of M recommendations can be served. Meanwhile, three categories Cat_ 1 , Cat_ 2 , and Cat_ 3 , are identified that contain particularly relevant prospective recommendation items. Thus, each of the categories involved in this example, Cat_ 1 , Cat_ 2 , and Cat_ 3 , are preferably allocated with a distribution of the inventory for presentation. For instance, some embodiments average and distribute the available inventory equally across the identified relevant categories. In this example of three relevant categories, one inventory distribution is to distribute M/3 inventory locations for each identified category.
An alternative implementation employs the categorical structures of the FIGS. 2 , 3 and 4 , illustrated above, to reduce the negative effects of clustering. This implementation combines the affinity scores with a distance metric to produce one total score. Some embodiments further include weighting parameters to adjust the importance of individual components. An example formula for combining the affinity score and the distance metric is:
Final_Score=Aff_Score+ C *Category_Distance.
In this example, the parameter C is a distance weighting parameter. With a larger value of the parameter C, the difference metric, in this case Category_Distance, receives a heavier weight, and thus, affinity items of more distant categories have higher scores, which increases a likelihood of being selected for recommendation to the user. Further, the parameter C of some embodiments provides scaling for the distance metric such that the distance score does not overwhelm the affinity score in the calculation of the final score. In some embodiments, the parameter C is adjusted by the user, and/or the parameter is optionally predetermined.
FIG. 5 illustrates a table 500 for the organization of predictor and/or affinity items. As shown in this figure, an exemplary predictor item 1 , is shown with scoring for three affinity items 2 , 3 and 4 . In the illustration, the affinity item 2 has an affinity score of 0.99, affinity item 3 has an affinity score of 0.98, and affinity item 4 has 0.01. In this illustration, the affinity score has a scale from 0.00 to 1.00, however, one of ordinary recognizes other scales such as, for example, 0 to 100, or another scale. Further, FIG. 5 illustrates operation at the item-level, however, operation upon categories, directories, or other structural objects is understood as well.
Preferably, the data in the table 500 are received from a relevance engine that is optimized to determine associations and scores between the different items. Some embodiments include affinity items that have low affinity scores. Some of these embodiments filter the affinity items that have low affinity scores such that no further calculations are expended for these items that have a lower likelihood of relevance to the user.
FIG. 6 illustrates a revised table 600 of such an embodiment. As shown in this figure, the affinity item 4 is illustratively stricken from the table 600 for having a low affinity score of 0.01. Some embodiments generate a new data set that contains only those affinity items having affinity scores above a threshold. In FIG. 6 , the affinity item 4 is stricken, however, to show that no additional computation such as distance precomputation, for example, is performed for the affinity item 4 . For the remaining affinity items (e.g., Items 2 and 3 ) having more significant relevance to the predictor item 1 , a distance metric is computed. Preferably, the distance metric is precomputed and stored in a format that facilitates rapid recall such as, for example, a lookup table or the like.
FIG. 7 illustrates an example 700 that includes the directories from an example given above. More specifically, the directory /Retail/Pets/Grooming is inserted as the predictor item 1 , /Retail/Pets is inserted as the affinity item 2 , and /Music/Classic is inserted as the affinity item 3 . As described above, the distance metric for the affinity item /Retail/Pets is computed as one, and the distance metric for /Music/Classic is computed as five, from the example above. Advantageously, additional computation is omitted for items having affinity scores that are too low.
FIG. 8 illustrates a process 800 that summarizes some of the embodiments described above. As shown in this figure, the process 800 begins at the step 802 , where a predictor item is selected. The predictor item has a relevance to a user such as, for example, an item within the category /Retail/Pets/Grooming for a user who has a significant interest for pet grooming supplies or services. Once the predictor item is selected, the process 800 transitions to the step 804 , where the process 800 receives a plurality of affinity items having affinity scores. As mentioned above, the affinity scores relate the predictor item to the affinity items. The generation of affinity scores typically involves a relevance engine, and may take place separately from the process 800 , or may be performed in conjunction with the process 800 . Regardless of how the scores are generated, the received affinity items, and/or scores are often in an advantageously arranged list format.
At the step 806 , the received affinity items are filtered based on the affinity scores. For instance, some embodiments sort the received affinity items in a sorted list format by using the affinity scores, and then identify affinity items having affinity scores greater than a threshold. These cases preferably forego further calculations for affinity items that have little relevance for the predictor item thereby advantageously reducing the amount of excessive calculation.
Accordingly, at the step 808 , a first set of affinity items is selected from the received affinity items. Then, at the step 810 , for each selected affinity item, a difference score is calculated that measures a difference from the predictor item. In a particular, embodiment, the predictor item and affinity items are represented in a tree structure, and the difference score is based on a distance metric that measures the distance between the predictor item and each affinity item within the tree.
At the step 812 , the process 800 further selects a first affinity item from the first set of affinity items, based on the difference score for the first affinity item. For instance, some embodiments calculate a total score for the first affinity item and for a second affinity item. In this example, the process 800 may select the affinity item that has a higher total score for presentation to the user, as the score having higher value in both relevance and difference (e.g., a non-clustered but still highly relevant item). Optionally, the process 800 may present the selected first item or an item relevant thereto, to the user. For instance, where the item comprises advertising, the item may be placed in an inventory location on a property page, for presentation to the user.
At the step 814 , a determination is made whether to continue. If at the step 814 , the process 800 should continue, then the process 800 returns to the step 800 . Otherwise, the process 800 concludes.
FIG. 9 illustrates a system 900 for presenting content including advertising to users through a network. As shown in this figure, the system 900 includes a plurality of users 902 and 904 that interact with a network 906 . The network includes local area networks, wide area networks, and networks of networks such as the Internet, for example. The network 906 typically includes several sites comprising a number of web pages having content and inventory. The inventory is for the presentation of advertising to the users 902 and 904 . Accordingly, the network 906 is coupled to an exemplary site or page 908 that includes several inventory placements 910 , 912 and 914 . The site 908 is coupled to a server 916 for data collection and processing. The server 916 receives data from a variety of sources, including directly from the users 902 and 904 , from the network 906 , from the site 908 , and/or from another source 907 . Typically, the site 908 is provided by a publisher, while the server 916 is typically provided by a network portal and/or an Internet portal. Further, as users 902 and 904 interact with the network 906 , and the site 908 , advertisements placed in the inventory of the site 908 , are presented to the users 902 and 904 .
The selection and/or presentation of advertising through the inventory is a non trivial process. The inventory are typically distributed across many varied sites and pages, there are many different users and types of users, and marketers, advertisements, and ad campaigns are usually numerous and varied as well. The foregoing describes a novel recommendation mechanism that promotes variety for recommendations in the selection and/or placement of content with inventory. The mechanism advantageously reduces user burn out rate, and further increases user engagement level. More specifically, particular implementations consider both affinity scores and semantic category distance. While the invention has been described with reference to numerous specific details, one of ordinary skill in the art will recognize that the invention can be embodied in other specific forms without departing from the spirit of the invention. For instance, while the embodiments above are described in relation to online content, one of ordinary skill recognizes applications in additional media and data types. Thus, one of ordinary skill in the art would understand that the invention is not to be limited by the foregoing illustrative details, but rather is to be defined by the appended claims.
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A method selects a predictor item that has a relevance to a user. The method receives a set of affinity items having affinity scores that relate the predictor item to the affinity items. The method filters the list of affinity items based on the affinity scores, and selects a first set of affinity items from the filtered items. For each selected affinity item, the method calculates a difference score from the predictor item, and selects a first affinity item based on the difference score for the first affinity item. Preferably, content is presented to the user based on the selected first affinity item. Additional embodiments include a system and/or computer readable medium having instructions for execution of the foregoing.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 07/686,021, filed Apr. 11, 1991, now abandoned.
FIELD OF THE INVENTION
This invention relates to the descaling of pipes carrying water, gasoline, or other fluids, and to the "conditioning" of such fluids.
BACKGROUND OF THE INVENTION
Water supplies typically contain chemicals, such as calcium carbonate, which are leached from the ground or from pipes carrying the water and are carried along with the water. Over time, these chemicals are deposited on the interior of the pipes and lead to buildup in the form of scale (e.g., calcite) within the pipes. Eventually, this buildup results in a constriction of the pipes and a reduction of the flow of water through the pipes. Similar materials also deposit on cooling towers, heat exchangers, and boilers, reducing their efficiency, which in turn results in increased operation costs. Material such as iron dissolved in water can be deposited on fountains or other surfaces that are constantly in contact with water, resulting in unsightly stains. In addition, water pools, lakes, fountains, and spas often contain microorganisms which result in poor quality and unattractive water.
Currently, removal of scale and microorganisms is achieved by treatment with chemicals, such as hexavalent chromium, hydrochloric acid, and sodium hypochlorite. Treatment with such chemicals results in a considerable cost for the continued use of the chemicals themselves and the constant monitoring which is required to ensure that the chemicals are at the correct "working" concentrations. The use of such chemicals may lead to increased rates of corrosion of the pipes and of other structures which are subjected to them. In addition, while treatment of scale on pipes with chemicals may lead to an increased water flow by enlarging the effective internal diameter of the pipes, the scale is not removed completely, and significant amounts of scale remain in place.
An additional cost of the use of chemicals is to the environment. Chemicals that are used in treating the water cause contamination of the water, and such water may require collection and dumping after use. Such dumping results in a significant economic, as well as environmental, cost.
Another source of environmental pollution is the inefficient burning of gasoline in internal combustion engines, where unburned gasoline is exhausted into the environment. Also, inefficient burning of gasoline in an internal combustion engine results in a buildup on spark plugs, which necessitates frequent tune-up of engines in order to maintain their operation at a reasonable level of efficiency.
Over the last fifty years, non-ionizing irradiation processes, such as magnetic fields, have been advertised as a kind of panacea for water treatment. It has been claimed that these devices require no technical training or control and will treat water non-chemically to control microorganism growth, prevent scale, and inhibit corrosion. Variable effectiveness and little scientific understanding of the process mechanisms have produced substantial skepticism.
Since the 1950's, many magnetic water-conditioning devices have claimed to require no addition of chemicals for scale and corrosion control. However, by the late 1950's, reports indicated that systems in operation were not effective in reducing scale and corrosion and suggested that the ineffectiveness was due to low field intensity. Skepticism continued, and by the 1970's, reports implied that these systems were contrary to the basic principles of science and were inoperative. Similar reports have cautioned against the use of these systems for industrial treatment.
Numerous studies on descaling, softening, and corrosion control have not observed any positive results, although some studies have reported the effectiveness of magnetic treatment processes. These studies have noted many problems, which can be divided into two categories:
1) operational and maintenance problems: One study found that, when boiler water was treated by a magnetic applied field process, large pieces of scale dropped from the upper tube and tank wall surface and accumulated on the tubes below. This scale resulted in "hot spots," requiring tube replacement and expensive downtime. Consequently, frequent inspection and removal of scale deposits were suggested. Accumulation of scale in the bottom of the boiler was also observed as cleaning progressed. Such accumulations can clog blowdown openings and cause a buildup in soluble salt concentrations, which could result in further scaling; and
2) process reliability: Magnetic systems have been reported to have problems with the influence of external magnetic fields, temperature, vibration, and masses of metals.
In view of the above, there is a need for a system which will prevent and remove scale buildup, inhibit the growth of microorganisms, and prevent staining from compounds contained in water. In addition, there is a need for a system which will aid in the complete combustion of gasoline in an internal combustion engine. The system should be a low-cost system that is non-polluting.
Furthermore, since pipes come in all sizes, it is desirable that such a system be adaptable to accommodate any conventional pipe size which may be encountered in the routine use of such a device.
SUMMARY OF THE INVENTION
The present invention relates to a magneto-hydrodynamic system, and method, for the treatment of pipes, and the fluid carried in the pipes, to prevent scaling and build-up of deposits in the pipe.
The magneto-hydrodynamic system comprises a pipe for carrying a fluid, at least one magnet unit abutting the exterior of the pipe and means of securing the magnet unit to the pipe. Additional units may be added to accommodate large diameter pipes.
The magnet unit comprises at least four magnets, each having a magnetic-field density about 6,700 gauss. End pole pieces are placed on each end of the magnet units, and a top pole piece covers the surface of the magnets on the sides of the magnets opposite the side in contact with the pipe to be treated.
BRIEF DESCRIPTION OF THE DRAWINGS
Features, aspects, and advantages of the present invention will be more fully understood when considered with respect to the following detailed description, appended claims, and accompanying drawings, where:
FIG. 1 is a semi-schematic perspective view of a magneto-hydrodynamic system;
FIG. 2 is a semi-schematic front elevation of a magnet unit with the housing removed;
FIG. 3 is a semi-schematic perspective view of the magnet unit shown in FIG. 2, except the top pole plate has been removed;
FIG. 4 is a semi-schematic perspective view of two magnet units placed on a pipe; and
FIG. 5 is an exploded view of a magnet unit and housing for use on fuel lines.
DETAILED DESCRIPTION
FIG. 1 illustrates a magneto-hydrodynamic treatment system 10. The system in one embodiment includes six magnet units 12, which abut a pipe 14 that is to be treated. Each magnet unit is held together by a housing 6. The magnet units are joined to each other and held in position around the pipe by a wire 17. In one embodiment, the magnet unit has dimensions of about 10 cm long, about 2 cm wide, and about 3 cm deep.
Each magnet unit, shown in FIGS. 2 and 3, includes a plurality of permanent magnets 18 and 19. The magnets are rare-earth cobalt magnets and/or iron/boron magnets. A suitable magnet for use in the present invention are CRUMAX® and/or CRUCORE®, supplied by All Magnetics, Inc. of Placentia, Calif.
The magnets are arranged so that a like pole of each of the magnets is adjacent a like pole of an adjacent magnet. End pole pieces 22 are placed at either end of the magnet unit, and a top pole piece 20 is placed between the end pole pieces and along the length of the magnet unit. It is thought that the top and the end pole pieces act to "focus" the magnetic field into the pipe to be treated.
In a six-magnet-containing unit, as shown in FIGS. 2 and 3, the arrangement of the components is, starting at the downstream side of the magnet unit: an end pole piece; a large magnet 18, the south pole of which abuts the pipe and the north pole of which abuts the top pole piece; two small magnets 19, both of which are oriented with their respective non-polar surfaces abutting the pipe and with the south pole of each of the magnets oriented to be downstream and the north pole of each of the magnets upstream; a second large magnet, the north pole of which abuts the pipe and the south pole of which abuts the top pole piece; and a second end pole piece at the end of the magnet unit. The space created between the small magnets and the top pole piece is filled with two cylindrical magnets 27. The cylindrical magnets are oriented so that their poles are oriented in the same direction as the large magnets adjacent them. Alternatively, the space between the small magnets and the top pole piece may be filled with a filler. Above the top pole piece is a filler 23, which fills the space between the top pole piece and the housing and which ensures that the magnets remain in contact with the pipe.
In one embodiment of the present invention, the magnets have a magnetic-field density of at least 6,700 gauss per magnet. It is desirable to use magnets with such a magnetic-field density so that the "descaling," for example, of a clogged pipe occurs over a time period of from about 90 to about 120 days or longer. If the descaling process occurs over a very short period of time, it is possible that clumps of scale will break free and clog the pipe downstream, resulting in damage to the pipe and disruption of the water supply. If the descaling process is performed relatively slowly, the scale is gradually released into the water flowing through the pipe and is carried away and out of the pipe. While a period of from 90 to 120 days is often sufficient to descale pipes, in some cases the scale buildup is so extensive that prolonged exposure is required. This prolonged exposure is in the order of from several months to one year. The magneto-hydrodynamic treatment system is effective for use with pipes constructed from materials such as galvanized steel, black iron, PVC, copper and glass.
In another embodiment of the present invention, each magnet has a rectangular cross-section. The end pole pieces also have a generally-rectangular cross-section, but have a flanged top 24 with a greater width than that of the principal cross-section. The flanged top connects into the housing 16, as shown in FIG. 4. The bottom of each pole piece is angled upward to form a concave section at its center, allowing the magnet units to conform to the shape of the pipe which they are to treat. The top pole piece comprises a flat strip, which extends from one end pole piece to the other end pole piece. In one embodiment, the end and top pole pieces are composed of powdered, pressed metal produced by a powder metallurgy process. Metals suitable for use as pole pieces in the present invention include ferromagnetic metals. Such metals can be obtained from Compax, Inc., of Anaheim, Calif. Each pole piece is preferably coated with TEFLON or other suitable coating to prevent corrosion.
The magnet unit, once assembled, is then placed in an aluminum housing. The housing has a roughly-rectangular, U-shaped cross-section and comprises an inset to slidably engage the flanged tops of the end plates. The housing is enclosed on three sides and open on the side which abuts the pipe. Molded into the housing, at the end of the base of the "U" and at each end of the housing, are holes 30 for receiving wire rests 32.
In a preferred embodiment, the wire rests comprise a pin 34 at one end to engage the holes of the housing, with a cylindrical head 35 at the other end. A groove 36 is cut around the circumference of the head to engage a wire 17. When the wire rests are placed in the holes of the housing, the cylindrical head overlaps the pole plate, thereby holding the pole plate and the magnets in place.
In operation, the magneto-hydrodynamic treatment system includes a plurality of magnet units, each disposed around the pipe to be treated. Each of the magnet units is held in position by a wire which slidably connects to each side of a housing of the magnet unit. The wires therefore form a perimeter around the pipe and the magnet units. The magneto-hydrodynamic treatment system, comprising magnet units each of about 10 cm in length by about 2 cm in width and about 3 cm in height, is effective on all pipe sizes from about 1 cm up to about 60 cm. Any pipe size larger than about 60 cm would require the use of magnet units of greater dimensions.
The number of magnet units used in the magneto-hydrodynamic treatment system of the present invention is determined by the diameter of the pipe. For example, a magneto-hydrodynamic treatment system for use on pipes with a diameter of from about 1 cm to about 2.5 cm includes two magnet units. The number of magnets desirable for different-diameter pipes is set forth in Table 1.
TABLE 1______________________________________Pipe Diameter Number of(in cm) Magnets______________________________________1-2.5 24 35 46.5 58 610 812.5 1015 1218 1420 1623 2030 2435 2840 3245 3650 4055 4460 48______________________________________
To assemble the required number of magnet units for the size of pipe to be treated, magnet units are placed around a pipe to be treated, and the units are secured in place with a bolt 38. The loose ends of the wire are wound around the bolt so that, when it is turned, the wire tightens and thus tightens the magnet units to the pipe. The magneto-hydrodynamic treatment system of the present invention can be varied to fit any desired pipe size, by minor adaptation procedures and at a relatively small cost. Such modification can be readily performed on site.
The present invention is described above in relation to one general working embodiment for use in descaling water pipes and is for illustration purposes. Variations will be apparent to those skilled in the art. For example, the pipe being treated may be grounded on the upstream side from the magneto-hydrodynamic treatment system. Such grounding enhances the descaling process. Multiple treatment systems can be used on a single pipe system to remove scale along its entire length or, alternatively, a single treatment system can be moved along the length of a pipe after one clogged region is cleared. For use in cooling towers, multiple treatment systems are used. In a typical cooling-tower installation, treatment systems are positioned on the return and make-up water lines, as well as on water lines which go to the chiller or the heat exchanger. Such a configuration results in descaling of the cooling tower being treated.
Additionally, the magneto-hydrodynamic treatment system can be used on the inlet pipes of recirculation water lines for ponds and lakes. The use of the magneto-treatment system results in an increased clarity of the water in the pond or the lake, due to a reduction in the number of microorganisms present in the water. The magneto-hydrodynamic treatment system can be used on the water inlet pipes of fountains. Such use prevents the buildup of rust stains and also aids in the removal of existing rust stains. In addition, permanent magnets other than rare-earth cobalt magnets could be used to achieve the desired results. Electro-magnets could be used in place of permanent magnets.
In another embodiment of the present invention, the magneto-hydrodynamic treatment system is used on very small pipes such as piping for ice makers or for fuel lines in an internal combustion engine to increase the efficiency with which fuel is burned, hence reducing the hydrocarbon emissions and buildup on engine components such as spark plugs. In one embodiment (see FIG. 5), the magnet unit for use on such fuel lines includes five permanent magnets 18. The magnetic-field densities of the rare-earth cobalt magnets are at least 6,700 gauss per magnet. The arrangement of the components in this embodiment is, starting at the downstream side of the magnet unit: an end pole piece; a first magnet, the north pole of which abuts the pipe and the south pole of which abuts the top pole piece; a second magnet, the north pole of which abuts the pipe and the south pole of which abuts the top pole piece; a third magnet, turned on its side relative to the first and second magnets so that its non-polar surface abuts the pipe (the space so created between the magnet and the top pole piece is filled with a spacer 26); a fourth magnet, the south pole of which abuts the pipe and the north pole of which abuts the top pole piece; a fifth magnet, the south of pole of which abuts the pipe and the north pole of which abuts the top pole piece; and a second end pole piece at the end of the magnet unit. In this embodiment of the invention, the dimensions of the magnet unit are about 3.1 cm in length, about 2.2 cm in width, and about 1.5 cm in height. The pole pieces 50 and magnets have a generally-rectangular cross-section. A semicircular groove 52 is cut into one side of the pole piece and the magnets to accommodate the fuel line being treated. Only a single magnet unit need be used for effective treatment of small-diameter pipes. The magnet unit is attached to the fuel line by a housing 54 and attachment plate 56. Screws 58 secure the housing to the attachment plate and hence to the fuel line. The housing is constructed of material such as aluminum or other suitable material. In operation, the magnet unit is located close to the carburetor or fuel-injection system. However, contact of the magnet unit with computer systems located in, or used in conjunction with, the internal combustion engine should be avoided, since damage to the computer may result.
The present invention is described above in relation to a second general working embodiment for use on fuel lines and is for illustration purposes. Variations will be apparent to those skilled in the art. For example, the magneto-hydrodynamic treatment could have larger or smaller dimensions than those recited for use with different-size fuel lines. Multiple magnet units could be used on large-diameter fuel lines. The magnet unit could include more individual magnets. The magnet unit could be attached to the fuel line or to the pipe to be treated by other suitable attachment means. Therefore, the present invention is not intended to be limited to the working embodiments described above. The scope of the invention is defined in the following claims.
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The present invention relates to a magneto-hydrodynamic system and method for the treatment of pipes and the fluid carried in the pipes to prevent scaling and build-up of deposits in the pipe. The magneto-hydrodynamic system comprises a pipe for carrying a fluid and at least one magnet unit abutting the exterior of the pipe to be treated. The magnet unit comprises at least four magnets, each having a magnetic-field density of about 6,700 gauss, end pole pieces on each end of the magnet units, and a top pole piece covering the surface of the magnets on a side of the magnets opposite the side in contact with the pipe to be treated.
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BACKGROUND OF THE INVENTION
1. Reference to Related Patent
The present application is a continuation-in-part application of U.S. Ser. No. 857,448, filed Mar. 25, 1992, which is a continuation of application U.S. Ser. No. 614,914, filed Nov. 19, 1990, now U.S. Pat. No. 5,143,357.
The present application is related to U.S. Pat. No. application Ser. No. 473,489, filed Feb. 2, 1990, by Paul V. Cooper, entitled "Melting Metal Particles," (hereinafter the "Melting Metal Particles Patent"), which is a continuation-in-part of U.S. Pat. No. 4,898,367, application Ser. No. 222,934, filed Jul. 22, 1988, by Paul V. Cooper, entitled "Dispersing Gas into Molten Metal," (hereinafter the "Dispersing Gas Patent"), the disclosures of which are incorporated herein by reference.
2. Field of the Invention
The invention relates to melting metal particles and, more particularly, to techniques for rapidly melting scrap particles of light metals such as aluminum and to dispersing gas and/or additives therein.
3. Description of the Prior Art
Light gauge, low density scrap metal particles such as chips, borings, and turnings are produced as a by-product of many metal processing operations. A significant amount of scrap metal also exists in the form of metal cans, particularly aluminum cans and used beverage containers. For convenience, all such scrap metal will be referred to herein as "scrap metal" and "particles". In order to recover the scrap metal for productive use, it is necessary to remelt it. Unfortunately, a number of problems are presented when scrap metal is attempted to be remelted. These problems are particularly acute in the case of light metal such as aluminum due to the tendency of the metal to oxidize when melted. The problems are worse for small particles of scrap metal than large ones, because (1) small particles have a relatively large surface-to-volume ratio and (2) small, lightweight particles tend to remain on the surface of a melting bath where they are oxidized while large, heavier particles sink rapidly beneath the surface without oxidizing.
Reverberatory furnaces have been used to melt scrap metal, but it has been necessary to use mechanical puddlers to achieve respectable recovery rates when small particles of scrap metal are being melted. Puddlers are expensive, bulky, mechanically complex, and are a source of iron contamination. Even with mechanical puddlers, melting of the scrap metal occurs slowly so that the metal tends to oxidize before it melts, resulting in recovery rates that are less than desirable. "Recovery rate" as used herein can be defined as follows: ##EQU1##
The situation is improved when induction furnaces are used. Strong inductive currents are set up in the molten metal which create a stirring action that rapidly submerges the scrap metal before additional oxide can form on the surface. Furthermore, the absence of high temperature combustion produces little or no oxide formation. The result is that recovery rates on the order of 97 percent can be attained. The chief drawback of the induction furnace melting technique is the high initial cost of the furnace and its relative small capacity with respect to a reverberatory furnace. The cost can be so great as to make the scrap recovery process uneconomical despite the high recovery rates available. A further drawback of the induction furnace melting technique is that it is a batch process, rather than a continuous process.
A different approach to the problem of recovering scrap metal is disclosed in U.S. Pat. No. 3,272,619 (hereafter the '619 patent), to V.D. Sweeney et al., the disclosure of which is incorporated herein by reference. In the '619 patent, molten metal is circulated from a reverberatory furnace, through an external crucible where a vortex is established, and back into the furnace. Melting of scrap metal does not occur in the furnace. Rather, the scrap metal is introduced into the vortex established in the external crucible. As the scrap metal swirls down in the vortex, the scrap metal particles eventually are melted. By appropriate control of such parameters as the temperature of the molten metal being circulated, the moisture content of the particles, and the rate at which the particles are fed into the crucible, recovery rates of about 90 percent can be attained.
Although the system described in the '619 patent has been reasonably effective, certain problems remain. The '619 patent states that the intensity of the vortex can be adjusted to produce desired submerging rates, but such adjustment has proven difficult to achieve in practice. The high surface tension of the molten metal in the crucible permits solid particles to remain on the surface of the vortex completely down into the return pipe to the furnace. The result is that solids and air can reach the furnace, with a consequent lowering of melting efficiency. In effect, the scrap metal being melted is exposed excessively to air such that undesired quantities of dross are formed. It is possible that oxide-covered metal drops (referred to hereafter as "agglomerations") can pass completely through the crucible and back into the furnace. An additional concern related to the device according to the '619 patent is the sensitivity of the crucible to flow variations. Because the crucible is most efficient with metal flowing near the top, a slight increase in flow rate can cause a spillover. Additionally, such a high operating level in the crucible can cause loss of heat through the crucible itself.
The apparatus disclosed in U.S. Pat. No. 4,747,583, issued May 31, 1988 to Elliot B. Gordon, et al. represents an improvement over the device according to the '619 patent. In the '583 patent, metal particles are mixed with molten metal flowing in a vortex in a crucible by means of stationary blades that project radially outwardly from a vertically-oriented sleeve disposed within the crucible. The blades are arranged relative to the surface of the molten metal such that particles deposited onto the surface of the molten metal are submerged substantially immediately after being introduced into the flow of molten metal. This result is brought about by encountering the blades which cause the molten metal, with the metal particles entrained therewith, to be deflected downwardly.
In U.S. Pat. No. 4,598,899, issued July 8, 1986 to Paul V. Cooper, melting of scrap metal particles is accomplished by disposing an auger in a bath of molten metal, rotating the auger so as to draw molten metal downwardly into the auger, and depositing metal particles onto the surface of the molten metal bath. By virtue of the action of the auger, the particles are drawn downwardly, through the auger, where they are forced into intimate contact with the molten metal and thereby are melted. Although the device disclosed in the '899 patent is very effective, certain concerns are not addressed. The auger disclosed in the '899 patent is a so-called shrouded auger, that is, it includes a plurality of radially extending blades, or flutes, that are surrounded by a hollow cylinder at their outermost ends. The relatively complex shape of the auger makes it relatively expensive and difficult to manufacture. The auger additionally is somewhat sensitive to the depth of molten metal in the bath, and the spaces defined by the blades and the surrounding hollow cylinder have the potential to become clogged with metal particles.
The device disclosed in the Melting Metal Particles Patent represents an improvement over the device according to the '899 patent. In the Melting Metal Particles Patent, a shaft-supported, rotatable impeller is immersed into a bath of molten metal and is rotated. Rotation of the impeller establishes a vortex-like flow. Metal particles are deposited onto the surface of the molten metal in the vicinity of the impeller. Due to the action of the vortex, the metal particles are submerged almost immediately.
The particular impeller used in the Melting Metal Particles Patent has proven very effective. The impeller is in the form of a rectangular prism having sharp-edged corners that provides an especially effective mixing action. The use of a shroud is not required. Due to the simplistic configuration of the impeller, it is inexpensive and reliable, while surprisingly being quite effective in operation.
Although the device disclosed in the Melting Metal Particles Patent is effective in quickly mixing the metal particles with the molten metal, certain concerns have not been addressed. One of these concerns relates to the strength of the vortex that can be established. The impeller in the Melting Metal Particles Patent must be operated relatively close to the surface of the bath in order to establish a strong vortex that will submerge the metal particles effectively.
Desirably, a technique would be available for rapidly mixing metal particles with molten metal that would be (1) inexpensive, (2) usable with a variety of containers (just not a crucible), (3) reliable, (4) long-lived, and (5) effective in its mixing action, particularly by being able to establish a strong vortex at a location relatively deep within a bath of molten metal. It also is desired that any mixer be able to be operated at the lowest possible speed while attaining good mixing results. It also is desired that any such device be configured so that it will be difficult or impossible to clog the device with metal particles.
SUMMARY OF THE INVENTION
In response to the foregoing considerations, the present invention provides a new and improved technique for melting metal particles wherein metal particles are mixed with molten metal contained in a bath and are submerged substantially immediately after being introduced into the molten metal. This result is accomplished by immersing a shaft-supported, rotatable impeller into the molten metal and rotating the impeller. Rotation of the impeller establishes a vortex-like flow. Metal particles then are deposited onto the surface of the molten metal in the vicinity of the impeller. Due to the movement of the molten metal and the impeller, the metal particles are submerged almost immediately.
In the preferred embodiment, the impeller is in the form of a generally plate-like rectangular prism having sharp-edged corners. The impeller includes an upstanding central portion to which the shaft is connected. A plurality of vanes extend radially outwardly from the central portion toward the corners of the prism. The vanes are disposed at right angles to each other, and they also are disposed generally perpendicular to the upper face of the prism. Desirably, the vanes taper from a thicker portion in the region of the central portion to a relatively narrow tip portion that is located at the corners of the prism.
Although the impeller is more complex than that disclosed and claimed in the Melting Metal Particles Patent, it still is relatively simplistic in configuration, thereby being relatively inexpensive to manufacture. The impeller is reliable in operation, and it provides an effective vortex-creating action. An advantage of the present invention is that the impeller can be disposed relatively deep in the bath while still being able to create a strong vortex. Accordingly, more metal particles can be melted in a given period of time than can be melted with prior devices, and the metal particles can be submerged quickly, so as to prevent the formation of undesired dross or other oxidation products.
The impeller according to the invention also cannot be clogged with metal particles due to the absence of orifices that can be clogged. In addition, the particular arrangement of the vanes relative to the plate-like prism insures that the vanes are supported adequately. Further, because the vanes project from the hub without any gaps therebetween, the inner portion of the vanes will break up any backflow of gas that may come out of solution during operation.
The impeller according to the invention also can be used to disperse gas into the molten metal. If such a result is desired, the techniques disclosed and claimed In the Dispersing Gas Patent can be utilized to provide in situ metal refining (degassing, demagging, alkali metal removal, etc.) during scrap melting by using a gaseous refining agent (unlike other purely scrap submergence devices). ln order to accomplish such a result, a longitudinal opening can be formed within the shaft, which opening extends through an opening formed in the bottom face of the impeller. Gas can be pumped through the shaft and out of the impeller along the lower face thereof. In such a circumstance, the impeller will shear the gas into finely divided bubbles as the gas rises along the sides of the rotating impeller.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view, with certain parts omitted for purposes of clarity of illustration, of apparatus according to the invention;
FIG. 2 is a top plan view of the apparatus of FIG. 1;
FIG. 3 is a cross-sectional view of the apparatus of FIG. 1 taken along a plane indicated by line 3--3 in FIG. 2;
FIG. 4 is a cross-sectional view of the apparatus of FIG. 1, taken along a plane indicated by line 4--4 in FIG. 3;
FIG. 5 is an enlarged view of the apparatus of FIG. 4, with an impeller and a shaft being illustrated in spaced relationship; and
FIG. 6 is a top plan view of the impeller of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1-3, apparatus for melting metal particles is indicated generally by the reference numeral 10. The apparatus 10 can be used in a variety of environments, and a typical one will be described here. A reverberatory furnace 12 includes a hearth 14 in fluid communication with a pump well 16, a charge well 18 and a skimming well 20. The hearth 14 includes a front wall 22 having an opening 24 that communicates with the pump well 16. A sidewall 26 defines a portion of the pump well 16. A front wall 28 and a floor 29 extend across the width of the furnace 12 and define a portion of the wells 16, 18, 20.
A sidewall 30 having a sloping inner surface connects the walls 22, 28 and defines a portion of the skimming well 20. A wall 32 extends between the walls 22, 28 and defines a portion of both the pump well 16 and the charge well 18. The wall 32 includes an opening 34 that permits fluid communication between the wells 16, 18. The wall 36 projects from the all 22 and divides the wells 18, 20. The wall 36 is not in contact with the wall 28, thereby defining a space 38 that permits fluid communication between the wells 18, 20. The wall 22 includes an opening 40 that permits fluid communication between the skimming well 20 and the hearth 14.
Molten metal is disposed within the reverberatory furnace 12 and the wells 16, 18, 20. The surface of the molten metal is indicated by the dashed line 42. As used herein, reference to "molten metal" will be understood to mean any metal such as aluminum, copper, iron, magnesium, zinc and alloys thereof. The invention is particularly useful with aluminum and alloys thereof.
A circulation pump 44 is disposed within the pump well 16. The circulation pump 44 can be of any type, provided that it performs the essential function of circulating metal from the pump well 16 through the opening 34 into the charge well 18. Suitable circulation pumps are commercially available from The Carborundum Company, Metaullics Systems Division, 31935 Aurora Road, Solon, Ohio 44139 under the model designation M-30, et al.
Referring particularly to FIGS. 2 and 3, a conveyor 46 is disposed adjacent the charge well 18, forwardly of the front wall 22. Particles 48 of scrap metal are conveyed by the conveyor 46 for discharge into the charge well 18.
The mixing apparatus 10 includes a drive motor and support 50. The drive motor and support 50 are disposed above the charge well 18 at approximately a central location relative to the charge well 18. A coupling 52 projects from the underside of the drive motor and support 50. A vertically oriented, elongate shaft 54 projects downwardly from the underside of the coupling 52. An impeller 56 is rigidly secured to the shaft 54 at a location remote from the coupling 52. As will be apparent from the examination of FIGS. 1-3, the impeller 56 is disposed within the molten metal 42 at a location relatively far beneath the surface of the molten metal 42. For best performance, the impeller 56 should be disposed within the range of about 4-12 inches beneath the surface of the molten metal 42.
The shaft 54 and the impeller 56 usually will be made of graphite, particularly if the molten metal being treated is aluminum. Other materials such as ceramics or castable refractory compositions could be employed, if desired. If graphite is used, it preferably should be coated or otherwise treated to resist oxidation and erosion. Oxidation and erosion treatments for graphite parts are practiced commercially, and can be obtained from sources such as The Carborundum Company, Metaullics Systems Division, 31935 Aurora Road, Solon, Ohio 44139.
Referring now to FIGS. 5 and 6, the impeller 56 includes a relatively thin rectangular prism having an upper face 58, a lower face 60, and sidewalls 62, 64, 66, 68. The faces 58, 60 are parallel with each other as are the sidewalls 62, 66 and the sidewalls 64, 68. The faces 58, 60 and the sidewalls 62, 64, 66, 68 are planar surfaces which define sharp, right-angled corners 70.
The sidewalls 62, 66 have a width identified by the letter A, while the sidewalls 64, 68 have a depth indicated by the letter B. The height of the impeller 56, that is the distance between the upper and lower faces 58, 60, is indicated by the letter C. Preferably, dimension A is equal to dimension B and dimension C is equal to about 1/20 dimension A. More preferably, dimension C is equal to about 1/2 to 1/10 dimension A and most preferably 1/3. Deviations from the foregoing dimensions are possible, but best performance will be obtained if dimensions A and B are equal to each other (the impeller 56 is square in plan view) and if the corners 70 are sharp and right-angled. Also, the corners 70 should extend perpendicular to the lower face 60 at least for a short distance above the lower face 60.
As illustrated, the corners 70 are perpendicular to the lower face 60 completely to their intersection with the upper face 58. It is possible, although not desirable, that the upper face 58 could be larger or smaller than the lower face 60 or that the upper face 58 could be skewed relative to the lower face 60; in either of these cases, the corners 70 would not be perpendicular to the low face 60. The best performance is obtained when the corners 70 are exactly perpendicular to the lower face 60. It also is possible that the impeller 56 could be triangular, pentagonal, or otherwise polygonal in plan view, but it is believed that any configuration other than a rectangular, square prism produces reduced mixing action.
The dimensions A and B also should be related to the dimensions for the charge well 18, if possible. In FIG. 4, the dimension D identifies the average inner diameter of the charge well 18. In particular, the impeller 56 has been found to perform best when the impeller 56 is centered within the charge well 18 and the ratio of dimensions A and D is within the range of 1:6 to 1:8. Although the impeller 56 will function adequately in a charge well 18 of virtually any size or shape, the foregoing relationships are preferred.
The impeller 56 includes an upstanding central portion, or hub, 72 that projects from the upper face 58 at the center thereof. A plurality of vanes 74, 76, 78, 80 extend radially outwardly from the hub 72. Each of the vanes 74, 76, 78, 80 includes a relatively thick inner position 82 that is connected to the hub 72, a relatively sharp-edged tip portion 84 that is disposed at one of the corners 70, and a pair of opposed sidewalls 86 that taper smoothly from the inner portion 82 to the tip portion 84. The uppermost potions of the hub 72 and the vanes 74, 76, 78, 80 define a surface identified by the reference numeral 88 in FIG. 5. The surface 88 is parallel to the upper and lower faces 58, 60. Each tip portion 84 terminates in beveled sections 90 and a sharp edge 92 located at the intersection of the beveled sections 90. Each of the edges 92 is coincident with a corner 70.
As is apparent from an examination of FIGS. 5 and 6, the vanes 74, 76, 78, 80 are disposed generally perpendicular to the upper face 58. The vanes 74, 76, 78, 80 are rigidly connected to the upper face 58 so as to be strengthened thereby. The vanes 74, 76, 78, 80 are disposed at right angles to each other, that is, any given vane is disposed equidistantly between adjacent vanes. Moreover, the vanes 74, 78 include longitudinal axes that are aligned with each other and that extend from one corner 70 to the opposed corner 70. Similarly, the longitudinal axes of the vanes 76, 80 are aligned with each other such that the vanes 76, 80 extend from one corner 70 to the opposed corner 70.
The shaft 54 includes an elongate, cylindrical center portion 94 from which threaded upper and lower ends 96, 98 project. Normally the shaft 54 and the impeller 56 are solid. However, as disclosed in the Dispersing Gas Patent, the shaft 54 can include a longitudinally-extending bore that opens through the ends of the threaded portions 96, 98. Gas dispersing capability can be created by appropriate machining of a bore in the standard shaft material configuration, or by use of a commercially available injection tube, merely by machining threads at each end of the tube. A typical injection tube suitable for use with the present invention has an outer diameter of 2.875 inches, a bore diameter of 0.75 inches and a length dependent upon the depth of the charge well 18.
As is illustrated in FIGS. 5 and 6, the lower end 98 is threaded into an opening 100 formed in the hub 72 until a shoulder defined by the cylindrical portion 94 engages the surface 88. When gas-dispersing capability is desired, the opening 100 extends completely through the impeller 56. The shaft 54 also could be rigidly connected to the impeller 56 by techniques other than a threaded connection, as by being cemented or pinned, although a threaded connection often is preferred for ease of assembly and disassembly. The use of coarse threads (41/2" pitch, UNC) facilitates manufacture and assembly.
In operation of the apparatus 10, the circulation pump 44 is activated so as to cause molten metal 42 to flow from the hearth 14 through the opening 24 and laterally from the pump well 16 into the charge well 18. Metal within the charge well 18 eventually is directed through the space 38 into the skimming well 20, and thereafter into the hearth 14 by way of the opening 40.
As illustrated, the impeller 56 is rotated clockwise when viewed from above. For molten aluminum and alloys thereof, the impeller 56 should be rotated within the range of 50-300 revolutions per minute; approximately 85-90 revolutions per minute is preferred for best submergence and metal-melting efficiency. At his rate of rotation, the impeller 56 creates a smooth, strong vortex within the molten metal 42 contained within the charge well 18. The impeller 56 also permits rotation in either direction.
As the conveyor 46 is activated, the particles 48 will be deposited onto the surface of the molten metal 42. Due to the mixing action imparted by the impeller 56, the particles 48 will be submerged substantially immediately for prompt melting. Due to the efficiency of the mixing action imparted by the impeller 56, virtually no oxides are formed and agglomerations are minimized or eliminated.
As has been indicated in the Dispersing Gas Patent, the apparatus 10 can be used to inject gas into the molten metal 42. As used herein, the term "gas" will be understood to mean any gas or combination of gases, including argon, nitrogen, chlorine, freon and the like, that have a purifying effect upon molten metals with which they are mixed. It is customary to introduce gases such as nitrogen, argon and chlorine into molten aluminum and molten aluminum alloys in order to remove undesirable constituents such as hydrogen gas, non-metallic inclusions, magnesium (demagging) and alkali metals (lithium, sodium and calcium). The gases added to the molten metal react chemically with the undesired constituents to convert them to a form (such as a precipitate or a dross) that can be separated readily from the remainder of the molten metal. In order to obtain the best possible results, it is necessary that the gas be combined with the undesirable constituents efficiently. Such a result requires that the gas be disbursed in bubbles as small as possible, and that the bubbles be distributed uniformly throughout the molten metal.
As is described more completely in the Dispersing Gas Patent, when the apparatus 10 is used as a gas disperser, the bore in the shaft 54 is connected to a gas source (not shown). Upon immersing the impeller 56 in the molten metal 42 and pumping gas through the bore in the shaft 54, the gas will be discharged through the opening 100 in the form of large bubbles that flow outwardly along the lower face 60. Upon rotation of the shaft 54, the impeller 56 will be rotated. Assuming that the gas has a lower specific gravity than the molten metal, the gas bubbles will rise as they clear the lower edges of the sidewalls 62, 64, 66, 68. Eventually, the gas bubbles will be contacted by the sharp corners 70 and the edges 92. The bubbles will be sheared into finely divided bubbles which will be thrown outwardly and thoroughly mixed with the molten metal 42 which is being churned by the impeller 56. In the particular case of the molten metal 42 being aluminum and the treating gas being nitrogen, argon, or chlorine, or mixtures thereof, the shaft 54 should be rotated within the range of 200-350 revolutions per minute. Because there are four corners 70 and four edges 92, there will be 800-1,400 shearing edge revolutions per minute.
Other additives in granular form may also be introduced to the molten metal through the bore in shaft 54. Particularly, alloying agents, those materials which form an alloy with the molten metal, such as silicon metal, manganese, copper, magnesium, iron, nickel, chromium, lead and/or zinc. Often, these alloying agents will be introduced as granular aluminum containing master alloys of the desired metal element. Fluxes, usually salt mixtures, as are known to those skilled in the art, may also be introduced through the bore to treat drosses, inclusions and reduce hydrogen. Modifying agents, such as titanium, boron, sodium, strontium, antimony, phosphorus and/or calcium, in the form of master alloys and/or salts, may also be added to the molten metal by this means.
When the apparatus 10 is being used as a gas-disperser, it is expected that the impeller 56 will be positioned relatively close to the bottom of the vessel within which the apparatus 10 is disposed. Rotation of the impeller 56 will not cause a vortex to be formed at the surface of molten metal, or at best only nominal vortex action will be created. By using the apparatus according to the invention as a gas-disperser, high volumes of gas in the form of finely divided bubbles can be pumped through the molten metal 42, and the gas so pumped will have a long residence time. The apparatus 10 can pump gas at nominal flow rates of 1-2 cubic feet per minute (c.f.m.), and flow rates as high as 4-5 c.f.m. can be attained without choking. The apparatus 10 is very effective at dispersing gas and mixing it with the molten metal 42.
The apparatus 10 is exceedingly inexpensive and easy to manufacture, while being adaptable to all types of molten metal storage and transport systems, as well as all types of techniques for depositing particles onto the surface of molten metal. An important advantage of the apparatus 10 is that when the apparatus 10 is used as a scrap melter, the impeller 56 can be disposed relatively far beneath the surface of the molten metal. Accordingly, a stronger, deeper vortex can be created than can be created with prior vortex-creating devices. In turn, more metal particles can be melted in a given period of time, and with greater efficiency, than is possible with prior devices.
The apparatus 10 does not require precision-machined, intricate parts, and thereby has greater resistance to oxidation and erosion, as well as enhanced mechanical strength. Because the impeller 56 and the shaft 54 present solid surfaces to the molten metal 42, there are no orifices or channels that can be clogged by dross or foreign objects such as the particles 48 or agglomerations.
Although the invention has been described in its preferred form with a certain degree of particularity, it will be understood that the present disclosure of the preferred embodiment has been made only by way of example and that various changes may be resorted to without departing from the true spirit and scope of the invention as hereinafter claimed. It is intended that the patent shall cover, by suitable expression in the appended claims, whatever features of patentable novelty exist in the invention disclosed.
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Metal particles are melted by mixing them with molten metal contained in a bath. A shaft-supported, rotatable impeller is immersed into the molten metal and rotated so as to establish a vortex-like flow of molten metal. Metal particles are deposited onto the surface of the molten metal in the vicinity of the rotating impeller. The particles are submerged substantially immediately after being deposited onto the surface of the molten metal. The impeller includes a thin rectangular prism having sharp-edged corners and vanes that extend upwardly from the prism. The impeller also can be used to disperse gas into the molten metal by pumping the gas through a bore extending the length of the shaft and out of the impeller along the lower surface of the impeller. The gas is sheared into finely divided bubbles as it rises along the sides of the impeller.
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RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application Ser. No. 61/364,673, filed Jul. 15, 2010, which is herewith incorporated by reference. U.S. Patent Application Ser. No. 61/264,988, “Camera-Based Color Correction of Displays Using Linear Subspace Projections” filed Nov. 30, 2009, is also herewith incorporated by reference.
BACKGROUND
Multi-display systems are typically composed of a set of disparate display devices, e.g., projectors, that are used in concert with one another to render a single image. The approach has advantages such as very-high resolution, large-format, and flexibility. However, differences in the underlying displays detract from the composite image and should be addressed. The present system and method addresses the color differences that exist due to engineering/tolerance differences in the underlying display devices, degradation of the display image over time, and even differences in the underlying display technologies (e.g., a display composed of LCD and DLP projection units).
Traditional approaches to color alignment range from by-hand tuning of the projectors and ICC profiling to semi-automatic methods that directly communicate with the projector. Clearly, methods that require human interaction suffer from the additional time and cost of tuning the projectors. Typically methods require an expert user and may mean that displays go without by-hand color alignment for long periods of time. In addition, not all projectors support the type of controllability that a by-hand solution requires.
In addition, current color alignment solutions use projector-specific settings to modify the color transform. This limits these approaches to particular projectors and restricts the corrective transform to the available transforms in the projector.
SOLUTION
The present method provides automatic color correction for multi-display systems. In particular, when combining multiple displays into a single coherent display (either by overlapping multiple projectors or by tiling display panels into a large array), it becomes important that the individual displays exhibit similar color characteristics. For example, when one display depicts a color triplet (R G B) whose values are [200 10 10], other displays displaying the same RGB triplet should show the same color so that a viewer sees a single uniform color across the entire display array. Without a method to calibrate and correct for color differences, different display devices will generate different color responses for a given input RGB value. The present system detects and corrects these color response differences to enable a uniform (in color and intensity) display across multiple display devices.
The present system uses a software-based solution that first models the color response of each projector with a camera and then applies a corrective transform in the rendering pipeline. This ensures maximum flexibility in applying the corrective transform and supports a more accurate color alignment for any set of projectors. If needed, the system is also able to translate this color transform into hardware instructions for any device that can support color correction. For example, color correction can be supported in hardware warp/blend devices as well as directly on the projector.
A camera or other sensor is used to observe each display for a set of color input values. Once measured, the color response of the individual displays can then be compared to other displays in the system. The system then determines an appropriate modification to apply to each display device that will drive the different towards a color value that matches.
SUMMARY
A sensor observes the output energy of each of the displays in a multi-display system and measures the difference in the color responses for a given input color. This difference is used to derive a modification function that is applied to each display. The displays are modified accordingly, and then the color is displayed again. This process is repeated until the measured values from each of the displays are within a minimum measurement error tolerance, so that the differences in displayed colors observed among the displays are minimized.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating exemplary components of the present system; and
FIG. 2 is a flowchart showing an exemplary set of steps performed by the present system in providing automatic color alignment across multiple displays.
DETAILED DESCRIPTION
The present color alignment system operates via a closed-loop control and optimization process. The system iteratively controls the output of multiple display devices, modifies the behavior of one or more of the display devices based on measurements, and the re-measures the display output. This process continues until the difference between the displays is minimized.
FIG. 1 is a block diagram of exemplary components of the present system 100 . As shown in FIG. 1 , in an exemplary embodiment, a closed-loop search process, controlled by a PC or other computer 110 , drives two displays 105 ( 1 ) and 105 ( 2 ) towards a similar color response by controlling the color response of corresponding projectors 106 ( 1 ) and 106 ( 2 ) using a sensor 104 , a measurement module 101 , an optimization module 102 , and a display controller 103 . It should be noted that the present system is operable with more than two displays, and that the displays may overlap and/or be positioned relative to each other in any desired configuration.
Initially, the color response of each display is measured for either for single or multiple color values. An optimization module then computes an error function that relates the observed color differences to a particular error metric. This error metric, possibly combined with earlier errors and observations, determines how the projectors need to be modified to reduce the observed error. This modification is passed to the display controller and the process is repeated. The process terminates when alignment has been reached.
The Measurement Process
FIG. 2 is a flowchart showing an exemplary set of steps performed by the present system in providing automatic color alignment across multiple displays. As shown in FIG. 2 , at step 205 , each projector 106 in the present system is driven by display controller 103 to generate a test image that contains a range of color values. Each of these test images is captured by camera 104 , at step 210 , to derive a color response profile for the corresponding projector 106 /display 105 , at step 215 .
It should be noted that the color response profile being measured at any given moment is modified by the current control function embedded in the display controller 103 . The color response profiles can be gathered via a variety of sensors including digital cameras and radiometric sensing devices. The present method may, alternatively, use any sensing device capable of measuring the color response of a display device. The observed values can be modified to improve their accuracy through image processing or statistical analysis operations such as computing a mean measurement repeatedly or computing a mean color response over a range of pixels in a CCD.
The use of a specialized radiometer to generate an ICC (International Color Consortium) profile allows a user to characterize the color response of the projection device in a standardized way. These profiles can be used by graphics drivers, applications that support them (e.g., design software for users that are sensitive to the color response of a display, such as Adobe Pagemaker), and the profiles are sometimes used to inform the by-hand tuning process. It should be noted that the present color alignment system supports the use of a radiometer and can directly load ICC profiles. This industry standard support is valuable to those who would like to use the same measurement process they have been using in the past, but want the correction quality provided by the present color alignment system.
Computing a Corrective Step
Once the color response profile of each display has been captured, the current color behavior of each of the displays is known. The color difference between the multiple displays is then computed at step 220 . In an exemplary embodiment, the mean color intensity difference as measured in RGB space is used as a difference measure. Other distance measures that may be used include the current maximum difference of any measured color or the difference in volume of the complete color gamuts of the display. This color difference, e, is associated with the current operating mode of each of the projectors.
In an exemplary embodiment, the system operating mode is represented as a vector of operating modes that represents the current color transfer function of each of the k displays in the system, O=[o1 o2 . . . oi . . . ok]. This vector describes, for a given input color value [R G B] into each of the projectors what the actual input value to the system should be. For example, consider a projector that was deemed by the difference metric to be displaying more red than the other displays in the system. Given an input value of [100 10 10], a corresponding color transfer function that may improve the color alignment of the display may map that color to a value with less red, for example, oi(100, 10, 10)=[90 10 10].
The goal of the computing a corrective step is to modify the operating mode vector O for an observed error e so that the expected error at the next measurement will be reduced. This entails modifying the underlying color transfer functions in an intelligent manner that will yield a more similar observed color across all displays. This can be accomplished through a variety of methods include gradient descent techniques or more sophisticated iterative search methods including Levenberg-Marquardt optimization or covariance analysis.
In an exemplary embodiment, the present system employs a modified gradient descent optimization approach. The system iteratively modifies display input (RGB) values, and measures the corresponding output value as observed by a sensor. The observed value is compared to a target value, and a correction factor is computed. In traditional gradient descent techniques the correction value is based on derivative information computed from previous iterations (numerical derivative). External (previously measured) knowledge about the global projector response function may be used to provide derivative information, which is in turn used to compute the next input value. Using this external data is helpful to avoid local gradient instability due to measurement error ('noise) that is inherent to the sensor feedback step.
At step 225 , either the entire vector O is updated or some subset of color transfer functions are modified. In an exemplary embodiment, only a single transfer function is updated (i.e., a single display's color space is modified) until that display converges. In any case, this stage produces a new value for vector O that describes a new color response behavior for the entire display system.
Applying the Correction
Once a set of color transfer functions have been derived for the projector set, optimization module 102 informs display controller 103 of the modified color transfer functions so that each of the displays can now take into account its own color transfer function when colors are displayed, at step 230 . The color transfer function can be implemented in hardware as a transform that is applied directly on the projector, in video processing hardware that modifies the video signal, or in software, as the colors used to drive the projector are being derived.
Once stored, these new functions modify the behavior of the displayed image so that subsequent measurements can observe the changes effected by the new transfer function. This process is iteratively performed until the system converges.
Convergence
The process of measuring a display (block 201 ), deriving an error metric, determining how to modify the color transfer functions of the display, and then applying that modification continues until the system converges at step 217 . At convergence, either the error metric is within a predetermined tolerable level or some other convergence property has been reached. For example, a system is considered to have converged if the measured error is within the error tolerance for the sensing device. If the error has not improved over some number of iterations, or the number of iterations is simply too large, the process is terminated.
Once converged, the color transfer functions for the last iteration are now the set of functions that are applied to each of the displays in order to bring them into color alignment.
The above description of certain embodiments of the invention is not intended to be exhaustive or to limit the invention to the precise forms disclosed. The terms used in the claims should not be construed to limit the invention to the specific embodiments disclosed in the specification, rather, the scope of the invention is to be determined by the following claims.
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A system for automatic color matching of multiple displays in a multi-display system. A sensor observes the output energy of each of the displays in a multi-display system and measures the difference in the color responses for a given input color. This difference is used to derive a modification function that is applied to each display. The displays are modified accordingly, and then the color is displayed again. This process is repeated until the measured values from each of the displays are within a minimum measurement error tolerance, so that the differences in displayed colors observed among the displays are minimized.
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This invention relates to a composition for and process of treating sheet steel, and more particularly to a composition for and process of treating sheet steel with a buffered chelating agent.
BACKGROUND OF THE INVENTION
A special steel widely used in many of the industries is sheet steel. Sheet steel is used in automobiles, appliances, and similar goods. It is manufactured in primary mills. Also scrap steel from vehicles, refrigerators and other sources is used in secondary mills with additional iron ore and coke to form more steel, including sheet steel.
It is a problem, especially in the primary mills, to produce a sheet steel free and clear of corrosion and stain. Customers are more and more demanding in that they desire efficiently produced, and clean sheet steel. This combination of requirements is extremely difficult to obtain. In the processing of sheet steel, any delay or slow down results in stain or other undesirable material being formed on the sheet steel.
It is an uneconomical and an inefficient use of resources to simply discard this steel or to forward it for reprocessing as has been done in the past. It is very desirable to process the steel and avoid the stain in the first place. Such a procedure for treating sheet steel is extremely difficult to carry out. Yet, in this process, difficulty is caused by the high speed processing and the reduced time for achieving these desired results. It is very desirable to develop a process for removing the stain from sheet steel during the course of manufacturing in a simplified efficient fashion.
Such a simplified, efficient process of removing stain from sheet steel is difficult to obtain. While many compositions are known to remove the stain from steel in other forms, it is extremely difficult to apply the compositions and remove the stain from sheet steel at high speed.
By achieving such removal at high speed, inefficiencies can result. Where such stain removal is achieved by the process of the prior art, it is done at a slower pace or with environmentally hazardous materials. It is very desirable to achieve this stain removal quickly, yet in an environmentally efficient fashion and avoid such stain reforming on the sheet steel. It is further desirable that the waste therefrom be environmentally neutral and easily disposable. Accordingly, if the development of a process or composition to accomplish these goals is achieved, great advantages are obtained both for environmental needs and other societal needs.
Hot rolled sheet steel processed on high speed coil lines (FIG. 1), when pickled with hydrochloric acid suffers from iron and chloride staining. Hot rolled sheet steel must be pickled to remove the scale that is formed during the hot rolling process. The scale is an oxide that is predominantly ferric oxide. However, the stains occur after the pickling tanks used in this sheet steel process, and in the subsequent rinse sections during line stops where residual iron and chloride ions react with and precipitate onto the sheet steel.
The composition of the stain varies with its proximity to the pickle tanks. Predominantly the stain comprises of ferrous and ferric hydroxides. There are also ferrous and ferric chlorides present. The percentage of ferrous and ferric chlorides present in the stain gradually increases as the stain nears the pickle section. While in the past, primary producers of sheet steel did not find these stains detrimental, these stains are now a major problem.
An increasing percentage of the hot rolled sheet steel is designated for commercial use. The commercial hot rolled sheet steel, which is stained, is usually sent to a service pickling company. This service company buys and pickles the hot rolled sheet steel before it is sold to the end users.
The service pickler buys the stained coils at a discounted price. Then, in turn, that service pickler sells the repickled coils at commercial prices. The service pickler does not experience the "staining" problem to the extent of the primary producer, because the service pickler runs the line at substantially lower line speeds.
The pricing differential between the primary producer's discounted price and the service pickler's commercial price causes the impetus for the primary producer to compete in this market. The widening price differential is greatly due to increases in costs of transporting and reprocessing of the stained coils. The primary producers need to find another way to produce this portion of the commerical grade hot rolled sheet steel within their own production facilities. Current technology does not allow for maximum capacity to produce a commercial grade hot rolled sheet steel. Producers must slow the high speed coil lines down from about 400 meters per minute to about 60 meters per minute to prevent the line stops, which create staining.
The line stops occur due to welding and cutting operations. The high speed coil lines are continuous coil lines. At the beginning of the process, the sheet steel coils are welded to the previous coil. At the end of the process, the steel coils are cut from the continuous steel strip. The high speed coil lines have sections to take up coil so that during welding and cutting operations there is enough sheet steel in the system to keep the strip moving through the pickling and rinse sections and to prevent stops. However at speeds of about 400 meters per minute there is not enough accumulated coil to prevent a line stop.
The user of proprietary chemicals attempts to minimize staining of the sheet steel. Chelating chemicals can form soluble complexes with iron ions in the rinse water, thus preventing the formation of iron precipitates. When the rinse water dilutes the residual acid film after pickling and its pH rises to about pH 6.0, hydrated iron oxides precipitate on the ferrous surface of the sheet steel. Wetting agents can aid in the removal of acid residues and minimize hydrochloric acid pickle carry over due to the wetting agents effect to produce thinner surface films on the sheet steel. The thinner films will contain less iron and chloride ions, which in turn reduces the extent of the stain formed during line stops.
The efficiency of the stain removing chemicals are directly related to rinsing techniques. Residual chloride ions contribute to the formation of the stain. The chloride ions are present due to the hydrochloric acid carry over. Rinsing is of major importance in order to remove these residual chloride ions. The rinsability of chloride ions are achieved by the method of rinsing (spray, immersion, or a combination of both), spray pressure and flow, and spray pattern Also, the use of squeegee rolls and their placement are critical for better rinsing. All of these rinsing techniques for high speed coil lines effect chloride removal. However, none of these techniques are completely effective at removing all of the chloride ions that help to create the stain.
Formulations designed to prevent iron and chloride staining are not effective due to pickle line configurations. This is especially true in areas of the pickle line before and after the squeegees, and the inaccessible areas of the sheet steel, which cannot be rinsed because of their proximity to the pickle tanks.
Known in the art is a method of removing iron- and copper- containing scale from the interior metal surface of a boiler utilizing an admixture of polycarboxylic acids and phosphonic acids and their salts thereof. Scale is also removed from steam boilers, petrochemical process equipment, feedwater heaters and associated piping, and in various types of pressure vessels, such as high pressure steam generating equipment utilized in electric power generation and other applications, in which water is circulated and heat transfer occurs. These metallic surfaces are internal parts of process equipment. Such treatments are used to restore the efficiency of the process equipment by removing the scale, as a maintenance procedure.
The characteristics of stain and scale also differ with regard to composition and creation Stain is the steel industry's jargon for hydrated ferrous and ferric oxides, and ferrous and ferric chlorides. The scale may also include cuprous and cupric oxides, and water-soluble salts such as calcium carbonate, calcium hydroxide.
The stain is produced on sheet steel in a relatively short time (less than 15 minutes) when the hydrochloric acid pickle line stops. During line stops the stain is formed from residual ferrous and ferric chlorides that remain on the sheet steel surface after hydrochloric acid pickling. When the rinse water dilutes the residual acid film left on the surface, and its pH rises to about pH 6.0, hydrated iron oxides can form and can be left on the surface as an insoluble precipitate. This flash rusting or staining may occur especially in the first rinse stage at low line speeds, or if the sheet steel dries out during line stops.
The formation of scale is only similar to the formation of stain in so much that both are formed due to the phenomenon of insolubility, such as is described in U.S. Pat. No. 4,666,528, incorporated herein by reference. The primary reason for scale formation is the fact that the solubilities of the scale-forming salts decrease with increases in temperature and concentrations. When feedwater is elevated to boiler water temperature and concentrations, the solubility of the scale forming salts is exceeded. Scale forms by one or a combination of the following mechanisms.
1) The improper precipitation of relatively insoluble feedwater hardness compounds (for example, calcium carbonate precipitating at the metal surface by the following possible mechanism):
2 Ca(HCO.sub.3).sub.2 +Heat, yields,
2 CaCO.sub.3 +2 H.sub.2 O+2 CO.sub.2.
2) The supersaturation, or crystallization, of relatively soluble dissolved solids (CaSO 4 ,SiO 2 ) in water contacting heat transfer surfaces. This undesired coating on the sheet steel is usually a mixture of calcium sulfate and silicon dioxide (CaSO 4 ,SiO 2 ).
3) The accumulation of corrosion products (iron and copper oxides) or other suspended matter in the feedwater with subsequent deposition on the high heat transfer metal surfaces.
This complex or group of complexes is very stable. Such stability makes it hard to dissolve or otherwise remove the complexes as desired.
SUMMARY OF THE INVENTION
Accordingly among the many objectives of the present invention is to provide an improved composition for and process of removing stain or scale from sheet steel with a substantially, environmentally acceptable composition.
It is a further objective of this invention to provide an improved process of removing stain from sheet steel quickly.
A still further objective of this invention is to reduce customer rejection of sheet steel.
Yet a further objective of this invention is to provide a process of improving efficiency at a primary mill.
Also an objective of this invention is to provide a process of removing iron and chloride containing stains from the hot rolled sheet steel.
Another objective of this invention is to provide a process of avoiding a rinse stain on sheet steel.
Yet another objective of this invention is to avoid extra transportation in sheet steel manufacturing.
Still another objective of this invention is to provide a process for reducing stains in the manufacture of sheet steel.
It is a further objective of this invention to provide an improved process of maintaining the solubility of the iron ion to prevent redeposition of the stain.
A still further objective of this invention is to remove the stain without interfering with the overall quality of the ferrous substrate.
Yet a further objective of this invention to provide an improved composition for removing stain from sheet steel quickly.
These and other objectives of the invention (which other objectives become completely clear by considering the specifications, claims and drawings as a whole) are met by providing a solution of buffered chelating agent and applying the same to the sheet steel during processing and prior to coiling.
BRIEF DESCRIPTION OF DRAWINGS
FIGS. 1A, 1B, and 1C combine to depict a block diagram of sheet steel forming apparatus 100 usable with a destaining apparatus 120 of this invention.
FIG. 2 depicts a perspective view of destaining apparatus 190 of this invention, using a spray tank 200.
FIG. 3 depicts a perspective view of destaining apparatus 190 of this invention, using a dip tank 270.
FIG. 4 depicts a perspective view of destaining apparatus 190 of this invention, using a spray tank 200 and a dip tank 270 in combination.
FIG. 5 depicts a top, plan view of destaining apparatus 190 of this invention, using a spray tank 200 and a dip tank 270 in combination.
Throughout the figures of the drawings, where the same part appears in more than one figure, the same number is applied thereto.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Iron and chloride containing stains are removed from the hot rolled sheet steel. By treating the sheet steel with a buffered chelating agent to remove the stain, once removed, the chelating agent maintains the solubility of the iron ion to prevent redeposition of the stain on the sheet steel. This method and composition removes the stain (destaining) without interfering with the overall quality of the ferrous substrate or sheet steel.
The waste from this method is generally considered environmentally neutral. In the areas that regulate phosphorous for environmental reasons, a known method of treatment can be applied to remove the phosphorous used in the treatment of this invention from the rinse water in a simple fashion.
Polyphosphonic acid, or the alkali metal or amine salt or the ammonium salt of this acid is used to remove copper and iron-containing scale from a ferrous metal surface, especially sheet steel, provided a long contact time is used. Also, a method of removing iron and copper containing scale from a metal surface by contacting the scale with a composition of an admixture of an aminopolycarboxylic acid, such as ethylenediaminetetraacetic acid (EDTA), or the alkali metal salts or ammonium salts or amine salts of the polycarboxylic acid and a polyphosphonic acid such as aminotrimethylenephosphonic acid (ATMP),or an alkali metal salt or amine salt or ammonium salt of the phosphonic acid is now usable, provided, a long contact time is used.
It is the custom of the intended industry, steel producers, to refer to the ferrous and ferric chlorides and the hydrated ferrous and ferric oxides as a "stain." This invention describes a method of and composition for removing iron oxide and chloride stain from a ferrous metal surface by contacting the stain with a composition of one or more components selected from the group consisting of a phosphonic acid or salt thereof, a polyphosphonic acid or salt thereof, and a polycarboxylic acid or salt thereof.
The key factor in removing the undesired stains and simplifying the manufacture of substantially stain-free sheet steel is clearly the buffered chelating agent of this invention. This method of treatment with a composition of this invention improves the appearance of the sheet steel and avoids the problems inherent in sheet steel having stains thereon.
An acid used herein to remove such stains is a phosphonic acid such as 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). Salts thereof, which are suitable, include an alkali metal salt, an amine salt, an ammonium salt or combinations thereof. Also useful is a polycarboxylic acid such as nitrilotriacetic acid (NTA). Salts thereof, which are suitable, include an alkali metal salt, an amine salt, an ammonium salt or combinations thereof.
Referring now to FIG. 1, a standard steel-making apparatus 90 is shown in block diagram form. Limestone 100, iron ore 102, and coke 104 is deposited in blast furnace 106. Slag 108 is taken out of blast furnace 106 and discarded. Molten pig iron 110 is taken from the blast furnace 106 and placed in the oxygen furnace 112.
Also added to the oxygen furnace is lime 114 and other metals 116. In this fashion, molten steel 118 is formed. The molten steel can be divided into two classes, ingots 120 and continuous casting 122. The ingots 120 proceed on to the rolling mill 124 then to the steel slab 126. The steel slab 126 is split into casting 128, billitting 130, and skelping 132. Casting 128 goes into commercial uses such as engine blocks and crankshafts 134. Forging goes into commercial girders and rails 136. Skelping goes to rolling then to commercial tubes 140. Continuous casting 122 can also lead to steel slab 126.
This steel slab 126, as one option, is taken to a continuous strip mill 150 where the slab 126 is treated to hot rolling 152 to form a sheet 262 (shown in FIG. 2) and then pickling 154. After pickling, the sheet 262 may undergo cold reduction 160 and then galvanizing 162 and followed by forming coils in commercial 164. The cold reduced sheet steel 262 may also go directly to commercial 164. The cold reduced sheet steel 262 may also undergo tinning 168.
After pickling 154, sheet steel 262 may also undergo annealing 170 and go to commercials 164. It is after the pickling 154, that the treatment destaining apparatus 190 of this invention is required to remove the stains off the sheet steel 262.
The destaining apparatus 190 is plugged into FIG. 1 and the steel making apparatus 100, after the pickling step 154. The sheet steel 262 may be cleaned or otherwise relieved of scale or stain. The destaining apparatus 190 may use a spray tank 200, an immersion tank 270, or both a spray tank 200 and an immersion tank 270 together in any order.
In FIG. 2, a spray tank 200 includes a set of upper nozzles 204 and a set of lower nozzles 216. The upper nozzles 204 include a first upper nozzle 206 a second upper nozzle 208 and a third upper nozzle 210. The upper nozzles 204 are mounted by appropriate pipes over the sheet steel 262. Below the sheet steel 262 and within the spray tank 200 are the lower nozzles 216. There is a first lower nozzle 218, a second lower nozzle 220 and a third lower nozzle 222.
The nozzles are fed from a supply tank 230 by the pump 232 through the connecting pipe 234. The supply pipe 236 feeds from the supply tank 230 into the pump 238. The feed pipe 242 handles the feed of the destaining composition from connecting pipe 234 to the nozzles.
The feed of the upper nozzles 204 is handled by the upper pipes 222. In this fashion, the sheet steel 262 can be sprayed from upper nozzles 204 and lower nozzles 216. The spray tank 200 catches the sprayed material and recirculates to the supply tank 230.
The feed of the lower nozzles 216 is handled by the lower pipes 242. In this fashion, the sheet steel 262 can be sprayed from upper nozzles 204 and lower nozzles 216. The spray tank 200 catches the sprayed material and recirculates to the supply tank 230.
The spray tank 200 is fed by an entrance roller 250 over which the sheet steel 262 passes. A feed roller 252 is centrally located in the spray tank 200 and receives the sheet steel 262 so that the sheet steel 262 may be fully exposed to all nozzles. An exit roller 254 feeds the sheet steel 262 to the next tank or treatment process.
Referring now to FIG. 3, the immersion tank 270 has an immersion feed roller 272 an exit feed roller 274. Situated therebetween is a first coil support roller 280 and a second coil support roller 282 in order to force the sheet steel 262 into the immersion tank 270 to be completely submerged into the desired stain or scale removing agent. The immersion tank 270 is of course deep enough so that the sheet steel 262 is successfully immersed therein to achieve the desired stain removing or scale removing.
In FIG. 4 and FIG. 5, the combination of the spray tank 200 and immersion tank 270 is shown. The tanks are combined whereby the immersion tank feed roller 272 serves a dual function of being the exit roller 254 for the spray tank 200. In this fashion, the sheet steel 262 can receive both treatments. This structure is especially suitable for treating the heavy duty stains on sheet steel 262.
In this fashion, the cleaning material is used efficiently and effectively. Both the spray tank 200 and the immersion tank 270 can be of any suitable size as desired. Generally speaking, it is preferred that the spray tank 200 have a capacity of about 500 cubic meters. It is preferred that the immersion tank 270 have a capacity of about 1000 cubic meters.
The current invention discloses a method of removing iron oxides and iron chlorides from a ferrous metal surface. The ferrous metal surface is sheet steel 262 that has been pickled, fresh water rinsed with the water alone, fresh water rinsed with an aqueous solution of an admixture of phosphonic acids and polycarboxylic acids and their salts thereof, dried, oiled and recoiled. The metal surface in this instance is a product of the steel making process. This invention is a product of the steel making process. This invention provides a treatment for the sheet steel 262 that subsequently produces sheet steel 262 with better quality, more quickly, and more efficiently, therefore in a more profitable manner.
This invention is used to remove the stain with an aqueous stain removing composition having a pH from about 4.0 to about 10.5 contacting the stain at temperatures of about 75° C. to about 105° C. Complete stain removal occurs with these parameters in about 5 seconds to maximum of 2 minutes. The time to remove scale and stain is the fundamental difference in the operating processes.
Basically, it is desired that the pickling solution be in the 6 to 9 pH range. It is generally a buffered phosphonate. With the buffered phosphonate and treatment of the steel for 25 to 45 seconds at 80° C. to 95° C. at a desired concentration of up to 10 grams per liter of chelating agent, tremendous results are obtained in removing the steel and making the sheet steel 262 stain-free. An especially preferred phosphonate is one 1-hydroxyethylidene-1,1-diphosphonic acid. Salts of that acid include the potassium salt, the sodium salt, the ammonium salt, the triethenolamine salt, the diethanolamine salt and the monoethanolamine salt. In this fashion, the appropriate chelating agent can be used.
Specifically the other salts desired are an ethylenediaminetetraacetic acid (EDTA) salt, a citrate, a gluconate, or a phosphonate. These compositions are applied to the sheet steel 262 by combination of spray and immersion process, or a separate spray process or a separate immersion process to achieve the desired results.
The buffering agent can be potassium hydroxide, sodium hydroxide, ammonium hydroxide, triethanolamine, monoethanolamine, and diethanolamine. The concentration of the chelating agent can vary from a concentration of 1 gram per liter to 100 grams per liter. More preferably the concentration of chelating agent is 5 grams per liter to 50 grams per liter. Most preferably, concentration of the chelating agent is 10 grams per liter to 25 grams per liter.
Preferably, the pH is adjusted to a range of 6 to 9. More preferably, the pH is adjusted to a range of 6.5 to 8. Most preferably, the pH is adjusted to 6.6 to 7.5.
Preferably, the treatment temperature is in the range of 65° to 110° Centigrade. More preferably, the treatment temperature is in the range of 75° to 105° Centigrade. Most preferably, the treatment temperature is in the range of 75° to 95° Centigrade.
If an immersion procedure is used, the immersion time of the sheet steel is 5 to 90 seconds. More preferably, the immersion time of any stained section of sheet steel is 15 to 80 seconds. Most preferably, the immersion time of the sheet steel is 25 to 70 seconds.
If the buffered chelating agent is applied by a spray, the preferable spray time is 5 seconds to 60 seconds. More preferably, the spray time is 10 seconds to 45 seconds. Most preferably, the spray time is approximately 10 to 30 seconds.
The length of the spray section, or immersion rinse tank sections is a constraint. After a line stop, the coil drive units are programmed to run at a reduced speed for a limited time before returning to normal operating speed. The speed and time limitations are a function of the rinse section's length. That is the duration of reduced line speed is determined by the length of the rinse section.
In the following examples, which are intended to illustrate without unduly limiting the invention, all parts and percentages are by weight unless otherwise specified.
EXAMPLE 1
A pickle line for sheet steel is modified to include a tank containing a liquid being set up. Into the tank is placed a 40,000 liter water solution of a 1-hydroxyethylidene-1,1-diphosphonic acid having a concentration of ten grams per liter. The solution is buffered to a pH of 8.4 with potassium hydroxide. Sheet steel having a stain of ferrous and ferric chlorides and oxides is passed therethrough. The stain is sufficient to otherwise have the sheet diverted. The tank is heated to a temperature of 90° Centigrade. After a line stop, the sheet of steel is passed through the rinse tank at a temporary line speed of 23 meters per minute, before returning to a standard line speed of 320 meters per minute.
The tank is of sufficient size to permit a section of sheet to remain therein 40 seconds. The tank is about 15 meters long, and wide and deep enough to receive the sheet steel. Upon removal of the sheet steel from the tank, the stain no longer exists.
EXAMPLE 2
A series of tests are conducted to demonstrate the iron oxide dissolving capability of this invention. The chemical compositions utilized have a pH of about 8.5 and comprised of a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) as the phosphonic acid and potassium hydroxide as the alkali metal hydroxide, which is used to buffer the compound.
The first part of this example involves a test for determining the effectiveness of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) in dissolving iron oxide at a pH of 8.5, comparing HEDP against citric acid, gluconic acid, and ethylenediaminetetraacetate, tetrasodium salt, tetrahydrate (EDTA-Na 4 ).
______________________________________ Citric HEDP acid Gluconic acid EDTA--Na.sub.4______________________________________gram/liter 30 30 60 60chelantppm Fe (5) 1800 51 52 49dissolved 1800______________________________________
where
HEDP is 60% active acid;
citric acid is 100% active acid;
gluconic acid is 50% active acid;
EDTA-Na 4 is 40% solids; and
ppm means parts per million
ppm Fe determined by atomic
emission spectroscopy.
The test itself consisted of bubbling nitrogen gas into a solution containing 7.5 grams per liter Fe 3 O 4 (5420 ppm Fe) and 5 grams/liter of ammonium bifluoride at 60° C. for 12 hours. The pH of these solutions is adjusted to pH 8.5 using potassium hydroxide, 45% liquid.
The optimum iron oxide dissolving ability of HEDP is at pH 3.5.The dissolving efficiency decreases gradually through pH 8.5 and falls off very steeply at pH 10.5. In contrast the optimum iron oxide dissolving ability for citric acid falls at pH 5.0 and drops off very rapidly at pH 7.0. The iron oxide dissolving capability of gluconic acid at a pH range from 5.0 to 12.5 is very poor when compared to HEDP and citric acid.
HEDP is considerably more effective at pH 8.5 than citric acid, gluconic acid, and EDTA-Na 4 . The data indicates that increasing the concentration of either citric acid and gluconic acid would not make them comparable to HEDP.
The next table shows the effect of pH on dissolving iron oxide by various chelants. The various chelants for this example are (1) HEDP, (2) Citric Acid, (3) Gluconic Acid, (4) Citric Acid and HEDP mixture, (5) Gluconic Acid and HEDP mixture.
______________________________________gram/liter (1) (2) (3) (4) (5)chelant 30 30 60 15/15 15/30______________________________________ ppm Fe dissolvedat pH 3.5 4800 2100 -- -- --at pH 5.0 3800 4600 490 3900 1800at pH 7.0 2000 164 -- -- --at pH 8.5 1800 51 52 1200 1500at pH 10.5 36 10 8 15 35at pH 12.5 24 -- 13 -- 11______________________________________
The test itself is conducted by bubbling nitrogen gas into a solution containing 7.5 grams/liter Fe 3 O 4 , (5420 parts per million Fe) and 5 grams/liter ammonium bifluoride at 60° C. (140° F.) for 12 hours. The pH of the solutions tested are adjusted with potassium hydroxide, 45% liquid, when necessary. The ppm of iron determination is done using atomic emission spectroscopy.
HEDP dissolves iron oxide much faster at pH 3.5 than citric acid. The maximum dissolution rate for HEDP, under conditions examined in this study, is achieved at pH 3.5. The rate of dissolution of iron oxide slows as the pH is increased.
The next table shows the effect of time on dissolving iron oxide by chelants.
______________________________________ HEDP Citric Acid______________________________________gram/liter 30 30chelantDissolving 1 2 3 1 2 3time (hours)ppm Fe 4200 4800 4700 1900 2200 2900Dissolved______________________________________
Again, the test is conducted by bubbling nitrogen gas into a solution containing 7.5 grams/liter Fe 3 O 4 (5240 ppm Fe) and 5 g/l ammonium bifluoride. The test is conducted at 60° C., and the pH values for both the HEDP and citric acid solutions are 3.5 where:
HEDP is 60% active acid;
citric acid is 100% active acid; and
Fe is determined by atomic emission spectroscopy.
In general, iron oxides are dissolved by chelants most effectively at pH values between 3.0 and 7.0. The solubility of the oxides in chelant solutions drops off very rapidly at a pH above 7.0. A blend of HEDP, and trisodium nitrilotriacetate (NTA) is also better than either of the two used alone. However, it is not as effective as the three component blend. The HEDP/NTA/citric acid blend dissolves the iron oxide in a single step within a pH range from 3.0 to 7.0 very effectively. The HEDP alone passivates the base metal (sheet steel) during the iron oxide dissolving step and helps to prevent the base metal's corrosion.
The following table shows the ability to dissolve iron oxide by using chelants in a tap water solution.
______________________________________ Grams/liter percent iron oxide dissolved at pH:Chelant type Chelant 3 5 7______________________________________HEDP 22.5 92 84 16Citric acid 77.0 89 79 8NTA 64.0 ppt. 73 50Blend 1 46.5 97 86 70Blend 2 32.6 87 88 60______________________________________
The water source used is from St. Louis County, which is considered to be in a hard water area. Again, nitrogen gas is bubbled through each solution and the temperature is 77° C. The test is conducted for 4 hours. Each solution started with 1.40 grams/liter of Fe 3 O 4 , which has 1012 ppm Fe. The percent iron dissolved is determined first by using atomic absorption spectroscopy to find out how much free iron is left in solution, then determining the percentage iron oxide that is dissolved. The pH of the solutions is adjusted with potassium hydroxide, 45% liquid, when necessary.
Blend 1 consists of the following: 11.3 grams per liter HEDP, 19.2 grams per liter citric acid, and 16.0 grams per liter NTA.
Blend 2 consists of the following: 16.8 grams per liter HEDP, and 16.0 grams per liter NTA.
EXAMPLE 3
A second series of tests are conducted to demonstrate the ability of this chemical solution to dissolve iron and chloride stains on a hot rolled steel sheet. The chemical composition utilized had a pH of 8.5 and comprised of a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), as the phosphonic acid and potassium hydroxide as the alkaline metal hydroxide, which is used to buffer this composition. The test is conducted in a standard fashion on a steel coupon, the steel coupon being a small piece of sheet steel used for testing.
A 1:1.16 ratio of HEDP/KOH, 45% liquid is tested with 1% w/w of active HEDP. Hot rolled steel coupons are pickled in a hydrochloric acid pickling bath for 3 minutes at 82° C. (180° F.) in order to remove the oxide layer on the surface of the coupon. The coupons are then rinsed in tap water (Mundelein, Ill.) and left to air dry for 3, 5, and 10 minutes respectively. During these time intervals, the iron and chloride stains are formed. After the stain had formed for the given time frame, the hot rolled steel coupons are immersed in the chemical solution for 35 seconds. The temperature of the chemical solution is 82° C. (180° F.) The results of the tests are as follows:
3 minute stain: Completely removed;
5 minute stain: Completely removed;
10 minute stain: Completely removed.
The definition of "Completely removed" is a term that can be understood as when the colored stain (greenish/gold for this particular lab experiment) that is formed on the hot rolled steel coupons during the 3, 5 and 10 minute intervals is removed or dissolved off of the surface of the coupons (sample pieces of sheet steel).
EXAMPLE 4
A third series of tests are conducted to demonstrate the stain removing capibility of the chemical solution used in Example 3 in a spray system. This test involved using the same chemical solution at different pH values. The procedure for forming the stain is identical to the procedure in Example 3, but the only time frame that is used for this test is the 10 minute interval. The 10 minute interval is considered to be the most severe case in terms of stain formation. The results of the spray testing is as follows:
______________________________________pH Values Results______________________________________6.1-6.2 The stain is completely removed.7.1-7.2 Approximately 80-90% of the stain remained on the surface of the coupon.8.2-8.3 Approximately 90-95% of the stain remained on the surface of the coupon.______________________________________
These spray tests are conducted at 66° C. for 7-8 seconds at a spray pressure of 10-12 psi.
The results indicate that, by lowering the pH value of the HEDP/KOH mixture, it is possible to remove the stain that is produced during the 10 minute interval.
EXAMPLE: 5
This series of tests are conducted to demonstrate the iron oxide dissolving/removing capability of another process of this invention. The chemical compositions utilized are comprised of a mixture of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP) as the phosphonic acid, and various alkaline materials which are used to neutralize the chemical composition.
Solutions containing 1% w/w of active HEDP are prepared and neutralized to a pH of about 8.5 using various alkaline materials. These solutions are heated to 85° Centigrade (185° F. ) for this test. Again, hot rolled steel coupons are processed in order to produce an objectionable stain (see Example 3). The 10 minute stain is used for this particular example because it is the most severe case. The results of the testing are as follows:
______________________________________Item Grams per Liter______________________________________#1) Water, cold 978.5 HEDP, 60% Liquid 10.0 Potassium Hydroxide, 45% liquid 11.5 1,000.0 pH = 8.2 30 second immersion______________________________________
Result: The stain is completely removed from the surface of the coupon. By "coupon" is meant a sample of sheet steel.
______________________________________Item Grams per Liter______________________________________#2) Water, cold 982.7 HEDP, 60% Liquid 10.0 Sodium Hydroxide, 50% liquid 7.3 1,000.0 pH = 8.3 30 second immersion______________________________________
Result: The stain is completely removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#3) Water, cold 983.2 HEDP, 60% Liquid 10.0 Ammonium Hydroxide, 26° Be 6.8 1,000.0 pH = 8.1 30 second immersion______________________________________
Result: The stain is completely removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#4) Water, cold 965.0 HEDP, 60% Liquid 10.0 Triethanolamine, 99% liquid 25.0 1,000.0 pH = 8.4 30 second immersion______________________________________
Result: 90% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#5) Water, cold 979.5 HEDP, 60% Liquid 10.0 Diethanolamine, Liquid 10.5 1,000.0 pH = 8.3 30 second immersion______________________________________
Result: 90% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#6) Water, cold 984.0 HEDP, 60% Liquid 10.0 Monoethanolamine, Liquid 6.0 1,000.0 pH = 8.2 30 second immersion______________________________________
Result: 95% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#7) Water, cold 975.9 HEDP, 60% Liquid 10.0 Lithium Hydroxide, monohydrate 14.1 1,000.0 pH = 8.5 30 second immersion______________________________________
Result: The stain is completely removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#8) Water, cold 980.0 HEDP, 60% Liquid 10.0 Sodium Carbonate, Natural 10.0 1,000.0 pH = 8.5 30 second immersion______________________________________
Result: 80% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#9) Water, cold 971.5 HEDP, 60% Liquid 10.0 Tetrapotassium Pyrophosphate 18.5 1,000.0 pH = 8.1 30 second immersion______________________________________
Result: 70% of the stain is removed from the surface of the coupon.
______________________________________ Item Grams per Liter______________________________________#10) Water, cold 981.0 HEDP, 60% Liquid 10.0 N,N-Diethylethanolamine 9.0 1,000.0 pH = 8.2 30 second immersion______________________________________
Result: 75% of the stain is removed from the surface of the coupon.
Materials that will also work well other than the alkali metal hydroxides, alkali metal carbonates and alkali metal phosphates and alkaline amines are alkaline metal silicates and borates, alkaline organic compounds and most any non-chloride, non-cyanide alkaline materials.
EXAMPLE: 6
This series of tests are conducted to demonstrate the iron oxide dissolving/removing capability of another chelant for this invention. The chemical compositions utilized comprised of a mixture of citric acid as the chelating agent and potassium hydroxide, 45% liquid, as the alkali metal hydroxide, which is used to buffer the compound.
Hot rolled steel coupons are pickled in a hydrochloric acid pickling bath for 3 minutes at 88° C. (190° F. ) in order to remove the scale/oxide layer on the surface of the coupon. The coupons are then rinsed in tap water (Mundelein, Illinois) and left to air dry for 10 minutes. During this time, an objectionable stain is formed, which consists of iron oxides and residual chlorides. After 10 minutes, the hot rolled steel coupons are immersed in the chemical solution for approximately 30 seconds. The temperature of the solution is 85° C. (185° F.), and the pH values are varied to determine at which range this chemical composition can work best. The results are as follows:
______________________________________Item Grams per Liter______________________________________#1) Water, cold 976.0 Citric Acid, Granular 10.0 Potassium Hydroxide, 45% 14.0 1,000.0______________________________________
Result: The stain is completely removed from the coupon in 15 seconds at a pH of 6.0-6.1.
______________________________________Item Grams per Liter______________________________________#2) Water, cold 974.0 Citric Acid, granular 10.0 Potassium Hydroxide, 45% hate 16.0 1,000.0______________________________________
Result: The stain is completely removed from the coupon in 30 seconds at a pH of 7.0-7.1
______________________________________Item Grams per Liter______________________________________#3) Water, cold 971.5 Citric acid, granular 10.0 Potassium Hydroxide, 45% 18.5 1,000.0______________________________________
Result: the stain is completely removed from the coupon in 45 seconds at a pH of 8.5-8.6.
All three tests that are conducted use chemical solutions that contained 1% w/w of citric acid and enough potassium hydroxide, 45% liquid, to raise the pH to the desired value. The results show that the citric acid/potassium hydroxide mixture will remove the stain in a reasonable amount of time. The results also show that this chemical mixture will remove the stain more quickly at lower pH values.
EXAMPLE: 7
This series of tests are conducted to demonstrate the iron oxide dissolving/removing capability of another method of this invention. The chemical compositions utilized comprised of a mixture of ethylenediaminetetraacetate, tetrasodium salt, tetrahydrate (EDTA-Na 4 ) as the chelating agent and various alkaline materials, which are used to neutralize the chemical composition.
Solutions containing 1% w/w of active EDTA-Na 4 are prepared and neutralized to a pH of about 8.5, using various alkaline materials. These solutions are heated to 85° C. (185° F.) for this particular example. Again, hot rolled steel coupons are processed in order to form the objectionable stain (as shown in Example 3). Again, the 10 minute stain is used for this particular test. The results of the testing are as follows:
______________________________________Item Grams per Liter______________________________________#1) Water, cold 977.0 EDTA-Na.sub.4 10.0 Potassium Hydroxide, 45% liquid 13.0 1,000.0 pH = 8.3 30 second immersion______________________________________
Result: The stain is completely removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#2) Water, cold 983.6 EDTA-Na.sub.4 10.0 Monoethanolamine, liquid 6.4 1,000.0 pH = 8.2 30 second immersion______________________________________
Result: 95% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#3) Water, cold 977.8 EDTA-Na.sub.4 10.0 Diethanolamine, liquid 12.2 1,000.0 pH = 8.2 30 second immersion______________________________________
Result: 90% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#4) Water, cold 972.0 EDTA-Na.sub.4 10.0 Triethanolamine 99% liquid 28.0 1,000.0 pH = 8.3 30 second immersion______________________________________
Result: 90% of the stain is removed from the surface of the coupon.
______________________________________Item Grams per Liter______________________________________#5) Water, cold 978.0 EDTA-Na.sub.4 10.0 Sodium Hydroxide, 50% liquid 12.0 1,000.0 pH = 8.5 30 second immersion______________________________________
Result: The stain is completely removed from the surface of the coupon.
The results show that solutions containing 1% active EDTA-Na 4 will remove the stain in a reasonable amount of time. Other materials that can be used to neutralize the EDTA-Na 4 are alkaline metal carbonates, alkali metal phosphates, alkaline metal silicates, borates, and most any non-chloride or non-cyanide containing alkaline material.
EXAMPLE 8
A series of tests are conducted to determine the effect of temperature on stain removal. Hot rolled steel panels are immersed in a 30% v/v solution of 20° Be hydrochloric acid to remove scale formed in the hot rolling process. The panels are subsequently immersion rinsed with clean tap water (Mundelein, Ill.) for 5 seconds and set horizontally for 3,5, and 10 minutes to produce the iron oxide and chloride residual based stain.
The stain removing solutions are made up with 10 grams per liter of 1-hydroxyethylidene-1,1-diphosphonic acid and are adjusted to a pH of about 8.5 using potassium hydroxide, 45% liquid. The solutions are adjusted to various temperatures before immersing the stained panels to evaluate the stain removal. The results are an average of three tests per stain. The results are as follows:
______________________________________StainRemoving Removal Time (Seconds)Temperature/ 3 minute stain/ 5 minute stain/ 10 minute stain______________________________________55° C. 75 108 14160° C. 62 87 11065° C. 49 66 8470° C. 49 49 6375° C. 33 38 4680° C. 26 32 3585° C. 22 29 3290° C. 20 28 3095° C. 19 26 29100° C. 19 25 29______________________________________
The results show that at elevated temperatures it is easier to remove the stain, or that the stain will be removed more quickly.
EXAMPLE 9
A series of tests are carried out to compare the stain dissolving/removing capabilities of various chelating agents at a pH value of 8.5.Hot rolled steel coupons are immersed in a 30% v/v solution of 20° Be hydrochloric acid at 83° C. (180° F.)for 3 minutes, to remove the scale that is formed during the hot rolling process. The coupons are subsequently rinsed in clean tap water (Mundelein, Ill.) in a beaker for approximately 5 seconds and allowed to set horizontally for 5 minutes so that the iron oxide based stain will form.
Various chelating solutions are used to determine their stain dissolving/removing capabilities. All of the stain removing solutions are comprised of 10 grams per liter chelant adjusted to a pH of about 8.5 using potassium hydroxide and heated to 83° C.
______________________________________Chelant System Stain Removing Time______________________________________HEDP 27 secondsEDTA--Na.sub.4 42 secondsCitric Acid 62 secondsNitrilotriacetic Acid (NTA) 34 secondsHEDP/Citric Acid (1:1 ratio) 33 secondsHEDP/EDTA--Na.sub.4 (1:1 ratio) 28 secondsHEDP/NTA (1:1 ratio) 25 secondsEDTA--Na.sub.4 /NTA (1:1 ratio) 36 secondsEDTA--Na.sub.4 /Citric Acid (1:1 ratio) 47 secondsCitric Acid/NTA (1:1 ratio) 51 secondsHEDP/NTA/Citric Acid (1:1:1 ratio) 24 seconds______________________________________
The results indicate that mixtures of various chelants will remove or dissolve the stain in a reasonable amount of time. The results also show that mixtures of these chelants will also remove the stain quicker than if each chelant are 15 used separately.
EXAMPLE 10
Chloride ions will also contribute to the formation of the stain. The chloride ions are present due to the hydrochloric acid pickle carry over. Rinsing is of major importance in order to remove these residual chloride ions. The following table describes the importance of rinsing on different types of sheet steel:
______________________________________Chlorides on surface, mg/ft.sup.2, after ContaminationSteel Type In NaCl Solution 1st Rinse 2nd Rinse______________________________________Mild Steel 89 6.0 5.0Polished Steel 140 2.4 1.2Austentic steel 54 0.5 Less than 0.2______________________________________
The samples are all rinsed by still immersion in distilled water in bench scale tests. Samples had been contaminated by a 15 minute immersion in a one (1%) percent weight/weight (w/w; solute to solvent) solution of sodium chloride. The results show that rinsing is very important for removing the residual chloride ions from the surface of the sheet steel.
Better rinsing is critical for removing the chloride ions from the surface of sheet steel. Mechanical adjustments can be made to a typical high-speed coil line to further improve rinsing. The following table shows the effectiveness of removing chloride residue from sheet steel by modifying the water rinse spraying systems:
______________________________________Effect of modification of spray rinseon chloride residue on sheet steel.*Change made in Chloride on sheet, mg/ft.sup.2Spray rinse Samples tested Average Range______________________________________None 15 0.34 0.22 to 0.78Different spray 10 0.29 0.15 to 0.46pattern (1)Add squeege rolls (2) 13 0.19 0.08 to 0.44Lower spray press. (3) 16 0.12 0.05 to 0.21______________________________________
Changes in the spray pattern combined with lowering the spray pressure to provide flood rinsing contributes to better removal of chloride ion residues.
(1) Different spray pattern includes changing the spray angle of the nozzles. Changing the nozzles from v-jets to flood nozzles to help flood the sheet with water rather than a more direct impingement approach.
(2) A recent study of changes in the spray rinse stages of a continuous pickle line by a eastern producer, showed that the addition of another set of squeegee rolls between the two spray-rinse stages provided a great improvement in rinsing effectiveness.
(3) Lowering the spray pressure from approximately 14.3 kilograms per square centimeter (80 pounds per square inch) to approximately 4.5 kilograms per square centimeter (25 pounds per square inch).
This example is partially based on an article "Pickle Line Rinsing Practice", by L. E. Helwig, consultant, Glenshaw, Pa., which appeared in Iron Age, Apr., 1988.
Modifications to the rinse sections on high speed coil lines will help to improve or reduce the contamination of the surface of the steel sheet. However, none of these modifications are completely effective and some residual chloride will still remain on the steel surface.
The key factor is clearly the buffered chelating agent of this invention. This method of treatment with this composition improves the appearance of the sheet steel and avoids the problems inherent in sheet steel having stains thereon.
This application--taken as a whole with the specification, claims, abstract, and drawings--provides sufficient information for a person having ordinary skill in the art to practice the invention disclosed and claimed herein. Any measures necessary to practice this invention are well within the skill of a person having ordinary skill in this art after that person has made a careful study of this disclosure.
Because of this disclosure and solely because of this disclosure, modification of this method and apparatus can become clear to a person having ordinary skill in this particular art. Such modifications are clearly covered by this disclosure.
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Stain on sheet steel is removed by providing a solution of buffered chelating agent and applying the same to the sheet steel during processing and prior to coiling.
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CROSS RELATED APPLICATION
This application is a divisional of U.S. Non-Provisional Utility application Ser. No. 12/389,020, filed Feb. 19, 2009, and claims the benefit of U.S. Provisional Utility Patent Application 61/032,115, filed Feb. 28, 2008, the entirety of both of these applications are incorporated by reference.
BACKGROUND OF THE INVENTION
The present invention relates to pre-treatment of cellulosic biomass feed stocks, such as agricultural residues (including stalks, stover and hulls), straws and grasses, forest and sawmill residues (including wood chips and shredded thinnings). In particular, the invention relates to pre-hydrolysis and steam explosion pretreatment to extract carbon sugars from the biomass feed stocks.
High pressures and/or high temperatures are typical in pre-treatments used to generate alcohols, e.g. ethanol, from cellulosic feed-stocks. In these conventional pre-treatments, some C5 sugars are converted to components which inhibit the alcohol fermentation of C6 sugars in the fermentation step following pre-treatment. Removing these inhibiting components, such as aldehydes (e.g., HMF, furfural, and formaldehyde), monomeric phenolics (e.g., vanillin and coniferylaldehyde), acids (e.g., formic acid) and other inhibitors should increase the alcohol yield in the C6 fermentation step following pretreatment.
SUMMARY OF THE INVENTION
A system has been developed for pretreating cellulosic biomass feed stock including: a system for pretreating cellulosic biomass feed stock comprising: a first pressurized reactor receiving the feed stock, wherein the feed stock undergoes hydrolysis in the first pressurized reactor; a sealing device having a first pressurized coupling to a feedstock discharge port of the first pressurized reactor, and a second pressurized coupling to a second pressurized reactor; a drain for a liquid including dissolved hemi-cellulosic material extracted from the feed stock in at least one of the first pressurized reactor and the sealing device; the second pressurized reactor assembly receiving the pressurized feed stock from the sealing device at a pressure substantially greater than the pressure in the first pressurized reactor, and an expansion device downstream of the second pressurized reactor assembly, wherein the expansion device rapidly releases the pressure of the feed stock discharged from the second pressurized reactor such that the feed stock undergoes a steam explosion reaction, wherein the first reactor and the second reactor each include a steam phase receiving direct steam heating and reacting or heating the feedstock.
In another embodiment, the system for pretreating cellulosic biomass feed stock may comprise: a first pressurized reactor receiving the feed stock, wherein the feed stock undergoes hydrolysis in the first pressurized reactor at a gauge pressure in a range of 1.5 bar gauge to 6 bar gauge or higher, and at a temperature of at least 110 degrees Celsius; a sealing and extraction device having a first pressurized coupling to a feedstock discharge port of the first pressurized reactor and a second pressurized coupling to a second pressurized reactor; a wash stage introducing a wash liquid into the feed stock in at least one of the first pressurized reactor and the sealing extraction device; a drain for removing a liquid including dissolved hemi-cellulosic material extracted from the feed stock in at least one of the first pressurized reactor and the sealing and extraction device; the second pressurized reactor assembly receiving the pressurized feed stock from the sealing and extraction device and infusing a steam and water vapor into the feed stock in the second pressurized reactor, wherein the reactor assembly applies a gauge pressure to the feed stock in a range of 8 bar gauge to 25.5 bar gauge, and the second pressurized reactor assembly having a pressurized discharge coupled to a discharge conduit, and an expansion device downstream of the second pressurized reactor assembly, wherein the expansion device rapidly releases the pressure of the feed stock discharged from the second pressurized reactor such that the feed stock undergoes a steam explosion reaction.
A method has been developed pretreating cellulosic biomass feed stock comprising: pretreating the feed stock in a first pressurized reactor, wherein the feed stock undergoes hydrolysis in the first pressurized reactor; discharging the feed stock from the first pressurized reactor to a pressurized sealing device having a first pressurized coupling to a feedstock discharge port of the first pressurized reactor; maintaining a vapor phase in the first pressurized reactor by injecting steam into the first pressurized reactor, wherein the injected steam provides heat energy to the feedstock in the first pressurized reactor; washing the feed stock in a downstream region of the first pressurized reactor or the pressurized sealing device; draining a liquid including dissolved hemi-cellulosic material extracted from the feed stock from at least one of the first pressurized reactor and the pressurized sealing device; discharging the feed stock from the pressurized sealing device through a second pressurized coupling to a second pressurized reactor, wherein the feed stock is maintained at a higher pressure in the second pressurized reactor than in the first pressurized reactor; in the second pressurized reactor, infusing cells of the feed stock with steam or water vapor by injecting steam or water vapor into the second pressurized reactor, and rapidly releasing a pressure applied to the feed stock to cause steam expansion in the cells of the feed stock and the feed stock may be refined.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a schematic diagram of a flow through a two reactor process for pre-treatment of cellulosic biomass feed stock.
FIG. 2 depicts a reactor system with an inclined first reactor with an input lower than the discharge and a horizontal second reactor.
FIG. 3 depicts a reactor system with an inclined first reactor with an input higher than the discharge and a horizontal second reactor.
FIG. 4 depicts a reactor system with a conical second reactor.
FIG. 5 depicts a reactor system with a plurality of cyclone separators.
FIG. 6 depicts a reactor system with a plug screw feeder.
FIG. 7 depicts a reactor system with a vertical first reactor.
FIG. 8 depicts an alternative arrangement of a reactor system with a conical second reactor.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a flow sketch of a cellulosic biomass feed stock pre-treatment process 10 having a first pressurized reactor 12 to hydrolyze and dissolve hemi-cellulose from feed stock 14 . The hemi-cellulose is dissolved into a liquid to extract C5-sugars before the feed stock flows to a second pressurized reactor 16 to cook the remaining cellulose in the feed stock. A pressurized seal 18 allows for a continuous flow of pressurized feed stock directly from the first reactor 12 to the second reactor 16 .
The feed stock 14 may be a cellulosic biomass material such as agricultural residues (e.g., stalks, stover and hulls), straws, grasses, and forest and sawmill residues (e.g., wood chips and shredded thinnings). The feed stock 14 is fed to a storage bin 20 where the stock is maintained, at least temporarily, at atmospheric pressure. The storage bin may provide pre-steaming to heat the feed stock. From the storage bin 20 , the feed stock is carried by a conveyor 22 to a pressure sealing device 24 , such as a rotary valve, plug screw feeder or a MSD Impressafiner® sold by Andritz Inc. of Glens Falls, N.Y., USA. The pressure sealing device 24 serves as an input portal for the feed stock to the first pressurized reactor 12 .
In the first pressurized reactor 12 , the cellulosic biomass feed stock is pretreated using hydrolysis, e.g., pre-hydrolysis or auto-hydrolysis, to extract carbon sugars, preferably C5-sugars, from the feed stock prior to the second pressured reactor 16 . The first pressurized reactor may be horizontal, inclined or vertical. The hydrolysis cooking in the first reactor 12 may be a continuous process in which the feed stock continuously enters, flows through and is discharged from the reactor 12 to the pressurized seal 18 and through the second reactor 16 .
In the first pressurized reactor 12 , hemi-cellulose, which is mainly 5-carbon sugars (referred to herein as “C5-sugars”), is dissolved and hydrolyzed. The hemi-cellulose is extracted in a liquid from the first pressurized reactor 12 via a conduit 26 extending from the reactor 12 to a blow down tank or drum 28 .
Hemi-cellulose in soft-woods is mostly gluco-mannan which is dissolved and hydrolyzed in pre-hydrolysis and auto-hydrolysis processes of the first reactor 12 . The hemi-cellulose in, for example, hard-woods, cereal straws and grasses may dissolve and be hydrolyzed in the acid solution in the first reactor 12 (optionally in the presence of catalyst(s)) into low molecular weight C5-sugars, such as xylose and arabinose, and to a certain extent into amorphous C6-sugars. The low molecular weight C5 and amorphous C6 sugars are dissolved in the reactor 12 and drained as a liquor (liquid) from the reactor 12 to pipe 26 . Examples of C5-sugar by-products that are preferably removed as liquor from the feed stock in the first reactor 12 include: aldehydes (HMF, furfural and formaldehyde), monomeric phenolics (vanillin and coniferylaldehyde) and acids (such as acetic acid and formic acid). Removal of these C5-sugar by-products is desirable as they, or their reaction by products, could inhibit the fermentation of C6-sugars if not separated in the first reactor 12 from the feed stock.
In the first pressurized vessel reactor 12 , the feed stock may be processed in an acid solution that promotes pre-hydrolysis or auto-hydrolysis to dissolve and hydrolyze the hemi-cellulose in the feed stock to low molecular weight C5-sugars and amorphous C6-surgars. The reactor 12 may not be filled with feed stock to allow for a steam phase in the reactor. The steam phase provides heat energy for the feed stock and to promote the hydrolysis reaction in the feedstock that may be in either or both of the steam phase or a liquid phase of the reactor. The steam to the reactor 12 may be supplied from a steam source 13 which injects steam directly into the reactor at one or more positions of the reactor 12 , and preferably near the feedstock inlet of the reactor. The steam may also be injected in the feedstock conveyors 22 , 24 immediately upstream of the inlet the reactor 12 . Injection of steam upstream of the inlet to the reactor 12 enhances the mixing of steam and the feedstock before the mixture enters the reactor.
Hydrolysis, and particularly pre-hydrolysis and auto-hydrolysis, generally refers to the cooking of the cellulosic biomass feed stock at temperatures of, for example, between 110 degrees Celsius (° C.) and 160° C. or 110° C. to 175° C. at a gauge pressure of 1.5 bar to 6 bar (150 to 600 kilopascals) or 1.5 bar to 10 bar (150 to 1000 kilopascals), for approximately ten (10) minutes to sixty (60) minutes (min.) and preferably 20 to 30 minutes. To promote hydrolysis and provide pressurization, the first pressurized reactor 12 may receive flows of one or more of a mild acid, sulfur dioxide gas (SO 2 ), oxygen, compressed air, ammonia, water, water vapor, steam (for heating and maintaining temperature) and catalyzing agents from sources 30 , 13 of each of these compounds. The received flow(s) 30 , 13 may be introduced to the first pressurized reactor 12 proximal to where the feedstock enters the reactor and distal from where the feed stock exits the first pressurized vessel. As an alternative to adding acids, the first reactor 12 may utilize auto-hydrolysis conditions such as by using the wood acids released by the feed stock under auto-hydrolysis conditions.
The feedstock may be discharged wet or dry from the first reactor 12 . Dilution water or liquor 32 may be optionally added to the first reactor 12 or to the sealing and extraction device 18 . Adding dilution water benefits the removal of any dissolved substance from the sealing and extraction device 18 , and increases the amount of sugars recovered in the streams flowing through conduits 26 and 48 .
Further, a wash stage 15 may be include in or immediately downstream of the first reactor 12 and upstream of the second reactor 16 and preferably upstream of the sealing and extraction device 18 to wash the feedstock with dilution water to, for example, ensure that the hydrolysis reaction has ceased. For example, the wash stage may be located at the flow end of the first reactor 12 or in the sealing and extraction device 18 . The wash stage 15 introduces clean water, such as from the dilution water source 32 , to the feed stock in a wash zone (see FIG. 7 ) near the outlet of the first reactor or in the sealing and extraction device 18 . The wash water from source 32 may have a temperature of no more than 160 degrees Celsius, no more than 140 degrees Celsius or no more than 110 degrees Celsius. The temperature of the wash water is lower than the temperature in the first reactor 12 to suppress the hydrolysis reaction in the wash zone. The wash zone extracts filtrate 17 from the feed stock through, for example, the drain conduit 48 .
The wash stage should be upstream of the steam explosion process, such as upstream of valve 34 . It is more economical and efficient to wash the feedstock upstream of the steam explosion process than to wash the feedstock after the steam explosion process. The steam explosion process reduces the particle size of the feedstock and thus increases the specific surface area of the feedstock. The small particles and the resulting large specific surface area increase the difficulty of dewatering and washing feedstock. Washing upstream of the steam explosion process avoids these difficulties because the feedstock particles are relatively coarse and have a smaller specific surface prior to steam explosion.
Because washing feedstock with larger particles is more efficient as compared to washing smaller particles, the washing equipment, such as wash zones, water injectors, filtrate screens and extraction devices, may be less cumbersome and less expensive than the wash equipment needed for washing downstream of the steam explosion process. Similarly, the costs associated with washing, such as costs for providing wash liquid and extracting filtrate, is less if the washing step is upstream of the steam explosion process than if the step is downstream of the process.
The blow-tank 28 collects the dissolved components such as C5-sugars from the hemi-cellulose extracted from the feed stock in the first reactor 12 and the sealing and extraction device 18 via pipes (also referred to as conduits) 26 and 48 . The liquid solution of dissolved hemi-cellulose, e.g., C5 sugars, extracted from the reactor 12 may be de-pressurized through a pressure reduction valve 49 in the pipe 48 to the blow-tank or at the discharge of the blow-tank 28 . Having been separated from the feed stock and stored in the tank 28 , the C5-sugars in the hemi-cellulose may be converted by conventional processes to Xylose for use as food additives, biogas by aerobic and anaerobe fermentation, methyl-furan by high octane oxygenate, and to an aqueous sugar for conversion to alcohols, such as ethanol. The conversion of C5-sugars may use special micro-organisms, e.g., enzymes, to promote the conversion reaction.
For any of the reactor systems in this disclosure, an optional washing apparatus may be included between the first and second reactors to wash the feedstock. The washing apparatus may include an input for a solvent (such as the acid solutions used in the first reactor, water, steam or a combination thereof) to be mixed with the feedstock before or after the removal of the dissolved hemi-cellulose. The solvent may further dissolve hemi-cellulose associated with the feedstock that was not removed after the first removal of the dissolved components. The solvent may be introduced at a temperature or pressure that is below the temperature or pressure of the first reactor. Since the temperature or pressure or both is below that of the first reactor, the solvent has the additional benefit of stopping the chemical reaction(s) induced in the feedstock by the first reactor. The output of the washing apparatus containing solvent with additional hemi-cellulose may be processed separately or may be combined with the previously extracted dissolved component in blow tank 28 . The washing apparatus may further comprise additional steam ports and inputs for maintaining the temperature and pressure of the process. The washing apparatus may be incorporated into the first reactor ( 12 ), or the sealing extraction device ( 18 ) such that additional hardware is not required to implement the washing step. For example, the first reactor or the sealing extraction device may include an input port for the additional solvent for further washing the feedstock. The solvent may be removed using the regular solvent removal ports of the reactor system such as conduit 26 or 48 .
After removal of the dissolved hemi-cellulose, the remaining feed stock is discharged from the first reactor 12 to the sealing or extraction device 18 . The feed stock remains pressurized and flows from the first reactor to the sealing and extraction device 18 . The sealing and extraction device 18 conveys the feed stock from the first reactor 12 to the second reactor 16 . The sealing or extraction device 18 may increase the pressure applied to the feed stock to a level above the pressure in the first reactor 12 and to a level suitable for a steam explosion that will occur after the second reactor 16 . The second pressurized reactor may include a horizontal or conical reactor vessel.
The pressurized sealing and extraction device 18 may be a (MSD) Impressafiner®, an extruder like screw device, or a plug screw feeder or a similar unit which squeezes the pre-processed feed stock to extract the dissolved components (mainly hemi-cellulose) which are discharged via conduit 48 to a blow-tank 28 or similar device. The sealing and extraction device may increase the pressure of the feed stock from the gauge pressure, e.g., 1.5 bar to 10 bar, at the discharge of the first reactor to the gauge pressure in the second reactor 16 of 8 bar to above 25 bar.
The pressurized feed stock may flow from the first reactor 12 to the sealing and extraction device 18 by the force of gravity, by the continuous flow of feed stock in the reactor (as is shown in FIGS. 2 to 6 ) or by a discharge scraper or a discharge screw 51 as is shown in FIG. 7 . The extraction device 18 provides a pressured seal between the first and second pressurized reactors 12 and 16 . Because the feed stock is discharged from the first reactor 12 under pressure, the sealing and extraction device 18 preferably has an inlet configured to receive feed stock under pressure. For example, the inlet to the sealing and extraction device 18 is sealed to the outlet of the first reactor 12 and does not release the pressure on the feed stock entering the device 18 .
The second reactor 16 may be, for example, a vertical, horizontal or a conical reactor. Vertical reactors are shown in FIGS. 7 and 8 and may include a bottom section to promote the downward flow of feedstock, such as a diamondback section disclosed in U.S. Pat. Nos. 5,617,975 and 5,628,873, which are incorporated by reference. Suitable vessels for the second reactor 16 are conventional and are typically used in steam explosion pulping processes.
The second reactor is preferably operated at a higher pressure than the first reactor. From the second reactor assembly (which may include a second reactor 16 or a second reactor 16 and a reactor discharge device 36 ), the feed stock is discharged at high gauge pressures, such as between 8 bar to 25.5 bar. The second reactor assembly may include a discharge device 52 , such as a discharge screw feeder that moves the feed stock to a reactor discharge device 36 . The process 10 maintains the feed stock at a substantially high gauge pressure, e.g., above 1.5 bar, from the first reactor 12 , through the sealing extraction device 18 , the second reactor 16 , the reactor discharge device 36 and to the blow-valve 34 .
The second reactor 16 processes the cellulosic biomass feed stock at temperatures of, for example, 170° C. to 230° C. for approximately two to five minutes (or longer), and at a gauge pressure of eight (8) bar to 25.5 bar (800 kilopascals to 2,550 kilopascals). The second reactor 16 may include a steam phase in which steam is injected directly in the reactor to provide heat energy for the feedstock. In the second reactor 16 , one or more of steam, vapor and liquid water from sources 53 , 32 diffuses into the inner structure of ligno-cellulosic material of the feed stock. In addition, the sources of steam, water vapor or liquid water 53 , 32 may provide other liquids such as a liquid source of catalyzing agents to be injected into the second pressurized reactor 16 .
Water 32 may be directly injected into the second reactor 16 or the sealing and extraction device 18 to provide diluted water to be infused into the feed stock. The dilution water 32 and sources 53 of steam, vapor and catalyzing agents may be injected into the second reactor 16 at point(s) proximate to where the feedstock enters the reactor.
The steam or water vapor is infused into the feedstock in the second reactor 16 . The steam and water vapor partially condense as liquid water in the capillary-like micro-porous structure of the inner structure of the lingo-cellulosic material being processed in the second reactor.
The pressure of the feed stock is reduced dramatically by passing through a blow-valve 34 downstream of the second reactor assembly. The pressure drop across the blow-valve 34 is preferably at least a ten (10) bar reduction in pressure. The pressure of the feed stock may be reduced by the blow-valve 34 to one to two bars gauge, wherein zero bar gauge is at substantially atmospheric air pressure. The large pressure drop across the valve 34 is suitable for steam explosion pulping. The rapid pressure drop, e.g., “flashing”, converts to steam the condensed liquid water in the cells of the lingo-cellulosic material of the feed stock. The conversion to steam of the water in the cells of the feed stock causes a massive disruption, e.g., an “explosion”, of the cells in the cellulosic biomass feed stock. The disruption occurs because the volume occupied by the steam is much greater than the volume occupied by the water in the cells. The massive disruption includes bursting individual cells of the feed stock and rupturing the fibers along amorphous cellulose, such as between the cylindrical tubes and fibers of the cellulosic structure of the feed stock.
The feed stock pressure at the discharge of the second reactor 16 may be sufficient for steam explosion pulping, as is shown in FIG. 8 . Alternatively, a discharge device 36 may be included in the second reactor assembly to boost the pressure of the feed stock to above the pressure in the second reactor. The reactor discharge device 36 may further increase the pressure of the feed stock to a pressure suitable for steam explosion pulping, such as from 8 bar gauge to 25 bar gauge.
The second pressurized reactor 16 may discharge the feed stock under a high pressure to a reactor discharge device 36 between the second reactor and the blow-valve 34 . The second pressurized reactor assembly may comprise the reactor 16 with or without a reactor discharge device 36 . The reactor discharge device 36 may be, for example, one or more of a scraper or sweeper at the feedstock discharge port of the second reactor, a disc mill refiner, a medium density fiber board (MDF) disc refiner, a disc high pressure compressor or a discharge plug feeder. For example, an embodiment of the reactor discharge device 36 may be a single disc refiner operating at a rotational speed of 1,200 revolutions per minute (RPM) to 3,000 RPM driven by an electrical motor powered by 150 horsepower (110 kilowatts). The disc mill refiner embodiment of the reactor discharge device 36 may also partially refine the pressurized feed stock before the feed stock undergoes steam explosion reefing by passing through the blow valve 34 .
During the steam explosion, the particles of the treated feed stock are separated from the cellulosic network of the feed stock. The cyclone separator or blow tank 38 includes a lower discharge 39 for particles and an upper vapor discharge 41 for the steam, non-condensable gases (NCG), compressible gases and other chemical vapors 40 . These vapors 40 , which may include volatile organic compounds (VOCs), may be recovered such as by passing the vapors through a heat exchanger to recover the heat energy in the vapor.
The separated particles of the treated feed stock discharged from the lower discharge 39 port of the cyclone or blow tank 38 may be cooled in a cooling device 42 , which may include a belt or screw conveyor. The treated feed stock may be processed by further reactor(s) 44 that may apply acid or enzyme treatments to the treated feed stock. The treated feed stock is ultimately discharged as pre-treated feed stock 46 .
The process 10 shown in FIG. 1 may be embodied in various configurations of reactors and other devices. Several embodiments of such configurations of reactors and other devices are shown in FIGS. 2 to 8 . The reference numbers in FIGS. 2 to 8 that are common to FIG. 1 refer to devices performing same function identified by the common reference number in FIG. 1 .
As shown in FIGS. 2 to 8 , the first reactor 12 , e.g., a pre-hydrolysis reactor, may be: inclined as shown in FIGS. 2 to 8 ; arranged vertically as shown in FIG. 9 , or arranged substantially horizontal as shown in FIG. 10 .
The first pressurized reactor 12 may be a conventional reactor such as a pandia-type reactor having an internal auger or screw to move feed stock through the reactor. The feed stock may enter the first reactor 12 through a pressure sealing device 24 (in FIG. 1 ) which may be a rotary valve 60 (such as shown in FIGS. 2 , 4 , 5 , 7 and 8 ), a plug screen feeder 62 , e.g., a MSD Impressafiner® (such as shown in FIGS. 3 and 6 ) or other feed system that introduces unpressurized feed stock to a pressurized reactor.
The dissolved hemi-cellulose discharged from the reactor 12 may drain into the conduit 26 (as shown in FIGS. 2 , 4 , 6 and 7 ) or drain entirely into the pressurized sealing and extraction device 18 (as show in FIGS. 3 and 5 ). As shown in FIGS. 2 , 3 , 4 and 5 , the inclined first reactors 12 with the lower end 50 opposite to an upper end 54 which discharging the feed stock will drain most or all of the dissolved hemi-cellulose, e.g., C5-sugars, as a liquid at a lower end 50 of the reactor. The upper end 54 of these inclined first reactors has a pressure maintaining coupling to the pressurized sealing device 18 , which may be a plug screw feeder. Additional liquor having the dissolved hemi-cellulose may be extracted from the sealing device 18 and directed via conduits 48 and 26 to the reduction valve 49 and to the blow tank or drum 28 . As shown in FIG. 3 , the first reactor 12 may be inclined such that the lower end 56 of the reactor vessel has a pressure maintaining coupling to the pressurized sealing device. The lower end 56 of the reactors 12 shown in FIG. 3 discharges feed stock and the entirety of the liquid hemi-cellulose material to the pressure sealing device 18 . A conduit 48 drains the liquid hemi-cellulose from the pressure sealing and extraction device 18 and directs the liquid to the pressure reduction valve 49 and tank or drum 28 .
FIGS. 4 to 6 show that the feed stock, after passing through the blow valve 34 and being treated by steam explosion, may be separated into different flows each having a different cyclone separator 382 , 384 and 386 and different discharge devices and further reactors 422 , 424 , 426 . For example, a portion of the cellulose from the feed stock may be retained to be separated and processed separately for pulp (paper) or special chemicals applications.
The inclined first pressurized reactor 12 shown in FIG. 8 has a lower end 56 coupled to the pressurized seal 18 . The upper end 58 of the reactor may have an optional drain conduit 26 that allows the hemi-cellulose liquid to flow from the reactor to the reduction valve 49 and tank 28 .
The vertical first pressured reactor 12 , shown in FIG. 7 , includes a feed stock sweeper and conveyor 51 that discharges the feed stock from the reactor vessel and drains the hemi-cellulose liquid to the conduit 26 that directs the liquid through the reduction valve 49 and to the blow tank or drum.
A benefit of an embodiment of the cellulosic biomass feed stock pre-treatment process 10 is that the reactor vessels are preferably of constant or expanding cross-sections to allow for an expansion of the feedstock flow volume or flow rate without concern as to varying cross-sectional loading, channeling or clogging of the reactor vessels. For example, each of the reactor vessels 12 , 16 may be oriented vertically, inclined and horizontal. Similarly, the reactors feedstock flow through the each of reactors may be downwards, upwards or horizontal depending on the orientation of the reactor vessel.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
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A method including: pretreating biomass feed stock in a first pressurized reactor, wherein the feed stock undergoes hydrolysis in the first pressurized reactor; discharging the feed stock from the first pressurized reactor to a pressurized sealing device having a first pressurized coupling to a feedstock discharge port of the first pressurized reactor; maintaining a vapor phase in the first pressurized reactor by injecting steam; washing the feed stock; draining dissolved hemi-cellulosic material extracted from the feed stock; discharging the feed stock from the pressurized sealing device through a second pressurized coupling to a second pressurized reactor; in the second pressurized reactor, infusing cells of the feed stock with steam or water vapor, and rapidly releasing the pressure applied to the feed stock to cause steam expansion in the cells of the feed stock and refine the feed stock.
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RELATED APPLICATIONS
[0001] This application claims the benefit of the earlier filing date under 35 U.S.C. §119 of Korean Patent Application No. 2006-0069422 filed Jul. 25, 2006, entitled “Joint Apparatus and Hand Apparatus for Robot using the same”; the entirety of which is incorporated by reference.
FIELD OF THE INVENTION
[0002] Embodiments of the invention relate to a robot, and more particularly, to provide humanoid joints associated with structure, joint and an actuator for improving performance of a robot capable of human-like sense or touch.
BACKGROUND OF THE INVENTION
[0003] A humanoid robot is a robot with its overall appearance based on that of the human body. In general, humanoid robots have a torso with a head, arms, hands and legs. Some forms of humanoid robots may model only part of the body, for example, face, eyes, mouth and hands.
[0004] These humanoid robots resemble a human body and are capable of performing a variety of complex human tasks on commands or by being programmed in advance. However, there exist difficulties in mechanically embodying such function of the human body, especially requiring structuring mechanism in order to embody the mechanism in body motions.
[0005] As an example, the humanoid robot hand has a plurality of finger mechanisms (e.g., a thumb, an index finger, a middle finger, a ring finger and a little finger) extended from distal ends of a main body, and each finger mechanism is provided with a plurality of joint portions and a plurality of link members which are respectively disposed between the joint and connected portions in order.
[0006] A number of techniques have been developed to propose a robot hands as mimic a functionality of human hand. To achieve this, actuators for driving joint portions of each finger mechanism are provided at a place corresponding to the each finger mechanism. As such, it is required that each of the joint portions is driven by using the actuator directly or through a wire associated with a pulley on which the wires are wound. Some of these traditional approaches for configuring such hand mechanism are fully disclosed in Japanese Patent Laid-Open Publication Nos. sho 60-207795 and Hei 6-8178.
[0007] However, these conventional techniques suffer from many drawbacks. For example, in a conventional hand apparatus having a plurality of fingers that require plurality of actuators that are provided at every finger mechanism. As such, even though expanding and contracting action of each finger mechanism can be controlled independently, there exist disadvantages that require separate spaces associated with members for embodying this approach. Consequently, the approach does not permit practical way—it may require complicated structure and significant time to deploy the apparatus.
[0008] Furthermore, separate wires for connecting the finger mechanism and actuators corresponding to each movable point can be a burden. For example, spaces through which the wire is passed for electrical connection to actuate the robotic hands that are needed at each joint mechanism for a finger. It is evident that all of these requirements make the structure more complicated.
SUMMARY OF THE INVENTION
[0009] These and other needs are addressed by the invention, in which an approach is presented for accounting for the types of applications as to effectively accommodate for a humanoid joint for a robotic system.
[0010] According to one aspect of an embodiment of the invention, a joint apparatus includes a supporting part; and a rotating part configured to be rotated by a rotational force transmitted to the supporting part, wherein the rotating part is coupled to the supporting part; and a joint part configured to convert the rotational force into a rotational motion using a sliding force that is generated at abutted surfaces formed at the end of the joint part in contact, wherein a first joint part resides within the rotating part and a second joint part resides within the supporting part.
[0011] According to another aspect of an embodiment of the invention, a hand apparatus for a robot is disclosed. The hand apparatus includes a wrist part; a plurality of finger parts disposed in parallel to the wrist part having a plurality of link members; a joint part disposed between the link members the joint part configured to convert a rotational force generated by a first joint part into a rotational motion of a second joint part, wherein the rotational force is converted into a hand motion occurred at contact surfaces of the each joint part abutted each other; and a thumb part formed at the wrist part configured to be rotated.
[0012] According to another aspect of an embodiment of the invention, an apparatus for providing humanoid robot hands is disclosed. A plurality of joint members being coupled within a plurality of structures means for configuring a humanoid robotic hand, wherein the each joint member is a pair and each pair has a symmetrical shape at end; means for disposing the pair within the structure and the each structure is hinged each other, wherein a space is formed at hinged part; and means for providing a rotational force to a joint member, wherein the provided rotational force can be converted to a rotational motion through a sliding force occurred at the contact formed by the symmetrical shape of the each pair abutted against each other, wherein the rotational motion is converted into hand motion by the rotational motion is restricted within the space, wherein a desired motion for the humanoid robot hand can be achieved.
[0013] According to yet another aspect of an embodiment of the invention, a method for providing a humanoid joint for a robotic system is provided. The method includes configuring a plurality of elements for embodying the humanoid robotic system, wherein the elements can include a supporting part, a motion part and a joint part; forming a first contact at a hemispherical shape at the end of one joint part; forming a second contact at a hemispherical shape at the end of the other joint, wherein the joint part is a pair; disposing the joint part within the supporting part and the motion part respectively, wherein the supporting part and the motion part are hinged; providing a power to a joint part having the first contact for generating a rotational force, wherein the rotational force is transmitted to the second contact abutted at the first contact at which a sliding force is occurred, wherein the sliding force causes the second contact to move, wherein the movements of the contact are restricted within the space formed at the hinged portion, wherein various motions can be achieved for the humanoid joint.
[0014] Still other aspects, features, and advantages of the embodiments of the invention are readily apparent from the following detailed description, simply by illustrating a number of particular embodiments and implementations, including the best mode contemplated for carrying out the embodiments of the invention. The invention is also capable of other and different embodiments, and its several details can be modified in various obvious respects, all without departing from the spirit and scope of the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The embodiments of the invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
[0016] FIG. 1A is a perspective view of a joint apparatus in accordance with an embodiment of the invention;
[0017] FIG. 2 is an exploded perspective view of the joint apparatus in accordance with an embodiment of the invention;
[0018] FIG. 3 is a cross-sectional view of the joint apparatus in accordance with an embodiment of the invention;
[0019] FIG. 4 is a perspective view of a hand apparatus for a robot using the joint apparatus in accordance with an embodiment of the invention;
[0020] FIG. 5 is a lower perspective view of the hand apparatus for the robot using the joint apparatus in accordance with an embodiment of the invention;
[0021] FIG. 6 is an enlarged perspective view of the hand apparatus for the robot using the joint apparatus in accordance with an embodiment of the invention; and
[0022] FIG. 7 is a partially cut-away perspective view showing an internal structure of an index finger part of the hand apparatus for the robot using the joint apparatus in accordance with an embodiment of the invention;
DETAILED DESCRIPTION
[0023] A device, and method for providing humanoid joint for a robotic system are described. In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It is apparent, however, to one skilled in the art that the embodiments of the invention may be practiced without these specific details or with an equivalent arrangement. In other instances, well-known structures and devices are shown in block diagram form in order to avoid unnecessarily obscuring the embodiments of the invention.
[0024] Although the embodiments of the invention are discussed with respect to a humanoid robotic hand, it is recognized by one of ordinary skill in the art that the embodiments of the inventions have applicability to any type of robotic system as well any mechanism.
[0025] As shown in FIGS. 1 to 3 , a joint apparatus 100 of the present invention includes a supporting unit 110 and a rotating unit 120 which are respectively formed into an external frame and rotatably coupled with each other, a joint unit 130 which is provided at an inside of the supporting unit 110 and rotating unit 120 so that the rotating unit 120 is rotated by a sliding frictional motion generated when power is transmitted to the supporting unit 110 , and a power unit (not shown) for providing a rotational torque to the joint unit 130 .
[0026] In this example, the supporting unit 110 and the rotating unit 120 are separated by an operational state. Therefore, the roles of the supporting unit 110 and the rotating unit 120 may be exchanged according to the operational state.
[0027] The supporting unit 110 and the rotating unit 120 are formed with an outer coupling part 112 and an inner coupling part 122 at their ends adjacent to each other so that the outer and inner coupling parts 112 and 122 are rotatably coupled with each other, and a space for receiving the joint unit 130 is formed between the outer and inner coupling parts 112 and 122 . A rotational center of each of the outer and inner coupling parts 112 and 122 is formed to be the same as that of the joint unit 130 .
[0028] The joint part 130 is provided with a first joint 132 a which is rotatably disposed at an inside of the supporting unit 110 in a length direction of the supporting unit 110 , and a second joint 132 b which is rotatably disposed at an inside of the rotating unit 120 in a length direction of the rotating unit 120 . At each end of the first and second joints 132 a and 132 b , there are respectively formed with first and second pressure hemispherical parts 134 a and 134 b.
[0029] By way of example, the first and second pressure hemispherical parts 134 a and 134 b are respectively formed with first and second contact surfaces 136 a and 136 b which have the same shape and by which the first and second pressure hemispherical parts 134 a and 134 b are closely contacted with each other. The first and second contact surfaces 136 a and 136 b are inclined at the same angle, respectively. First and second shaft holes 138 a and 138 b are respectively formed at center portions of the first and second contact surfaces 136 a and 136 b so that a rotational shaft 139 is inserted into the first and second shaft holes 138 a and 138 b so as to be rotated in a state that the first and second contact surfaces 136 a and 136 b are closely contacted with each other.
[0030] The power unit is to provide a rotational force to the first joint 132 a which is rotatably disposed in the supporting unit 110 . A brushless DC motor (BLDC) is used as the power unit. Also, a reduction gear (not shown) for adjusting a rotational ratio, an encoder (not shown) for detecting a rotational level and the like may be further provided.
[0031] As an exemplary embodiment, the operation of the joint apparatus is described in detail. It is noted that each element to be described below shall be understood with reference to FIGS. 1 to 3 and the above descriptions.
[0032] In the joint apparatus 110 as described above, the power unit generates power to rotate the rotating part 120 coupled with the supporting part 110 . Therefore, the power generated from the power unit is transmitted to the first joint 132 a disposed in the supporting unit 110 so as to rotate the first joint 132 a . By the rotation of the first joint 132 a , the power is transmitted from the first joint 132 a to the second joint 132 b . As evident from the joint, the second joint 132 b is also rotated.
[0033] The first joint 132 a and the second joint 132 b are closely contacted with each other through the first and second contact surfaces 136 a and 136 b of the first and second pressure hemispherical parts 134 a and 134 b . The first and second contact surfaces 136 a and 136 b are contacted and coupled with each other by a rotational shaft 139 in a state of being inclined at a desired angle with respect to a rotational center of the first and second joints 132 a and 132 b.
[0034] Therefore, if the rotational force of the first joint 132 a is transmitted to the second joint 132 b , a sliding motion is occurred between the first and second contact surfaces 136 a and 136 b and thus the second joint 132 b is rotated with the rotational shaft 139 in the center.
[0035] However, since the first and second supporting units 132 a and 132 b are constrained by the outer and inner coupling parts 112 and 122 of the supporting unit 110 and the rotating unit 120 , the rotating unit 120 is rotated with respect to the supporting unit 110 in a state that the rotational motion of the second joint 132 b is limited to a direction that the rotating unit 120 can be rotated. Therefore, the rotational force of the power unit can be converted into the rotational motion of the rotating unit 120 with respect to the supporting unit 110 .
[0036] The hand apparatus for the robot using the joint apparatus according to an embodiment of the invention has a similar shape to a human hand. That is, like the human hand, the hand apparatus is provided with a thumb, an index finger, a middle finger, a ring finger and a little finger. However, if necessary, the number of fingers of the hand apparatus may be changed.
[0037] Further, the number of link members and joints forming each finger in the hand apparatus may be the same as that of the human hand. However, if necessary, it may be also changed.
[0038] Furthermore, the structure of the link member and joint applies the joint apparatus. Now, a structure and operation of the joint will be described with reference to the drawings.
[0039] As shown in FIGS. 4 and 5 , the hand apparatus 200 using the joint apparatus according to an embodiment of the invention includes a wrist part 210 which is rotatably disposed at an arm part (not shown) of the robot (not shown) and a plurality of finger parts (a thumb part 220 , a index finger part 230 , a middle finger part 240 , a ring finger part 250 and a little finger part 260 ) extended from the wrist part 210 .
[0040] The thumb part 220 is rotatably disposed at an outside of the wrist part 210 , which is adjacent to a side of the index finger part 230 . That is, the thumb part 220 can be rotated to a lower side of the index finger part 230 from the side of the index finger part 230 .
[0041] The thumb part 220 includes a supporting link 226 for rotatably supporting the thumb part 220 with respect to the wrist part 210 , and a rotating link 224 of which one end is rotated by a rotating motor 226 a and the other end is coupled with a desired part of the thumb part 220 .
[0042] If the rotating link 224 is rotated by the rotating motor 226 a , the thumb part 220 coupled with the other end of the rotating link 224 is rotated, and the thumb part 220 is rotated to the lower side of the index finger part 230 while being supported by the rotating link 224 . The rotating motor 226 a may be further provided with an encoder 226 b for detecting the rotation of the rotating motor 226 a , and a reduction gear 226 c for adjusting the rotational ratio of the rotating motor 226 a.
[0043] The index finger part 230 , the middle finger part 240 and the ring finger part 250 are extended from a center portion of the wrist part 210 in one direction with the middle finger part 240 in the center. The index finger part 230 and the ring finger part 250 disposed at both sides of the middle finger part 240 are disposed to be rotated in a horizontal direction with respect to the extended direction of each finger part 230 , 240 , 250 , 260 .
[0044] Further, each of index finger part 230 , the middle finger part 240 , the ring finger part 250 and the little finger part 260 is provided with a plurality of link members 232 a , 232 b , 232 c and 232 d , and a plurality of joints 234 a , 234 b , 234 c and 234 d interposed between adjacent link members. Preferably, each finger part 220 , 230 , 240 , 250 and 260 has a similar structure to the human hand.
[0045] In this example, since the index finger part 230 , the middle finger part 240 , the ring finger part 250 and the little finger part 260 have the same structure and shape except the directions of the link members and the joints which form each finger part, only the index finger part will be described and the description for the other finger part will be omitted.
[0046] As shown in FIGS. 6 and 7 , the index finger part 230 of the hand apparatus 200 for the robot, according to an embodiment of the invention, is coupled with the wrist part 210 so as to be rotated horizontally, and includes a first link member 232 a forming a palm portion of the hand apparatus 200 , a second link member 232 b coupled with the first link member 232 a to be rotated vertically, a third link member 232 c coupled with the second link member 232 b to be rotated vertically, a fourth link member 233 d coupled with the third link member 232 c to be rotated vertically.
[0047] A horizontal hinge part 212 is formed at the wrist part 210 so that the first link member 232 a can be rotated horizontally with respect to the palm portion formed by the finger parts. A horizontal rotating part 236 a coupled with the horizontal hinge part 212 is formed at an end of the first link member 232 a . Further, at a lower side of the horizontal hinge part 212 and the horizontal rotating part 236 a , there is provided a first joint part 234 a of which one side is coupled with the wrist part 210 and the other side is coupled with the first link member 232 a.
[0048] A first vertical rotating part 236 b is provided between the first link member 232 a and the second link member 232 b so that the second link member 232 b is supported to be rotated vertically with respect to the first link member 232 a . A second joint part 234 b is provided at an inside of the first vertical rotating part 236 b so as to be rotated the second link member 232 b with respect to the first link member 232 a.
[0049] In addition, a second vertical rotating part 236 c is provided between the second link member 232 b and the third link member 232 c so that the third link member 232 c is supported to be rotated vertically with respect to the second link member 232 b . A third joint part 234 c is provided at an inside of the second vertical rotating part 236 c so as to be rotated the third link member 232 c with respect to the second link member 232 b.
[0050] Finally, a third vertical rotating part 236 d is provided between the third link member 232 c and the fourth link member 232 d so that the fourth link member 232 d is supported to be rotated vertically with respect to the third link member 232 c . A forth joint part 234 d is provided at an inside of the third vertical rotating part 236 d so as to be rotated the fourth link member 232 d with respect to the third link member 232 c.
[0051] As an exemplary embodiment, the first, second and third vertical rotating part 236 b , 236 c and 236 d have respectively the same structure as the outer and inner coupling parts 112 and 122 of the joint apparatus 100 according to an embodiment of the invention.
[0052] Meanwhile, the second, third and fourth joint parts 234 b , 234 c and 234 d as described above are mounted in a direction orthogonal to the mounting direction of the first joint part 234 a . That is, when the joint parts 234 a , 234 b , 234 c and 234 d are respectively operated at their initial positions, the second, third and fourth joint parts 234 b , 234 c and 234 d are operated in a direction orthogonal to an operation direction of the first joint part 234 a.
[0053] In this example, the first, second, third and fourth joint parts 234 a , 234 b , 234 c and 234 d apply the joint apparatus 100 (referring to FIG. 1 ) according to an embodiment of the invention. The joint parts 234 a , 234 b , 234 c and 234 d are respectively provided with first joints 234 a 1 , 234 b 1 , 234 c 1 and 234 d 1 and second joints 234 a 2 , 234 b 2 , 234 c 2 and 234 d 2 . Each of the first joints 234 a 1 , 234 b 1 , 234 c 1 and 234 d 1 has a separate power unit 235 a , 235 b , 235 c and 235 d.
[0054] At each end of the first joints 234 a 1 , 234 b 1 , 234 c 1 and 234 d 1 and second joints 234 a 2 , 234 b 2 , 234 c 2 and 234 d 2 which are adjacent to each other, there is formed a pressure hemispherical part having an inclined contact surface at a desired angle. The contact surface formed at the pressure hemispherical part is restricted to be rotated around a rotational axis orthogonal to the contact surface. When the rotational force is generated at the first joints 234 a 1 , 234 b 1 , 234 c 1 and 234 d 1 , the rotational force is transmitted from the first joints 234 a 1 , 234 b 1 , 234 c 1 and 234 d 1 to the second joints 234 a 2 , 234 b 2 , 234 c 2 by the sliding motion between the contact surfaces so that the second joints 234 a 2 , 234 b 2 , 234 c 2 are rotated. The first joints 234 a 1 , 234 b 1 , 234 c 1 and 234 d 1 and the second joints 234 a 2 , 234 b 2 , 234 c 2 and 234 d 2 shall be understood with reference to the description of the first joint 132 a and the second joint 132 b of the joint apparatus.
[0055] By way of example, the each of the power units 235 a , 235 b , 235 c and 235 d includes a motor for generating the rotational force, an encoder for detecting the rotational force of the motor, and a reduction gear for adjusting the rotational ratio of the motor.
[0056] The power units 235 a , 235 b , 235 c and 235 d disposed in the first, second, third and fourth joint parts 234 a , 234 b , 234 c and 234 d may be operated independently or may be operated at the same time by applying a desired voltage. Further, the first, second, third and fourth joint parts 234 a , 234 b , 234 c and 234 d may be operated using the power supplied from one of the power units 235 a , 235 b , 235 c and 235 d by linking the power of the first, second, third and fourth joint parts 234 a , 234 b , 234 c and 234 d to each other.
[0057] When the index finger part 230 disposed at the wrist part 210 is rotated horizontally, the power unit 235 a of the first joint part 234 a disposed at the lower side of the horizontal hinge part 212 of the wrist part 210 and the first link member 232 a of the horizontal rotating part 236 a is operated. Thus, the first joint 234 a 1 of the first joint part 234 a is rotated by the power unit 235 a and then the power is transmitted to the second joint 234 a 2 .
[0058] Therefore, while the sliding motion is occurred between the contact surfaces of the pressure hemispherical parts formed at each end of the first and second joints 234 a 1 and 234 a 2 , the contact surfaces are rotated around the rotational shaft provided between the contact surfaces. Sequentially, while the second joint 234 a 2 is rotated with the rotational shaft in the center, the first link member 232 a coupled with the second joint 234 a 2 is reciprocated horizontally. Thus, the first link member 232 a is rotated horizontally by the horizontal rotating part 236 a coupled with the horizontal hinge part 212 of the wrist part 210 .
[0059] Now, the vertical rotating motion of the second and third and fourth link members 232 b , 232 c and 232 d will be described. Herein, the vertical rotating motion of the second and third and fourth link members 232 b , 232 c and 232 d is performed through the equivalent processes, and thus the operation of the second link member 232 b is described and the description of the third and fourth link members 232 c and 232 d are the equivalent processes that are shown in FIGS. 6-7 in order to avoid unnecessarily obscuring the embodiments of the invention.
[0060] First of all, in order to rotate the second link member 232 b couple with the first link member 232 a to be rotated vertically, the power unit 235 b of the second joint part 234 b provided between the first and second link members 232 a and 232 b is operated. Thus, the first join 234 b 1 forming the second joint part 234 b is rotated by the power unit 235 b and the power is transmitted to the second joint 234 b 2 .
[0061] Therefore, while the sliding motion is occurred between the contact surfaces of the pressure hemispherical parts formed at each end of the first and second joints 234 b 1 and 234 b 2 , the contact surfaces are rotated around the rotational shaft provided between the contact surfaces. Sequentially, while the second joint 234 b 2 is rotated with the rotational shaft in the center, the second link member 232 b coupled with the second joint 234 b 2 is reciprocated vertically.
[0062] In a way of example, the third and fourth link members 232 c and 232 d are also reciprocated through the same processes. Smooth finger motion can be obtained by controlling the third and fourth link members 232 c and 232 d independently.
[0063] As described above, according to the joint apparatus of an embodiment of the invention, since each joint has a simple structure and can be operated independently, there is an advantage to provide the smooth finger motion.
[0064] Further, according to the hand apparatus using the joint apparatus of an embodiment of the invention, there is another advantage to provide a hand apparatus which can be smoothly operated like a human hand by using the joint apparatus which has a simple structure and can be operated independently.
[0065] While the invention has been described in connection with a number of embodiments and implementations, the invention is not so limited but covers various obvious modifications and equivalent arrangements, which fall within the purview of the appended claims. Although features of the invention are expressed in certain combinations among the claims, it is contemplated that these features can be arranged in any combination and order.
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An approach is disclosed for providing a humanoid joint for a robotic system. A joint apparatus includes a supporting part, a rotating part and a pair of joint part, wherein the supporting part and the rotating part are coupled in which the joint part is disposed, wherein a rotational force is initially driven by a joint part and the rotational force is transmitted to the other joint part using a sliding motion generated at an abutted surface of each joint part, wherein the surface is formed at the end of the joint part, wherein the transmitted rotational forces can be converted into a motion by the restriction of movement of joint part occurred within the limited space formed by the coupling of rotational part and supporting part.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved method for production of phenol and acetone by decomposition of cumene hydroperoxide to phenol, acetone, and α-methylstyrene in the presence of an acidic catalyst. The improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine.
2. Related Background Art
One of the predominant commercial processes for manufacture of phenol is the cumene oxidation process, in which cumene is oxidized in air to produce cumene hydroperoxide (CHP). The CHP is then cleaved to phenol and acetone in the presence of an acidic catalyst. This process also produces α-methylstyrene (AMS), along with other byproducts, including acetophenone, dimethylphenylcarbinol, and cumylphenols. Typically, the acidic catalyst is a strong, and not heavily corrosive inorganic acid, such as sulfuric or phosphoric acid. The acidic catalyst must be removed or neutralized to prevent further, unwanted reactions in the downstream purification steps that produce the phenol and acetone products.
Typically, commercial processes for manufacture of phenol from CHP use inorganic bases, ion exchange resins, or a combination thereof to remove acidity from the crude product stream. Since ion exchange resins are temperature sensitive, the crude product stream must be cooled substantially prior to contact with the resin. The need to cool the product stream increases energy costs significantly because the crude product stream must then be re-heated prior to downstream purification operations. A further drawback of ion exchange resins is that they must be regenerated frequently, a labor-intensive and costly process which also results in formation of large amounts of aqueous waste. Moreover, ion exchange resins give a highly variable final pH in the crude product stream, adversely affecting final product yields, and can also release alkali salts which cause fouling of equipment.
The use of a strong base, such as sodium hydroxide or potassium hydroxide to neutralize the acidic catalyst is not desirable because it is difficult to achieve accurate pH control in a neutralization reaction between a strong acid and a strong base. Moreover, metal hydroxides generate salts that have a propensity to deposit on heat exchange surfaces, causing fouling and decreasing efficiency.
The use of ammonia to neutralize the acidic catalyst is disclosed in U.S. Pat. No. 5,254,751 to Zakoshansky. In the process described in this reference, neutralization with ammonia is performed during the CHP decomposition, rather than after the decomposition. The disclosure states that the ammonium salts produced from addition of ammonia to the reaction mixture act as acidic catalysts for the remainder of the CHP decomposition reaction. This reference suggests that hydrazine and alkylamines having one to five carbon atoms are suitable for neutralization during CHP decomposition, but that ammonia is preferred, especially for neutralizing sulfuric acid. Zakoshansky also suggests a maximum operating temperature of 110° C.
SUMMARY OF THE INVENTION
The present invention is directed to an improved method for production of phenol and acetone from cumene hydroperoxide by decomposition of cumene hydroperoxide in the presence of an acidic catalyst, wherein the improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine selected from the group consisting of: (i) a secondary or tertiary amine having from 4 to 21 carbon atoms and not having hydrolytically unstable substituents or acidic substituents; and (ii) a primary amine of formula
wherein R 1 and R 2 are independently hydrogen or C 1 -C 12 alkyl, and R 3 is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkyl substituted by hydroxyl, amino or dimethylamino, provided that at least two of R 1 , R 2 and R 3 are not hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
The term “alkyl” is used herein to refer to a saturated acyclic hydrocarbyl substituent group which may be linear or branched. The term “alkylene” is used herein to refer to an acyclic hydrocarbyl substituent group having at least one carbon-carbon double bond, and which may be linear or branched. The term “secondary or tertiary amine” is used herein to refer to an amine in which there is at least one nitrogen atom directly bonded to at least two carbon atoms.
The term “acidic substituents” is used herein to refer to substituents having a pKa value in aqueous media of less than about 5. Examples of acidic substituents include the acid forms of carboxylates, nitrates, phosphates, phosphonates, sulfates and sulfonates. The term “hydrolytically unstable substituents” is used herein to refer to those substituents that undergo substantial hydrolysis and/or condensation reactions at a pH in the range from about 3.5 to about 1.5 and a temperature in the range from about 30° C. to about 180° C. in a period of about two hours. Examples of hydrolytically unstable groups are esters, anhydrides, amides, acid halides, amidines, aminals, enamines, aldehydes, ethers, acetals, hemi-acetals, ketals, hemi-ketals, epoxides and alkynes. Preferably, a substituted amine employed in the present invention contains no elements other than carbon, hydrogen, nitrogen and oxygen, and no functional groups containing nitrogen or oxygen other than amine and hydroxyl groups.
The substituted amine employed in the present invention allows neutralization of product streams from decomposition of cumene hydroperoxide at elevated temperatures with minimal formation of byproducts from reactions between the amine and organic constituents of the product stream, e.g., acetone. Performing the neutralization at elevated temperatures, i.e., temperatures near the normal process temperature for decomposition of the hydroperoxide, eliminates the need to cool the process stream prior to neutralization, and then reheat prior to performing purification operations. The preferred temperature range for the neutralization process of this invention is from about 30° C. to about 180° C., more preferably from about 60° C. to about 160° C., and most preferably from about 120° C. to about 160° C.
Neutralization with relatively unsubstituted amines which are highly basic, relatively unsubstituted and sterically relatively unhindered, as suggested in the literature, e.g., ammonia, is not efficient, especially at elevated temperatures. This is believed to be due to consumption of the amine in reactions with acetone or other components of the process stream. As shown below in Example 33, addition of ammonium hydroxide to a typical product mixture at 140.3° C. produces a much smaller change in pH than the same amount added at 22.5° C., indicating that a substantial amount of the ammonia is consumed in side reactions. Even at 100.2° C., the pH is significantly lower than that observed at 22.5° C. Addition of the relatively unsubstituted amines DYTEK®-A, hexamethylene diamine, or n-propylamine also produces a much smaller change in pH at high temperatures, as shown below in Examples 1-3.
In contrast, the amines employed in the present invention exhibit a final pH at a high temperature that is much closer to the final pH observed at low temperature. These amines are more sterically hindered or are more highly substituted on the nitrogen. Without being bound to theory, it is believed that these amines do not undergo reactions with organic constituents of the product stream as readily due to the aforementioned characteristics, and are thus more efficient neutralizing agents, especially at high temperatures.
The method of the present invention allows better control of the post-neutralization pH of the product stream than conventional methods, especially when the neutralization is conducted at elevated temperatures. Preferably, the target final pH is in the range from about 2.0 to about 3.5, most preferably from about 2.2 to about 2.8.
In a preferred embodiment of the invention, the secondary or tertiary amine is selected from the group consisting of
wherein R 4 and R 5 are independently hydrogen or methyl, and R 6 , R 7 and R 8 are independently hydrogen or C 1 -C 4 alkyl;
wherein R 9 and R 10 are independently C 1 -C 12 alkyl, C 2 -C 12 alkyl substituted by hydroxyl, amino or dimethylamino, C 3 -C 7 alkylene or R 9 and R 10 join with NR 11 to form a cyclic aliphatic amine having from 5 to 7 ring atoms, e.g., hexamethyleneimine, and R 11 is hydrogen, C 2 -C 12 alkyl, C 2 -C 12 alkyl substituted by hydroxyl, C 5 -C 6 cycloalkyl or C 3 -C 7 alkylene, provided that R 9 , R 10 and R 11 taken together contain at least six carbon atoms; and
wherein R 12 , R 13 and R 14 are independently hydrogen or C 1 -C 4 alkyl.
In another preferred embodiment of the invention, the substituted amine is
wherein R 9 and R 10 are independently C 2 -C 6 alkyl or C 2 -C 6 alkyl substituted by hydroxyl, or R 9 and R 10 join with NR 11 to form a cyclic aliphatic amine having from 6 to 7 ring atoms; and R 11 is hydrogen, C 2 -C 6 alkyl or C 2 -C 6 alkyl substituted by hydroxyl. The substituted amine contains at least six carbon atoms. Preferred amines in this embodiment of the invention are triethylamine, tri-n-propylamine, triisopropylamine, triisopropanolamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-hexylamine and hexamethyleneimine. More preferably, R 9 , R 10 and R 11 are independently C 2 -C 6 alkyl or C 2 -C 6 alkyl substituted by hydroxyl. Particularly preferred amines in this embodiment of the invention are triethylamine, tri-n-propylamine, triisopropylamine and triisopropanolamine. Most preferably, R 9 , R 10 and R 11 are independently C 3 -C 6 alkyl or C 3 -C 6 alkyl substituted by hydroxyl. The most preferred amines in this embodiment are tri-n-propylamine, triisopropylamine and triisopropanolamine.
In another preferred embodiment of the invention, the substituted amine is
wherein R 1 and R 2 are independently C 1 -C 9 alkyl, and R 3 is C 1 -C 9 alkyl or C 1 -C 9 alkyl substituted by hydroxyl or amino. It is preferred that R 1 and R 2 are independently C 1 -C 9 alkyl, and R 3 is C 2 -C 9 alkyl. Preferred amines include tert-amylamine (1,1-dimethylpropylamine) and tert-octylamine (1,1,3,3tetramethylbutylamine). It is further preferred that R 1 and R 2 are methyl and R 3 is C 3 -C 9 alkyl. Most preferably, R 1 and R 2 are methyl and R 3 is C 5 -C 9 alkyl. The most preferred amine in this embodiment of the invention is tert-octylamine.
In another preferred embodiment of the invention, the substituted amine is selected from the group consisting of a 2,6-dialkyl aniline, N-methyl aniline and N,N-dimethyl aniline. Particularly preferred anilines of this type are 2,6-dimethyl aniline, 2,6-diethyl aniline and N-methylaniline.
Other organic bases are suitable for use in the method of the present invention, although not preferred. For example, tetraalkylammonium hydroxides, where the alkyl groups independently contain from one to ten carbon atoms, are efficient neutralizing agents under the conditions described herein, as illustrated by Examples 29 and 30.
The following Examples are intended solely to illustrate certain preferred embodiments of the invention, and not to limit the invention.
EXAMPLES
Example 1
Temperature Effects on Neutralization of Crude Product with “DYTEK® A” Amine.
A ½′ stainless steel tube capped at one end, with a ¼″ stainless steel ball valve at the other end, was used as a static reactor for the elevated-temperature runs. At temperatures above about 80° C., the exit of the valve was sealed with a septum cap which was secured with wire. The tube was sufficiently long so that a 10 mL charge of crude product at room temperature left about 1 cm of void space in the tube itself. The crude product had an acid content of 34-38 ppm as sulfuric acid. A solution of 1% 2-methyl-1,5-pentanediamine (available from Aldrich Chemical Co. under the name “DYTEK® A”) in water was added via a gas-tight syringe with a needle sufficiently long to reach the center of the void space, with vigorous shaking and mixing for 30 seconds after addition. For the low-temperature (22.5° C.) runs, the solutions were mixed in a glass beaker for pH measurement. The results of the pH measurement for each run are summarized in the following table, along with the amount of amine added in that run, and the temperature of the run in ° C. (T). The change in pH with temperature is reported as “% off target”, which is the pH of the low-temperature run minus the pH of the higher-temperature run divided by the pH of the low-temperature run, expressed as a percentage.
μL 1%
% off
T
DYTEK ® A
pH
target
22.5
40.0
2.70
0.0
100.2
40.0
2.12
21.5
140.3
40.0
1.29
52.2
22.5
40.0
2.64
0.0
100.5
40.0
1.99
24.6
140.5
40.0
1.20
54.5
22.5
40.0
2.60
0.0
100.3
40.0
1.98
23.8
140.7
40.0
1.13
56.5
Example 2
Temperature Effects on Neutralization of Crude Product with Hexamethylenediamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of hexamethylenediamine (HMDA). Results of pH measurement for each run are presented in the following table:
μL 0.5%
% off
T
HMDA
pH
target
22.5
80.0
2.74
0.0
100.5
80.0
2.26
17.5
140.5
80.0
1.40
48.9
Example 3
Temperature Effects on Neutralization of Crude Product with n-Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of n-propylamine. Results of pH measurement for each run are presented in the following table:
μL 0.3%
% off
T
n-propylamine
pH
target
22.5
60.0
2.48
0.0
100.5
60.0
1.91
23.0
140.5
60.0
0.92
62.9
Example 4
Temperature Effects on Neutralization of Crude Product with iso- Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of iso-propylamine. Results of pH measurement for each run are presented in the following table:
μL 0.3%
% off
T
iso-propylamine
pH
target
22.5
80.0
2.64
0.0
100.5
80.0
2.26
14.4
140.5
80.0
1.94
26.5
Example 5
Temperature Effects on Neutralization of Crude Product with tert-Amylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of tert-amylamine (“t-amylamine). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
t-amylamine
pH
target
22.5
50.0
2.84
0.0
100.5
50.0
2.71
4.6
140.5
50.0
2.54
10.6
Example 6
Temperature Effects on Neutralization of Crude Product with tert-octylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an a cumene solution of tert-octylamine (“t-octylamine”). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
t-octylamine
pH
target
22.5
70.0
2.61
0.0
100.2
70.0
2.51
3.8
140.3
70.0
2.35
10.0
Example 7
Temperature Effects on Neutralization of Crude Product with Bis(hexamethylene)triamine (“BHMT”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of BHMT. Results of pH measurement for each run are presented in the following table:
μL 0.5%
% off
T
BHMT
pH
target
22.5
120.0
2.64
0.0
100.5
120.0
2.48
6.1
140.5
120.0
1.81
31.4
Example 8
Temperature Effects on Neutralization of Crude Product with DYTEK®-EP.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of 1,3-diaminopentane (available from Aldrich Chemical Co. under the name DYTEK®-EP). Results of pH measurement for each run are presented in the following table:
μL 0.5%
% off
T
DYTEK ® EP
pH
target
22.5
80.0
2.67
0.0
100.5
80.0
2.26
15.4
140.5
80.0
1.98
25.8
Example 9
Temperature Effects on Neutralization of Crude Product with Di-n-Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-n-propylamine (“Di-n-PrNH2”). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
Di-n-PrNH2
pH
target
22.5
60.0
2.52
0.0
100.3
60.0
2.37
6.0
140.5
60.0
2.16
14.3
Example 10
Temperature Effects on Neutralization of Crude Product with Di-n-Butylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-n-butylamine (“Di-n-BuNH2”). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
Di-n-BuNH2
pH
target
22.5
80.0
2.70
0.0
100.2
80.0
2.53
6.3
140.5
80.0
2.34
13.3
Example 11
Temperature Effects on Neutralization of Crude Product with Hexamethyleneimine (“HMI”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of HMI. Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
HMI
pH
target
22.5
50.0
2.67
0.0
100.5
50.0
2.58
3.4
140.5
50.0
2.25
15.7
Example 12
Temperature Effects on Neutralization of Crude Product with N-Methylaniline.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of N-methylaniline (“N-MeAn”). Results of pH measurement for each run are presented in the following table:
μL 3.0%
% off
T
N-MeAn
pH
target
22.5
70.0
2.66
0.0
100.3
70.0
2.67
−0.4
140.5
70.0
2.56
3.8
Example 13
Temperature Effects on Neutralization of Crude Product with Aniline.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of aniline. Results of pH measurement for each run are presented in the following table:
μL 3.0%
% off
T
aniline
pH
target
22.5
80.0
2.65
0.0
100.3
80.0
2.14
19.2
140.5
80.0
1.78
32.8
Example 14
Temperature Effects on Neutralization of Crude Product with 1,4-Phenylenediamine (“1,4-PDA”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of 1,4-PDA. Results of pH measurement for each run are presented in the following table:
μL 0.4%
% off
T
1,4-PDA
pH
target
22.5
100.0
2.53
0.0
100.5
100.0
1.69
33.2
140.5
100.0
1.46
42.3
Example 15
Temperature Effects on Neutralization of Crude Product with m-Toluidine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of m-toluidine. Results of pH measurement for each run are presented in the following table:
μL 2.1%
% off
T
m-toluidine
pH
target
22.5
80.0
2.59
0.0
100.3
80.0
1.93
25.5
140.5
80.0
1.34
48.3
140.5
80.0
1.37
47.1
Example 16
Temperature Effects on Neutralization of Crude Product with o-Toluidine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of o-toluidine. Results of pH measurement for each run are presented in the following table:
μL 3.1%
% off
T
o-toluidine
pH
target
22.5
70.0
2.59
0.0
100.3
70.0
2.24
13.5
140.5
70.0
1.81
30.1
Example 17
Temperature Effects on Neutralization of Crude Product with 2-Ethylaniline.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-ethylaniline (“2-EtAn”). Results of pH measurement for each run are presented in the following table:
μL 3.0%
% off
T
2-EtAn
pH
target
22.5
80.0
2.61
0.0
100.3
80.0
2.18
16.5
140.5
80.0
1.76
32.6
Example 18
Temperature Effects on Neutralization of Crude Product with 2-n-Propylaniline (“2-n-PrAn”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-n-PrAn. Results of pH measurement for each run are presented in the following table:
μL 3.2%
% off
T
2-n-PrAn
pH
target
22.5
90.0
2.56
0.0
100.3
90.0
2.18
14.8
140.5
90.0
1.80
29.7
Example 19
Temperature Effects on Neutralization of Crude Product with 2-iso-Propylaniline (“2-i-PrAn”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-i-PrAn. Results of pH measurement for each run are presented in the following table:
μL 4.3%
% off
T
2-i-PrAn
pH
target
22.5
60.0
2.54
0.0
100.3
60.0
2.18
14.2
140.5
60.0
1.77
30.3
Example 20
Temperature Effects on Neutralization of Crude Product with Pyridine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of pyridine. Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
pyridine
pH
target
22.5
130.0
2.51
0.0
100.2
130.0
2.39
4.8
140.3
130.0
2.43
3.2
Example 21
Temperature Effects on Neutralization of Crude Product with Tri-n-Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of tri-n-propylamine (“Tri-n-PrNH2”). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
Tri-n-PrNH2
pH
target
22.5
60.0
2.53
0.0
100.3
60.0
2.41
4.7
140.5
60.0
2.38
5.9
Example 22
Temperature Effects on Neutralization of Crude Product with Tni-iso-Propylamine.
The method and apparatus described in Example I were used to determine temperature effects on neutralization of crude product with a cumene solution of tri-iso-propylamine (“Tri-i-PrNH2”). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
Tri-i-PrNH2
pH
target
22.5
70.0
2.60
0.0
100.3
70.0
2.44
6.2
140.5
70.0
2.38
8.5
Example 23
Temperature Effects on Neutralization of Crude Product with Triisopropanolamine (“TIPA”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TIPA. Results of pH measurement for each run are presented in the following table:
μL 1.14%
% off
T
TIPA
pH
target
22.5
70.0
2.65
0.0
100.5
70.0
2.53
4.5
140.5
70.0
2.50
5.7
Example 24
Temperature Effects on Neutralization of Crude Product with 2,6-Dimethylaniline (“2,6-Di-MeAn”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-MeAn. Results of pH measurement for each run are presented in the following table:
μL 5.0%
% off
T
2,6-Di-MeAn
pH
target
22.5
80.0
2.64
0.0
100.3
80.0
2.65
−0.4
140.7
80.0
2.65
−0.4
Example 25
Temperature Effects on Neutralization of Crude Product with 2,6-Diethylaniline (“2,6-Di-EtAn”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-EtAn. Results of pH measurement for each run are presented in the following table:
μL 8.5%
% off
T
2,6-Di-EtAn
pH
target
22.5
80.0
2.63
0.0
100.3
80.0
2.78
−5.7
140.7
80.0
2.70
−2.7
Example 26
Temperature Effects on Neutralization of Crude Product with 2,5-Di-tert-butylaniline (“2,5-Di-tBuAn”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,5-Di-tBuAn. Results of pH measurement for each run are presented in the following table:
μL 5.6%
% off
T
2,5-Di-tBuAn
pH
target
22.5
70.0
2.49
0.0
100.3
70.0
2.18
12.4
140.7
70.0
1.71
31.3
Example 27
Temperature Effects on Neutralization of Crude Product with 2,6-Diisopropylaniline (“2,6-Di-iPrAn”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-iPrAn. Results of pH measurement for each run are presented in the following table:
μL 15.0%
% off
T
2,6-Di-iPrAn
pH
target
22.5
80.0
2.87
0.0
100.3
80.0
2.92
−1.7
140.7
80.0
2.86
0.3
Example 28
Temperature Effects on Neutralization of Crude Product with Di-n-Hexyl amine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of di-n-hexylamine (“Di-n-HexNH2”). Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
Di-n-HexNH2
pH
target
22.5
110.0
2.57
0.0
100.3
110.0
2.44
5.1
140.7
110.0
2.21
14.0
Example 29
Temperature Effects on Neutralization of Crude Product with Tetramethylammonium Hydroxide (“TMAH”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TMAH. Results of pH measurement for each run are presented in the following table:
μL 0.7%
% off
T
TMAH
pH
target
22.5
50.0
2.56
0.0
100.3
50.0
2.43
5.1
140.7
50.0
2.36
7.8
Example 30
Temperature Effects on Neutralization of Crude Product with Tetra-n-Butylammonium Hydroxide (“TBAH”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TBAH. Results of pH measurement for each run are presented in the following table:
μL 1.1%
% off
T
TBAH
pH
target
22.5
90.0
2.65
0.0
100.3
90.0
2.55
3.8
140.7
90.0
2.48
6.4
Example 31
Temperature Effects on Neutralization of Crude Product with Triethylamine (“TEA”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TEA. Results of pH measurement for each run are presented in the following table:
μL 1.0%
% off
T
TEA
pH
target
22.5
60.0
2.63
0.0
100.3
60.0
2.51
4.6
140.5
60.0
2.50
4.9
Example 32
Temperature Effects on Neutralization of Crude Product with Diisopropylamine (“Di-i-PrNH2”).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-i-PrNH2. Results of pH measurement for each run are presented in the following table:
μL 0.5%
% off
T
Di-i-PrNH2
pH
target
22.5
100.0
2.62
0.0
100.1
100.0
2.46
6.1
140.8
100.0
2.33
11.1
Example 33
Temperature Effects on Neutralization of Crude Product with Ammonium Hydroxide.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with ammonium hydroxide. Results of pH measurement for each run are presented in the following table:
μL 0.33%
% off
T
NH 4 OH
pH
target
22.5
30.0
2.36
0.0
100.2
30.0
2.05
13.1
140.3
30.0
1.49
36.9
Example 34
Temperature Effects on Neutralization of Crude Product with Sodium Hydroxide.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with aqueous solutions of sodium hydroxide. Results of pH measurement for each run are presented in the following tables:
μL 0.8%
% off
T
NaOH
pH
target
22.5
30.0
2.71
0.0
140.3
30.0
2.51
7.4
μL 0.4%
% off
T
NaOH
pH
target
22.5
60.0
2.49
0.0
100.5
60.0
2.46
1.2
140.5
60.0
2.37
4.8
The preceding Examples are intended to describe certain preferred embodiments of the present invention. It should be appreciated, however, that obvious additions and modifications of the invention will be apparent to one skilled in the art. The invention is not limited except as set forth in the claims.
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An improved method for production of phenol and acetone by decomposition of cumene hydroperoxide in the presence of an acidic catalyst to phenol and acetone, wherein the improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a local heating apparatus for sheet glass and, more particularly, to a local heating apparatus suitably used in an apparatus for shaping window glass for a motor vehicle.
2. Description of the Prior Art
Sheet glass which is moderately curved as a whole and has both acutely curved side portions is frequently used as a windshield or rear window glass for a motor vehicle.
The sheet glass having such bent portions is obtained such that sheet glass is softened in a heating furnace and is curved in a bending mold by its own weight or curved by press bending molds consisting of female and male molds. A local heating means is arranged in the heating furnace to forcibly heat a glass plate portion having a smaller radius of curvature.
U.S. Pat. No. 4,441,907 by Nitschke describes that a elongated local heater is located above a bending line of sheet glass while sheet glass is fed at a constant conveyance speed in a heating furnace. The local heater is mounted on a carriage moved in a direction parallel to a conveyance direction of sheet glass and continuously heats a predetermined portion of glass. When the carriage reaches a downstream end of the heating furnace, it returns to an upstream end add performs the next heating cycle of another glass plate.
In the heating apparatus described in the above U.S. patent, the local heater must be moved together with sheet glass, and the structure of the heating furnace is complicated. In addition, a large opening must be formed in the heating furnace to move the heater, and a heat loss is undesirably increased. Furthermore, since the carriage of the local heater returns to the home position after local heating of one glass plate is completed, a shaping cycle is undesirably prolonged.
When the type of sheet glass is changed, the position of the local heater must be changed to align with a heating line. When various types of sheet glass are manufactured in a small volume, productivity efficiency is greatly degraded.
U.S. Pat. No. 4,726,832 by Kajii et al. describes an apparatus capable of coping with shapes of bending lines of various types of sheet glass by digitally controlling the position of a local heater and updating control data. The local heater of this apparatus is a spot-like gas burner which is fixed in the conveyance direction of sheet glass and can be position-controlled by a digitally controlled actuator in a widthwise direction of the heating furnace. Position control of the local heater is performed in synchronism with the conveyance speed of sheet glass in the heating furnace.
Synchronization control of the heater position is performed by digital tracking control. That is, basically, output pulses from a pulse generator arranged in a drive shaft of a conveyor in the heating furnace are counted to detect a current position of glass in the longitudinal direction of the heating furnace. Coordinate data of the heater in the heating furnace in the widthwise direction is read out from a memory area at an address corresponding to the current position. An actuator such as a servo motor is driven on the basis of the readout data to control the position of the heater. Coordinate data in the widthwise direction of the heating furnace which are calculated for a large number of control points on a glass bending line are stored by using the longitudinal coordinate positions as addresses.
According to the above digital control, an actual locus of the heater which is formed on the glass surface is offset from the glass bending line, and a heating temperature of a bent portion does not undesirably reach an optimal point.
The offset of the heating locus from the target heating position is caused by response delay of a heating positioning system and quantization errors inherent to digital control. In particular, the heating locus is not represented by a straight line but by a zig-zag or stepwise pattern having a step between adjacent control points.
In order to solve the above problem, the number of control points assigned with tracking addresses in the longitudinal direction of the furnace must be increased to effectively improve positioning precision. However, when the number of control points is increased, the memory capacity of position control data is increased, and high-speed response cannot be achieved.
SUMMARY OF THE INVENTION
It is an object of the present invention to set a heating locus to be linear and minimize an offset of the heating locus from a bending line even if a local heater is subjected to digital position control.
It is another object of the present invention to perform high-precision position control of the local heater by setting a smaller number of control points.
It is still another object of the present invention to prevent stepwise movement of the local heater even if the local heater is subjected to digital position control.
It is still another object of the present invention to compensate for an offset of the heating locus from the bending line which is caused by response delay of a position control system for the local heater and to perform high-precision position control.
According to an embodiment of the present invention, an elongated local heater substantially directed in a conveyance direction of sheet glass is located above glass, and positions of both ends of the local heater are independently controlled by numerical control data synchronized with conveyance of sheet glass in a direction perpendicular to the conveyance direction of sheet glass. A local heating locus can be linear even if digital position control is performed. Control data is updated in correspondence with various bending shapes of sheet glass, and therefore a heating locus can be easily changed.
According to another feature of the present invention, coordinates of both ends of the bending line on sheet glass are defined, and a large number of control point data on the bending line are obtained by linear interpolation of the coordinates of both the ends at a sheet glass current position in the heating furnace. Therefore, since the large number of control point data are generated from substantially the two control point data, high-precision digital control can be performed.
A difference between the current position of the local heater in the widthwise direction of the heater and the control point position generated by interpolation is used as a velocity component, and the position of the local heater is determined by velocity control. Therefore, movement of the local heater is not stepwise but smooth, and a linear heating locus which accurately matches with a desired bending line can be obtained.
In a preferred embodiment, control point data includes an offset correction component for correcting the offset of the actual heating locus from the desired bending line. This correction can greatly improve position control precision of the local heater.
The above and other objects, features, and advantages of the present invention will be apparent from the following detailed description in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a heating furnace in a glass shaping apparatus according to an embodiment of the present invention;
FIG. 2 is a plan view showing a local heater in the apparatus shown in FIG. 1;
FIG. 3 is a schematic plan view of the heating furnace;
FIG. 4 is a view showing various glass and heater constants;
FIG. 5 is a block diagram of a heater position controller in the apparatus shown in FIG. 1;
FIG. 6 is a detailed block diagram showing a tracking unit in the heater position controller;
FIG. 7 is a flow chart showing a tracking routine;
FIG. 8 is a flow chart showing an X-axis output routine; and
FIG. 9 is a graph showing X-axis control of the heater.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a view showing an overall arrangement of a heating apparatus which employs a local heating apparatus according to the present invention. A heating furnace 1 is a tunnel heating furnace. Heaters or gas burners are arranged near a ceiling of the heating furnace 1. A convey roller 2 rotatably extends between left and right side walls 1a to convey a glass plate G in a direction perpendicular to the drawing surface.
A frame 3 is arranged to surround the heating furnace 1. Units 4 constituting a local heating apparatus are mounted in the frame 3. In practice, the four units 4 are arranged for a pair of electric heaters 23. However, only two units 4, i.e., left and right units are illustrated in FIG. 1 since these units overlap in a direction perpendicular to the drawing surface.
Each unit 4 comprises a frame member 5 suspended from the frame 3 and a lifting member 6 which can be vertically moved with respect to the frame member 5. A motor 7 is fixed on the frame member 5. Rotation of the motor 7 is transmitted to a feed or ball screw 13 through gears 9 and 10. Rods 15 which are inserted in guides 14 fixed in each frame member 5 are fixed to the corresponding lifting member 6. A plate member 16 is bridged between the upper end portions of the rods 15. Nut members 17 fixed to the plate member 16 are threadably engaged with the ball screws 13, respectively.
Upon rotation of each motor 7, the corresponding ball screws 13 are rotated, and the corresponding lifting member 6 is vertically moved upon rotation of the ball screws 13.
A feed or ball screw 19 rotatable by a motor 18 in a direction perpendicular to the conveyance direction of the glass plate G is supported below each lifting member 6. A moving member 20 is threadably engaged with each ball screw 19, and a support member 21 is mounted on this moving member 20. The support member 21 is inserted into the heating furnace 1 through the corresponding vertical opening 22 formed in the corresponding side wall 1a of the heating furnace 1. Each electric heater 23 serving as a local heating member is supported at the distal end portions of the support members 21. The electric heaters 23 are shown in the plan view of FIG. 2. The both end portions of two heaters 23 in a substantially inverted V shape are mounted at the distal end portions of the support members 21 of the two pairs of left and right units 4.
Each motor 18 is driven to rotate the ball screws 19, and the moving members 20 and the support members 21 are moved back and forth in a direction perpendicular to the conveyance direction of the glass plate G upon rotation of the ball screws 19. The back and forth movement of the moving and support members 20 and 21 causes a change in position of the corresponding heater.
FIG. 3 is a schematic plan view showing the overall construction of the heating furnace 1. In practice, the eight pairs of electric heaters 23 are arranged in the rear half portion of the heating furnace 1 in its longitudinal direction, and positions of both the ends of each heater 23 are controlled by the corresponding units 4 shown in FIG. 1 in the widthwise direction of the heating furnace. Local heating is performed along the bending line of the glass plate G. Position control of each heater 23 is performed on the basis of coordinate data using the longitudinal direction as the Y-axis and the widthwise direction as the X-axis.
A pulse generator 26 is mounted on a motor 25 for driving the conveyance roller 2 in the furnace to output a y-coordinate. The pulse generator 26 generates one pulse whenever the glass plate G is fed by a distance, e.g., 100 mm in the furnace. The position of a photoelectric limit switch 27 arranged at the inlet of the furnace 1 serves as the origin of the Y-axis.
X-axis control is performed as shown in FIG. 4. Coordinates (x 1 ,y 1 ) of a start point P1 of the bending line on the glass plate G and coordinates (x 2 ,y 2 ) of an end point P2 are registered as data, and instantaneous X-axis object positions are obtained by linear interpolation between the start point P1 and the end point P2. The start point P1 is a control point when the rear end of the heater 23 reaches the glass plate G. The end point P2 is a control point when the front end of the heater 23 is separated from the glass plate G.
Referring to FIG. 4, assume that a position from a Y-axis origin (limit switch 27) of the support member 21a is defined as Y 3 , that an overall length of the heater 23 is defined as D, that a length from the support point of the heater 23 to the start point is d, that a length of the bending line on the glass surface is defined as L, and that a span width between the corresponding support members 21a and 21b is defined as S. A local coordinate system x-y of the glass plate G is defined by the x-axis passing through the leading end points of the glass plate G and the y-axis passing through the center of the glass plate G. Data of the coordinates (x 1 ,y 1 ) and (x 2 ,y 2 ) of the start and end points P1 and P2 are applied to the coordinate system x-y, and a distance from the x-y origin of a central leading point LS (position passing through the limit switch 27) of the glass is defined as y 0 .
A control start point (X iS ,y 1S ) and a control end point (X 1E ,Y 1E ) of the support member 21a which are obtained by converting the given values into the coordinate system X-Y in the furnace are given as follows: ##EQU1##
X.sub.1S =x.sub.1 -d×(x.sub.2 -x.sub.1)/L
Y.sub.1S =Y.sub.S -d×(y.sub.2 ×y.sub.1)/L+y.sub.1 -y.sub.0
X.sub.1E =X.sub.1S +(L+D)×(x.sub.2 -x.sub.1)/L
Y.sub.1E =Y.sub.1S +(L+D)×(y.sub.2 -y.sub.1)/L
A control start point (X 2S ,Y 2S ) and a control end point (X 2E ,Y 2E ) of the support member 21b are
X.sub.2S =X.sub.1S -S×(x.sub.2 -x.sub.1)/L
Y.sub.2S =Y.sub.1S
X.sub.2E =X.sub.1E -S×(x.sub.2 -x.sub.1)/L
Y.sub.2E =Y.sub.1E
Control start points (X iS ,Y iS ) (i=1 to 16) and control end points (X iE ,Y iE ) of all other support members 21 can be similarly obtained.
FIG. 5 is a block diagram of a position controller, and Y-axis tracking of the glass and X-axis servo control of the heater 23 are performed by a PLC (Programmable Logic Controller) 30. The glass constants y 0 , (x 1 , y 1 ), and (x 2 , y 2 ) are supplied from a master computer 34 to the PLC 30 through a communication interface 35 whenever the type of glass is changed.
The PLC 30 calculates a current position Y Gj (j=0 to 9) of each glass plate G in the heating furnace on the basis of the count of a counter 28. When the current position of the glass plate falls within a heating area of the heater 23, the PLC 30 instantaneously calculates the X-axis control positions (object positions) of the 16 support members 21 at predetermined time intervals.
The pulse generator 18a is coupled to the motor 18 for displacing each support end of the heater 23 in the X-axis. An output pulse from the pulse generator 18a is supplied to a counter 32 through a servo controller 33. Data X h of the x-axis current position is obtained from the count of the counter 32.
The PLC 30 calculates a difference between the object position X i and the current position X h and multiplies the difference with a constant. The product is output to a D/A converter 31. An output from the D/A converter 31 is supplied to the servo controller 33 as a velocity control value or voltage. Therefore, the X-axis motor 18 is controlled to generate a velocity corresponding to the difference between the object position and the current position.
Upon rotation of the motor 18, pulse outputs from the pulse generator 18a are counted by the counter 32, and the value of the current position X h is increased. Therefore, the difference between the object position X i and the current position X h is decreased, and the motor 18 is then decelerated. Servo locking is performed to cause the motor 18 to trace a change in object position X i as a function of time.
Y-axis tracking of the glass plate G and the X-axis servo control will be described in detail with reference to FIGS. 6 to 9.
FIG. 6 shows a tracking unit included in the controller 30 of FIG. 5 to monitor the glass position in the furnace. The tracking unit comprises the counter 28 for counting outputs from the pulse generator 26 and a memory 29 for storing outputs from the counter 28 at every output timing of the limit switch 27. The memory 29 has ten memory areas for tracking 10 Y-axis positions of the glass plates G (N, N+1, . . . , N+9) continuously conveyed in the furnace. Counts S N , S N+1 , . . . S N+9 from the counter 28 are stored in each area every time the leading end of the glass plate G reaches the position of the limit switch 27. The memory 29 is a FIFO memory. When the (N+10)-th glass plate G reaches the position of the limit switch 27, the oldest data S N is read out from the memory 29, and count data S N+10 is stored in the empty area.
FIG. 7 is a flow chart showing a tracking routine performed by the PLC 30. When the limit switch 27 is turned on, a PG count value is stored in the memory 29 (steps S1 and S2). In step S3, an offset ΔY matching with the conveyance speed of the glass plate G is added to the memory data. The offset component is added for the X-axis position correction.
In step S4, when a pulse output from the pulse generator 26 is detected, the data from the memory 29 is subtracted from the current PG pulse count of the counter 28. A difference Y Gj represents the current position of the glass plate G in the furnace (step S5). The operation in step S5 is repeated every time the pulse generator 26 generates an output pulse for all the glass plates (N to N+9).
The calculated current position data Y Gj is used in the X-axis output routine in FIG. 8.
In this routine, in step S6, it is determined whether the value of the current position Y Gj of the j-th glass falls within a heating area (Y iS to Y iE ) (where i=1, 2, . . . , 16, which represent 16 support members 21 for supporting the eight heaters 23 on one side shown in FIG. 3) (i.e., the control start point to the control end point) of the heater 23. For example, it is detected that the glass plate G represented by the alternate long and short dashed line in FIG. 3 reaches the control start position Y 13 , and X-axis control of the corresponding heater 23 is started.
When each glass plate G enters into the heating area of each heater 23, an X-axis object position X i of the i-th support member 21 is obtained in step S7 as follows:
X.sub.i =X.sub.iS +(Y.sub.Gj -Y.sub.iS)×(X.sub.iE -X.sub.iS)/(Y.sub.iE -Y.sub.iS)
That is, as shown in FIG. 9, linear interpolation is performed at the current position Y Gj between the control start point (X iS ,Y iS ) and the control end point (X iE , X iE ) of the support 21 to obtain X i .
In step S8, a constant K is multiplied with a difference between the object position X i and the current position X h , and the product is D/A-converted to obtain an X-axis velocity control value:
v.sub.x =K(X.sub.i -X.sub.h)
The velocity control value v x is output to the servo controller 33. As a result, the velocity v x shown in FIG. 9 is given to the support member 21, and smooth position control is performed. A composite velocity v of the velocity v X and the conveyance speed v Y of the glass plate G in the furnace is directed in the direction of a heating locus (bending line).
The X-axis output routine in FIG. 8 is performed every predetermined intervals for i (1 to 16) and j (0 to 9). Identical X-axis control data are supplied to the paired drive units for the heaters 23, and the drive units are symmetrically operated.
An actual heating locus R of the heater 23 is offset by ΔX from the calculated object locus T in the X-axis, as shown in FIG. 9. This offset includes the following components.
(i) a difference v x /K is required between the object position an the current position in order to obtain the velocity v x .
(ii) The glass plate is conveyed by a distance v Y Δt within a time lag Δt until the current position value is input and a velocity control value is output.
Therefore,
ΔX=v.sub.x /K+v.sub.Y ·Δt·(X.sub.iE -X.sub.iS)/(Y.sub.iE -Y.sub.iS)
The offset occurs by ΔX in the X-axis, and therefore, the corresponding offset in the Y-axis is given as
ΔY=v.sub.x /K+(X.sub.iE -X.sub.iS)/(Y.sub.iE -Y.sub.iS)+v.sub.Y ·Δt
In order to correct the offset ΔX, the start position is shifted to a point (X iS ,Y iS -Y). Alternatively, the offset value corresponding to the offset ΔX is added to the value of the object position X i between the start and end points.
In practice, as shown in step S3 of FIG. 7, the offset ΔY is subtracted from the data from the tracking memory 29. Therefore, the offset ΔY is added to the current position Y Gj of the glass which is calculated in step S5, and the control start position is relatively advanced by the offset ΔY.
The offset ΔY must be changed in accordance with a change in conveyance speed v Y of the glass. When the type of glass plate to be shaped is changed, the value ΔY is supplied from the master computer 34 to the PLC 30 in FIG. 5.
In the above embodiment, the elongated heater is used. However, a spot-like heater may be used to perform heating locus data control according to the present invention.
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A local heater is arranged in a heating furnace in which glass plates are continuously conveyed, and a bending line on each glass plate is forcibly heated. The local heater is elongated, and positions of both ends of the local heater are independently and digitally controlled in a widthwise (X-axis) direction of the heating furnace. Control point data along the bending line is obtained by interpolating coordinate values of both ends of the bending line. X-axis velocity control is performed such that the local heater is located on the glass bending line in synchronism with conveyance of the glass plate. A heating locus is linear, and the operation of the local heater is not stepwise. An offset of the actual heating locus from the bending line can be minimized.
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RELATED APPLICATION
[0001] This application claims priority from co-pending provisional application U.S. Ser. No. 60/946,815, which was filed on 28 Jun. 2007, and which is incorporated herein by reference in its entirety. This application is also a continuation-in-part of Ser. No. 11/412, 665, filed on 27 Apr. 2006 and which is additionally incorporated herein by reference in its entirety.
STATEMENT OF GOVERNMENT RIGHTS
[0002] The investigation leading to this application was supported at least in part by a grant from the National Science Foundation. The government may, therefore, have some rights in the invention, as specified by law.
FIELD OF THE INVENTION
[0003] The present invention relates to the field of nanotechnology and, more particularly, to nanoceria particles which carry a medicinal drug.
BACKGROUND OF THE INVENTION
[0004] Countless individuals suffer from the ocular disease glaucoma. This condition describes a destruction of optic nerve cells and deterioration of eyesight as a result of increased intraocular pressure. The pressure is caused in part by a buildup of carbon dioxide in the eye. An enzyme that aids in the production of CO2 is human carbonic anhydrase II (hCAII). This Zn 2+ containing metalloenzyme ( FIG. 1 ) catalyzes the reversible hydration of carbon dioxide to bicarbonate and is commonly found in living organisims.
[0005] Sulfonamide compounds have been shown to selectively inhibit hCAII even at low concentratons. 1 Therefore, inhibition of hCAII with sulfonamides constitutes one of the most physiological approaches for treatment of glaucoma. In 1958 Beasley et al. reported the in vitro binding of 4-carboxybenzene sulfonamide (CBS) to the carbonic anhydrase (CA) enzymes. 2 Since then, many other hCAII inhibitors based on this moiety have been reported. 3-5 A remarkable increase in the hCAII inhibition activity was observed for simple aliphatic esters of CBS. 5 Also, it is now extensively documented that significant enhancement of CA inhibition can be achieved through coupling the primary recognition aromatic sulfonamide motif with secondary binding elements. 3,5-9 The mechanism for inhibition of hCAII by CBS involves coordination of the sulfonamide group (as the anion) to the zinc atom in the active site of hCAII to form a complex in an exothermic reaction. 6, 10, 11.
[0006] In ophthalmic diseases such as glaucoma, treatment with conventional liquid eye drops is an inefficient mode of therapy because of lachrymal drainage losses. Because of the high elimination rate, only a very small amount of about 1-3% of the dosage actually penetrates through the cornea and is able to reach intraocular tissues. 12-14 Nanoparticles provide a promising potential as drug carriers for ophthalmic applications. The colloidal nanoparticles may be applied in liquid form just like eye drop solutions. After optimal drug binding to the nanoparticles, the ocular bioavailability of many drugs is significantly enhanced in comparison to normal aqueous eye drop solutions. 12 Also, smaller particles improve patient comfort during administration as a scratchy feeling tends to occur with larger particles. Nanoparticles and microspheres of various synthetic polymers such as poly-butylcyanoacrylate, 15,16 polylactic acid, 17 polymethylmethacrylate, 16 and so forth as well as natural biocompatible polymers like albumin 18,19 have been used for ophthalmic drug delivery applications.
SUMMARY OF THE INVENTION
[0007] With the foregoing in mind, in one embodiment, the present invention advantageously provides a composition comprising a plurality of nanoceria particles, a sufficient amount of at least one inhibitor of human carbonic anhydrase II associated with said plurality of nanoceria particles, and a pharmaceutically acceptable carrier containing said plurality of nanoceria particles with associated inhibitor. The at least one inhibitor of human carbonic anhydrase II preferably comprises 4-carboxybenzene sulfonamide. Preferably, the enzyme inhibitor is effective against human carbonic anhydrase II and the composition is used in treating an eye disease, particularly glaucoma, by contacting the eye with the composition.
[0008] The composition may also further comprise a detectable tag associated with the plurality of nanoceria particles. The skilled will recognize that the term “tag” indicates any atom or molecule which, when associated with the nanoceria, imparts a property which allows for tracking of the nanoceria during treatment. Tracking may be by any known method, for example, fluorescence responsive to ultraviolet light. In effect, the tag may be a fluorescent tag associated with said plurality of nanoceria particles and the fluorescent tag is preferably a fluorescein compound associated with said plurality of nanoceria particles, in particular, carboxyfluorescein.
[0009] In this preferred embodiment of the invention, the nanoceria particles are made by a method comprising a reaction according to Scheme 1A, shown in FIG. 3 . Moreover, the nanoceria particles associated with carboxyfluorescein are made by a method comprising a reaction according to Scheme 1B in FIG. 3 .
[0010] Another embodiment of the invention includes a composition comprising a plurality of nanoceria particles, a sufficient amount of at least one biologically active agent bound to said plurality of nanoceria particles, and a pharmaceutically acceptable carrier containing said plurality of nanoceria particles with bound inhibitor. Preferably, the biologically active agent comprises a medicinal drug and, particularly, an ophthalmically active drug, which could be an enzyme inhibitor. In particular, the biologically active agent could comprise a sulfonamide compound, especially one that inhibits human carbonic anhydrase.
[0011] Another preferred embodiment of the invention includes a method of treating a patient's eye condition. The method comprises providing a composition containing a plurality of nanoceria particles associated with a drug and suspended in a pharmaceutically acceptable carrier, and contacting the patient's eye with the composition.
[0012] In this embodiment, the drug preferably comprises an enzyme inhibitor and especially an inhibitor of human carbonic anhydrase. The eye condition comprises glaucoma and drug comprises 4-carboxybenzene sulfonamide. In the method, contacting the eye may be accomplished in any fashion known to the skilled but, typically would comprise a procedure selected from instilling, injecting, diffusing and combinations thereof.
[0013] Nevertheless, while this disclosure preferably comprises nanoceria compositions and treatments directed to eye conditions and, particularly, to glaucoma, the invention includes within its scope the concept of associating a drug with the nanoceria particles as carriers. The range of drugs that can be employed in the invention is rather broad and includes any drug or pharmaceutical composition that can be complexed, associated with or otherwise bound to the nanoceria particles without significantly adversely affecting the biological activity of the drug.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Some of the features, advantages, and benefits of the present invention having been stated, others will become apparent as the description proceeds when taken in conjunction with the accompanying drawings, presented for solely for exemplary purposes and not with intent to limit the invention thereto, and in which:
[0015] FIG. 1 is a cartoon diagram showing the structure of human carbonic anhydrase;
[0016] FIG. 2 depicts the molecular structure of (a) carboxybenzene sulfonamide (CBS) and (b) carboxylfluorescein (CBF);
[0017] FIG. 3 depicts schemes for synthesis of functionalized nanoceria; (A) for nanoceria-CBS; and (B) for nanoceria-CBS-CBF, according to embodiments of the present invention;
[0018] FIG. 4 shows high-resolution XPS spectra for the functionalized nanoceria particles at various conjugation steps; (a) O Is scan for epichlorohydrin-functionalized nanoceria; (b) O Is scan for the opened epoxide ring of epichlorohydrin; (c) O Is scan for carboxybenzene sulfonamide-functionalized nanoceria; and (d) C Is scan for carboxyfluorescein-functionalized nanoceria;
[0019] FIG. 5 are images from confocal fluorescence microscopy of (a) bare nanoceria and (b) nanoceria with fluorophores; and
[0020] FIG. 6 shows line graphs indicating the rate of hydrolysis of 4-nitrophenyl acetate by hCAII, determined using absorbance change at 400 nm, as a function of the nanoceria concentration.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0021] The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. Any publications, patent applications, patents, or other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including any definitions, will control. In addition, the materials, methods and examples given are illustrative in nature only and not intended to be limiting. Accordingly, this invention may be embodied in many different forms and should not be construed as limited to the illustrated embodiments set forth herein. Rather, these illustrated embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
[0022] The term “pharmaceutical composition” is used herein as commonly known by those skilled in the art and generally indicates a mixture containing ingredients that are compatible when mixed and which may be administered to a patient or biological system, whether human, animal or in vitro, in order to treat a condition or disease. A pharmaceutical composition may cause a degree of toxicity in the patient to whom it is administered but, typically, it would be given in a dosage form and/or amount that does not cause substantial harm to the patient or biological system being treated. Examples of this dichotomy would include pharmaceutical compositions for cancer chemotherapy, which are more toxic for cancer cells than for normal cells but, nevertheless, exert a level of toxicity on the patient's normal cells during treatment. A pharmaceutical composition may include one or more medicinal drugs, which may or may not be prescription drugs. Additionally, the pharmaceutical composition may include carriers, solvents, adjuvants, emollients, expanders, stabilizers and other components, whether these are considered active or inactive ingredients. The skilled will readily understand that the exact makeup of the composition will depend on the intended route of administration to the patient, for example, a composition intended for topical application to the skin will necessarily contain different components than one intended for ophthalmic instillation. Guidance for the skilled in preparing pharmaceutical compositions may be found in the U.S. Pharmacopeia-National Formulary and other recognized treatises in the science of pharmacy.
[0023] The figures illustrate the invention disclosed, which comprises inhibition of hCAII, a primary target enzyme for the treatment of glaucoma. Nanoceria, a nontoxic nanoparticle, was functionalized with hCAII inhibitors and was tested as a potential ophthalmic drug delivery tool. We have found various applications of cerium oxide nanoparticles in biotechnology. It was found that treatment with nanomolar concentrations of cerium oxide nanoparticles increases cell longevity 20 and protects the cells from damages caused by X-ray radiation 21 and reactive oxygen species (ROS). These previous studies have revealed that nanoceria particles are nontoxic and exhibit favorable biocompatibility.
[0024] Our studies related to use of nanoceria to protect the retina from oxidative stress caused by reactive oxygen species showed that the nanoparticles injected in the vitreous showed efficacy far away in the retina. 22 Moreover, the nanoceria's uptake in human lung fibroblast cells was shown to be faster than the physical transport to the cell 23 suggesting that these particles have favorable diffusive properties. Therefore, a composition of CeO2 nanoparticles was deemed as potentially very good candidate for serving as transport agent for the inhibitors. Since carbonic anhydrase n is a cytosolic enzyme, that is, it is found in cellular cytoplasm, the inhibitor-functionalized nanoceria were synthesized to allow easy entry into living cells.
[0025] The first step was to choose a molecule that can attach to the nanoceria and that can inhibit carbonic anhydrase. Carboxybenzene sulfonamide (CBS) ( FIG. 2 a ) was the primary choice on the basis of the literature data, where it is shown that these benzenesulfonamides can serve as inhibitors of carbonic anhydrases and can possess favorable carboxyl groups for attachment. 8,24 It was hypothesized that binding these molecules to the nanoceria would create an effective inhibitor of carbonic anhydrase that can be transferred into the cytosol. Additionally, we also decided to attach a tracking compound, a carboxyfluorescein molecule ( FIG. 2 b ), to visualize the cell permeation property of the nanoparticles through a confocal fluorescence microscope.
[0026] The attachment of carboxybenzene sulfonamide and carboxyfluorescein molecules to nanoceria was confirmed using X-ray photoelectron spectroscopy (XPS). The formation of the fluorophore-functionalized nanoparticles was further established through confocal fluorescence microscopy. Finally, the derivatized nanoceria were tested as inhibitors of the recombinant hCAII enzyme. This was accomplished by observing the effect of nanoparticles on the rate of hCAII-catalyzed hydrolysis of the substrate 4-nitrophenyl acetate. 26
Experimental Section
Functionalization of Cerium Oxide Nanoparticles (Scheme 1, FIG. 3 ).
[0027] Reaction of CeO2 Nanoparticles with Epichlorohydrin and Ammonia.
[0028] The 250 mg of cerium oxide nanopowder (obtained from Sigma-Aldrich Inc.) was suspended in 10 mL of 0.1 M NaOH solution for 5 min. Then, 5 mL of epichlorohydrin was added, followed by the addition of 0.5 mL of 2 M NaOH. The suspension was stirred at room temperature for 6-8 h. The reaction mixture was then centrifuged, and the supernatant was decanted. The nanoparticles were washed by water followed by centrifugation. This was done until the pH of the water was approximately 7.0. The nanoceria powder was then dried under vacuum. Next, the nanopowder was again suspended in water, 25 mL of 30% ammonium hydroxide solution was added, and the reaction mixture was stirred for 14 h. The product was purified by centrifugation, was washed with water, and was dried under vacuum again.
[0000] Reaction with Carboxybenzene sulfonamide and Carboxyfluorescein.
[0029] The nanoparticles from the previous step were functionalized with the carboxybenzene sulfonamide and carboxyfluorescein molecules. These molecules (either 200 mg, 1 mmol of the CBS or carboxyfluorescein) were sissolved in 15 mL of dimethylformadide (DMF) and 5 mL of dichloromethane. Three hundred sevent-five microliters (3.5 mM) of N-methylmorpholine (NMP) was added followed by the addition of 442.5 mg (1 mmol) of the benzotriazol-1-yl-oxy-tris-(dimethylamino) phosphonium hexafluorphosphage (BOP) reagent. The reaction mixture was stirred for 10 min at room temperature. The nanoparticles were then added. The mixture was stirred for approximately 20 h at room temperature. The reaction was stopped with 1 mL of water, and the mixture was centrifuged. It was then washed with DMF, water, and acetone three times each to get rid of the unattached carboxyfluorescein and finally was centrifuged. The nanoparticles were finally dried under vacuum.
[0030] The carboxyfluorescein-functionalized nanoparticles were taken through the same procedure to attach additional CBS. This resulted in nanoparticles functionalized with carboxybenzene sulfonamide, as well as particles with both the CBS and carboxyfluorescein as shown in Scheme 1.
X-ray Photoelectron Spectroscopy (XPS)
[0031] The surface functionalization chemistry of the nanoceria was examined using a 5400 PHI ESCA (XPS) spectrophotometer. The base pressure during the XPS analysis was approximately 10 −9 Torr, and Mg Kα X-radiation (1253.6 eV) at a power of 200 W was used. The instrument was calibrated using a standard gold sample with the binding energy at 84.0±0.1 eV for Au (4f 7/2 ). All the samples were placed on a carbon tape. Any charging shift produced during the scanning was subtracted by using a binding energy scale with the baseline set at 284.6 eV for the C (1s). 27 The XPS spectra were deconvoluted using PeakFit (version 4) software. The surface concentration of various conjugates was 158 evaluated from the integrated areas of the peaks corresponding to the respective conjugates.
Confocal Fluorescence Microscopy (CFM).
[0032] An Olympus 161 Fluoroview IX 81 confocal fluorescence microscope was used. Imaging was performed on prepared slides with nanoceria samples functionalized with carboxyfluorescein. The concentration of nanoceria was optimized to 1 mg/mL of water for imaging. The emission and excitation wavelengths for carboxyfluorescein were determined to be 520 and 480 nm, respectively.
Ultraviolet-Visible Spectrophotometry (UV-vis).
[0033] Cary 1E UV-vis spectrophotometer (UV-vis) from Varian Inc. was used to determine the inhibition potential of the nanoceria functionalized with the CBS. The enzyme activity was measured in 25 mM HEPES buffer, pH 7.0 at 25° C., containing 10% acetonitrile. The concentration of hCAII (obtained from Sigma-Aldrich Company) was kept constant at 1 uM for all the experiments. The concentration of the substrate, 4-nitrophenyl acetate (in acetonitrile), was 1 mM for experiments carried out with varying concentrations of functionalized nanoceria and varied between 1 and 5 mM for the kinetic parameter determination studies with constant concentration of the functionalized nanoceria at 0.16667 mg/mL. The initial rates of 4-nitrophenyl acetate hydrolysis by hCAII were monitored spectrophotometrically, at 400 nm, using the Cary Win UV Kinetics application. The molar absorption coefficient, ε of 18 400 M −1 cm −1 , was used to determine the concentration of 4-nitrophenolate formed by hydrolysis, as reported in the literature. 28
[0034] The substrate concentration dependent kinetic data in the absence and presence of functionalized nanoceria inhibitors was presented in the form of double reciprocal plots and was analyzed according to the Michaelis-Menten equation to obtain the K m and V max values. The inhibitor binding constant, K i , for the functionalized-nanoceria inhibitors was determined according to the following relationship: 29
[0000]
K
i
=
K
m
[
I
]
K
m
′
-
K
m
[0000] where, [I] is inhibitor (functionalized nanoceria) concentration; K m and K m′ are Michaelis constants in the absence and presence of the inhibitor, respectively.
Results
[0035] The expected functionalization of nanoceria was confirmed by XPS. The attachments of the epichlorohydrin linker, the inhibitor, and the fluorophore were established by examining the high-resolution C (1s) and O (1s) XPS spectra. The attachment of the fluorophore-functionalized nanoparticles was further confirmed by imaging using a confocal fluorescence microscope.
Functionalization Chemistry Using X-ray Photoelectron Spectroscopy (XPS).
[0036] The carboxybenzene sulfonamide and carboxyfluorescein were conjugated by first attaching epichlorohydrin to the surface of nanoceria particles. This is a standard S N 2 reaction where the oxygen atom of the nanoceria essentially replaces the chlorine atom of the epichlorohydrin. 30 This results in an oxygen atom that bonds the cerium with the carbon of the epichlorohydrin as seen in the first reaction of Scheme 1, as shown in FIG. 3 .
[0037] In case of nanocrystalline cerium oxide, the O (1s) spectra contain two peaks corresponding to the mixed valence state of Ce (Ce 3+ and Ce 4+ ) present in its crystal lattice. The peak at 530.5 eV corresponds to Ce 4+ while the higher binding energy peak at about 532.20 eV corresponds to Ce 3+0.31 The two additional peaks present in the spectra given in FIG. 4 a demonstrate that the expected functionalization occurred. These peaks include the O (1s) line of the epichlorohydrin's epoxy group at 533.30 eV and the O—C bond that connects the main part of the epichlorohydrin molecule to the cerium oxide at 534.10 eV. 32 The high-resolution O (1s) XPS spectra thus indicate the successful attachment of the epichlorohydrin molecule to cerium oxide nanoparticles. The loading of epichlorohydrin on the ceria nanoparticles, calculated from the integrated areas of O peaks corresponding to epichlorohydrin to those for Ce 3+ and Ce 4+ , was evaluated to be 3.18 mmol/gm of CeO2.
[0038] Ammonia was then used to open up the epoxide ring (S N 2 reaction) on the epichlorohydrin molecule to form amine (—NH 2 ) and hydroxyl (—OH) groups available for further reactions ( FIG. 3 , Scheme 1). The indication that this reaction occurred lies in the diminishment of the peak at 533.30 from FIG. 4 a . The new peak at 533.00 eV in FIG. 4 b corresponds to the newly formed —OH groups. 32 However, FIG. 4 b also confirms that the O—C bond that links the epichlrohydrin molecule bond to the nanoceria remained with the peak at 534.00 eV. Thus, the epichlrohydrin was still attached to the nanoceria and the epoxide ring opened as expected. The integrated area analysis of the peaks confirmed almost 100% ring opening for the epoxide group of the epichlorohydrin conjugated to the cerium oxide nanoparticles.
[0039] The nanoceria now possessed two functional groups that could be further functionalized by the carboxybenze sulfonamide and carboxyfluorescein molecules. Both of them have carboxyl groups that can react to the available amine and hydroxyl groups from the opened ring of the surface-functionalized nanoceria ( FIG. 2 ). The coupling reactions included standard peptide coupling reagents, N-methyl morpholine (NM)) and benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate (BOP). The reactions were conducted in dimethylformamide (DMF), a polar aprotic solvent that facilitates the coupling.
[0040] The attachment of the inhibitor, CBS, to the amine group was confirmed by the O 1 s XPS spectrum in FIG. 4 c . The locations of all of the peaks essentially remained the same from the previous spectrum in FIG. 4 b except for two additional peaks. These peaks at 531.13 and 531.70 eV correspond to the double-bonded oxygen atoms of the C═O and S═O bonds, respectively, that are part of the CBS. The XPS analysis thus indicated that the inhibitor bonded to the nanoceria particles. The loading yield determined from the deconvoluted peak areas was evaluated to be 3.14 mmol/gm of CeO 2 (98.8%).
[0041] Instead of the O 1s spectrum, the carbon (C 1s) spectrum was used to confirm the attachment of carboxyfluorescein, because this large molecule shielded many of the oxygen peaks seen in the previous oxygen spectra. FIG. 4 d shows the various peaks present in the XPS spectra corresponding to the different C positions in the structure of the carboxyfluorescein functionalized ceria nanoparticles. It confirms that the fluorophore was also attached successfully to the ceria nanoparticles via epichlorohydrin linkage. The XPS peak analysis gave the surface concentration of the fluorophore to be 6.0 mmol/gm of CeO 2 . The results of the high-resolution XPS spectra for all of the reactions are summarized in Table S 1 of the Supporting Information (not shown but incorporated herein by reference; this material is available to the public free of charge via the Internet at http://pubs.acs.orq a web site of The American Chemical Society).
Confocal Fluorescence Microscopy.
[0042] Further evidence that the fluorescent molecules bonded was presented in the confocal fluororescence microscopy images. As seen in FIG. 4 , the carboxyfluorescein-functionalized nanoparticles were clearly visible under a confocal fluorescence microscope (λ ex =480 nm; λ em =520 nm) as green dots while the bare nanoceria resulted in images showing a black background. An individual green dot represents a small agglomerate of the ceria nanoparticles (particle size: 10-20 nm) successfully functionalized with carboxyfluorescein. This further demonstrates that the fluorophores were attached to the nanoceria. The procedure for attaching these fluorescent molecules can be used in future studies to track the nanoceria as they are inserted into living cells. Future studies will involve inserting these particles in vivo and tracking their movement as they approach the expected locations of enzymes.
Inhibition Studies.
[0043] The final facet of the study involved determining whether the functionalized nanoceria inhibited the recombinant hCAII enzyme. This was accomplished by observing the effect of nanoparticles on the rate of hCAII-catalyzed hydrolysis of the substrate 4-nitrophenyl acetate. Essentially, the nanoparticles were mixed with a solution of the 4-nitrophenyl acetate and enzyme. The UV-vis spectrophotometer then measured the absorbance values at 400 nm as 4-nitrophenylacetate was hydrolyzed to form 4-nitrophenolate. The change in the absorbance values at different concentrations of nanoceria indicated the inhibiting effect of the conjugated nanoparticles.
[0044] The declining slopes in FIG. 6 reveal that, when the inhibitor-functionalized nanoceria bound to the active site of hCAII, the rate of formation of 4-nitrophenolate from 4-nitrophenyl acetate decreased. A decrease in the rate of its formation produced a solution that became tinted at a slower rate, which was represented by the decrease in the absorbance values as a function of time (see FIG. 6 ). hCAII's activity declined with increased concentration of nanoceria, as indicated by the decreasing rate for the hydrolysis of 4-nitrophenyl acetate to 4-nitrophenolate. Bare nanoceria did not affect the rate of hydrolysis of 4-nitrophenyl acetate. When the inhibitor was paired with the fluorophore, the inhibition was better than with nanoceria functionalized only with CBS. The kinetic parameters (K m , V max and K i ) for the functionalized nanoceria samples, determined using the double-reciprocal plots, are summarized in Table 1.
[0000]
TABLE 1
Kinetic Parameters of the hCAII-Catalyzed Reaction in the
Absence and Presence of Functionalized-Nanoceria Inhibitors
inhibitor
K m (mM)
V (mM/min)
K i (mg/mL)
no inhibitor
115.23 ± 1.36
3.02 ± 0.15
nanoceria with
125.40 ± 0.98
3.24 ± 0.08
1.89 ± 0.16
inhibitor (CBS)
nanoceria with
135.24 ± 1.10
3.12 ± 0.10
0.96 ± 0.09
inhibitor (CBS)
and fluorophore
(carboxyfluorescene)
indicates data missing or illegible when filed
Discussion
[0045] One of the emerging goals of nanotechnology is to functionalize inert and biocompatible materials to impart precise biological functions. Several hybrid organic/inorganic nanoparticles have been described for diagnostic or therapeutic use, 34,35 including quantum dots, 36,37 polymers, 38 and magnetofluorescent nanoparticles. 39 Although many coupling systems have been reported for polymeric nanoparticle conjugation with varying degrees of success, 40,41 the coupling and functionalization of inorganic nanoparticles with biomolecules has only been carried out with a limited number of chemical methods. Niemeyer42 has written an elaborate review on usage of various coupling agents such as citrate, streptavidin, and various other complex linker molecules with amide and carboxylic acid end groups for coupling of inorganic nanoparticles (Au, Ag, ZnS, CdS, SnO 2 , TiO 2 , etc.) and biomolecules (proteins, DNA, etc.).
[0046] In this disclosure, we have shown the simultaneous conjugation of the hCAII inhibitor, CBS, and the fluorophore, carboxyfluorescein, to cerium oxide nanoparticles via epichlorohydrin as a linker molecule. Epichlorohydrin is a highly reactive compound used in manufacture of epoxy and phenoxy resins. It is also used as a solvent and in the synthesis of glycerol. Anirudhan et al. 43 have developed a new adsorbent system for phosphate removal from wastewaters using epichlorohydrin to modify lignocellulosic residue. Also, it has been used in synthesis of lipopolyhydroxylalkylamines for gene delivery. 44 Weissleder et al. 45 cross-linked the monocrystalline magnetic nanoparticles, consisting of 3 nm core of (Fe 2 O 3 ) n (Fe 3 O 4 ) m covered with a layer of dextran, with epichlorohydrin and aminated them by reaction with ammonia to provide primary amine groups for the parallel synthesis of a library comprising 146 nanoparticles decorated with different synthetic small molecules. Similarly, in the present study, epichlohydrin was attached to the ceria nanoparticles via a condensation reaction between the orga-nochloride group from epichlorohydrin and the surface hydroxyl groups of the nanoceria particles and then was aminated to provide primary amine group for conjugation of enzyme inhibitor as well as the fluorophore to the nanoceria particles. The epichlorohydrin may have provided a spacer that allowed the inhibitor to reach the active site of the carbonic anhydrase and to reduce any steric hindrance of the enzyme's interaction with the inhibitors on the surface of the nanoparticles. Furthermore, the inhibition was nearly directly proportional with increased concentration of the functionalized nanoceria inhibitors ( FIG. 6 ). The analysis of the kinetic data conformed to the competitive type of inhibition model. Higher K m values in the presence of functionalized nanoceria inhibitors than in its absence eliminate the possibility of “noncompetitive inhibition”. In conclusion, these results demonstrate that inhibition of the hCAII enzyme can be achieved using nanoceria particles surface-functionalized with CBS.
[0047] The aim of the present application is to show that a successful conjugation of the ceria nanoparticles can be carried out using epichlorohydrin as a linker molecule and that such conjugated nanoparticles can be used for hCAII inhibition along with fluorescence-imaging capabilities. The inhibition results may be further enhanced using multiprong surface-binding groups. Our earlier studies in this regard have shown a potential strategy to improve inhibition of hCAII by attaching a surface-histidine recognition group to the inhibitor. Our on-going investigations include the usage of the same conjugation process for multiprong inhibitors of hCAII for improved results.
CONCLUSION
[0048] Nanoceria were successfully functionalized and tested as inhibitors for hCAII. High-resolution XPS C 1s and O 1s spectra were effectively utilized to follow the necessary steps in the reaction process. The fluorescence microscope images and quantitative observations further confirmed that the carboxyfluorescein molecules bonded to the nanoceria particles. These results are very promising, and more studies will likely evolve into an inhibition of hCAII in living cells and an effective treatment of glaucoma and other diseases.
[0049] Furthermore, inhibitors for other disease associated enzymes can be immobilized on the nanoceria and then applied to the enzymes. The potential applications for functionalized cerium oxide nanoparticles seem limitless as a potential nontoxic drug delivery tool.
[0050] Accordingly, in the drawings and specification there have been disclosed typical preferred embodiments of the invention and although specific terms may have been employed, the terms are used in a descriptive sense only and not for purposes of limitation. The invention has been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the invention as described in the foregoing specification and as defined in the appended claims.
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The invention provides a composition comprising a plurality of nanoceria particles, a sufficient amount of at least one inhibitor of human carbonic anhydrase II associated with said plurality of nanoceria particles, and a pharmaceutically acceptable carrier containing said plurality of nanoceria particles with associated inhibitor. One preferred inhibitor of human carbonic anhydrase II comprises 4-carboxybenzene sulfonamide. The disclosed composition is useful in treatment of glaucoma.
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FIELD OF THE INVENTION
This invention relates to bacteriological inoculating devices and, in particular, to a device which combines in a single integral unit an inoculating loop for transferring a quantitative bacteriological sample to a culture medium, an improved streaker for spreading the sample across the medium, and a built-in picker for selectively picking bacterial colonies when growth appears.
BACKGROUND OF THE INVENTION
Inoculating loops have been used to transfer bacteria from one medium to another, e.g. from pathogenic substances to a culture medium. In the past, the inoculating loop has been a long thin piece of wire looped at one end. The loop was usually made of platinum wire and was sterilized by exposing the wire to a heat source such as a flame or an electric heater.
Because the heating process and subsequent cooling of the loop was somewhat time consuming, disposable plastic inoculating loops were developed and used. The inexpensive plastic loops were used once and discarded, avoiding the step of resterilizing the loop. The use of plastic loops accordingly resulted in a time savings especially when processing large numbers of samples. Additionally, because a flame or heating unit was no longer required, inoculations could be done in places which were previously impractical, such as in the field, under hoods, in anaerobic chambers, in glove boxes, in doctors'offices and for satellite laboratory testing. Safety was also improved in that accidental fires were prevented and spattering of pathogenic substances, caused by heating the substance in a flame, was avoided. One of the early plastic loops is illustrated in FIG. 1. As shown, the device is simply a long thin member having a loop formed at one end.
An improvement made to the plastic inoculating loop is shown in FIG. 2. This device again has a loop formed at one end. The other end, however, is needle-shaped and used as a picker. The picker is used to selectively transfer a bacterial colony to another culture medium for further growth.
The prior art inoculating loop may also be used as a streaker. A streaker is used to spread bacteria on a culture medium, such as agar in a petri dish. In practice, a loopful of material is placed near one edge of the medium or agar and smeared back and forth to make a small but thickly smeared area which can then be studied to ascertain bacterial growth.
Because bacterial growth may be too excessive in the specified smeared area, it is sometimes necessary to prepare a less thickly smeared area in the petri dish. This is done by making a single stroke through the thickly smeared area, carrying this fresh stroke of material to an unused portion of the agar in the petri dish, and then streaking that single stroke of material along the unused portion of the agar. This process can be repeated as necessary. One disadvantage in using the loop itself for streaking is that it should be resterilized or replaced after preparing each smeared area. A clean loop for streaking insures a clear separation of bacteria on the agar from one smeared area to the next. However, the necessity of a clean loop results in either time consuming sterilization or excessive waste of plastic loops.
One prior art device developed to overcome this problem is depicted in FIG. 3. In this device, one end is formed in a loop and the other end has a spherical shape. The sphere may be used as a streaker and is an improvement over simply using the loop itself to streak because it allows the user to streak with an additional clean surface by rotating the sphere to an unused portion of its outer surface. This results in more efficient use of a single inoculating device.
The use of a sphere for streaking, however, also has disadvantages in that it does not always provide the clear separation of inoculum/bacteria desired. There is also a chance of carry-over and contamination from one portion of the sphere to another. Additionally, it is often difficult to determine what portion of the sphere has already been used.
Although there are a number of disposable plastic inoculating devices on the market as evidenced in FIGS. 1-3, none is able to effectively perform the functions of transferring, streaking and picking the sampled material. More than one of the devices is necessary to satisfy those functions resulting in excessive disposal and consequent waste of the used devices. In addition, the prior art streakers are also inadequate. As noted above, when preparing multiple and progressively less smeared areas, a clean surface is desired on the streaker for preparing each new area. The loop or needle is not adequate for this purpose because each should be replaced after each smeared area is complete to prevent contamination of any newly smeared area. The sphere, although an improvement, is also not guaranteed to provide a fresh sterile surface for each new smeared area desired.
SUMMARY OF THE INVENTION
The present invention overcomes the disadvantages of the prior art by combining in one device an inoculating loop, an improved streaking portion and a picker. The device is constructed of high impact polystyrene material which is injection molded to form a long thin member. One end of the device comprises a loop. The other end of the device forms a head having a plurality of distinct streaking surfaces. In the preferred embodiment, these distinct streaking surfaces have a convexity and come together to form a common point or apex, for example as in a curved pyramidal shape. The use of the pyramidal design provides both a plurality of distinct surfaces for streaking a sampled material and a point at the apex of the pyramid for selectively picking bacterial colonies when growth appears.
The distinct surfaces of the present invention are particularly advantageous when it is necessary to prepare a number of progressively thinner smeared areas in a culture medium which are then studied to ascertain bacterial growth. A fresh clean surface of the pyramid design is available to prepare each newly smeared area. Each distinct surface also provides a clear separation of bacteria with less chance of carryover or contamination upon one of the adjacent distinct surfaces. In addition, there is less waste as one device can be used for a plurality of smeared surfaces.
By having the distinct streaking surfaces come together to form a common point or apex, the device can be used to selectively transfer a bacterial colony to another culture medium for further growth. One of the distinct streaking surfaces can then be used to streak this colony of bacteria across the agar medium. All of this can be accomplished on the same pyramidal end of the device. Thus, having the picker and streaker in the same pyramidal end enhances the efficiency of the user/microbiologist.
Designing the distinct streaking surfaces to have a pyramidal form and adding a loop to the other end of the device, effectively combines in a single device an inoculating loop, a streaker and a picker. By combining all of the devices in one, the user may more efficiently go about performing the various tasks of transferring a sampled material, streaking the material on a culture medium and isolating selected portions as necessary. In addition, there is a subsequent reduction in waste due to the varied uses which may be performed of the present invention before a new sterilized device is required.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a prior art inoculating device.
FIG. 2 is a perspective view of a prior art inoculating device having a picker.
FIG. 3 is a perspective view of a prior art inoculating device having a spherical streaker.
FIG. 4 is a perspective view of one preferred embodiment of the present invention.
FIG. 5 is a cross-sectional view of the device shown in FIG. 4, taken along line 5--5.
FIG. 6 is an enlarged perspective view of the streaking portion of the device shown in FIG. 4.
FIG. 7 is an enlarged perspective view of a second preferred embodiment of the streaking portion of the present invention.
FIG. 8 is an enlarged perspective view of a third preferred embodiment of the streaking portion of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
An inoculating device embodying the features of the present invention is shown in FIG. 4, generally as 10. The device is injection molded with high impact polystyrene in one piece. Because the device is used for transferring bacterial samples to a culture medium for identifying the components of the sample, it should be sterilized, for example by gamma radiation.
The device 10 has a long thin handle 12. The handle 12 has a reduced cross-section, shown in FIG. 5, which reduces material costs and also reduces the time to cure the material when manufactured.
A first narrowed portion 14 is integrally connected at its inner end 16 to one end of the handle 12 and extends axially away from the handle. A second narrowed portion 18 is likewise integrally connected at its inner end 20 to the other end of the handle 12. The narrowed portions have a sufficient cross-section to allow them to resiliently and flexibly deflect when using the device.
The first narrowed portion 14 has an outer end 22 that is integrally connected to an inoculating loop 24. The loop 24 is of a predetermined size for transferring a known amount of material from one medium to another. Common sizes for inoculating loops are 1μ1 or 10μl.
The second narrowed portion 18 also has an outer end 26 which is connected to a curved pyramidal-shaped head 28 which serves as the streaking portion or picking portion of the device 10. Referring to FIG. 6, the head 28 has a four-sided base 30 and four distinct longitudinally extending surfaces 34. Each surface has a convexity in the longitudinal direction wherein all the surfaces 34 taper into a common point or apex 32. In addition, each surface 34 has a convexity in the lateral direction (i.e. a direction parallel to the intersection between the surface 34 and the base 30). Each side of the base 30 is similarly convex-shaped. The convexities help prevent cross-contamination between the surfaces during streaking.
As also shown in FIG. 6, the base 30 of the head 28 is integrally attached to the outer end 26 of the second narrowed portion 18. The apex 32 of the head 28 is disposed along the axis of the handle 12 of the device 10. preferably, each surface 34 has the same shape and surface area.
The curved pyramidal-shaped head 28 may be used as both a streaker and a picker. The four distinct convex-shaped surfaces 34 of the head 28 may each be used for streaking a sample on a medium, such as agar in a petri dish. The apex 32 of the head 28 may be used to isolate bacterial colonies or to remove the colonies from a culture medium. The apex 32 should not be so sharp as to make it dangerous to hold, however, it should be sleek enough to reach in between colonies and isolate them as desired. In addition, the corners between the base 30 and the surfaces 34 and between the surfaces 34 themselves, may be rounded to prevent damage to the medium or agar when streaking.
The advantages of the above described inoculating device are best illustrated by an example of how a microbiologist would use a single such device for a variety of purposes. First, a microbiologist uses the loop 24 of the device to pick up a known amount, for example 10μl, of a sample. The loopful of material is then deposited near one edge of the agar in a petri dish. The microbiologist then uses the other end of the device, namely one of the convex-shaped surfaces 34 of the head 28 to smear the sample material back and forth to make a small, but thickly smeared area on a portion of the agar. This thickly smeared area should not cover more than 1/5 of the total area of the plate. If it is desired to prepare successively thinner smeared areas of the sample on the agar, the same device is used. By rotating the device 90 degrees about its axis, a fresh clean convex-shaped surface 34 of the head 28 is used to prepare a less thickly smeared portion of the sample material on the agar. A single stroke is made with the fresh convex-shaped surface 34 through the thickly smeared area and the fresh stroke is carried back and fourth across an uninoculated portion of the agar on the plate, making 8 to 10 parallel lines about 0.5 to 1.0 cm apart. Rotating the device another 90 degrees again exposes another fresh clean convex-shaped surface 34 and another series of strokes may be made at right angles to the parallel lines previously prepared and about the same distance apart. This step is repeated as necessary.
It is important in making each newly smeared area, that the previously smeared areas not be touched when making the parallel lines. Also, it is important that the device be held at a point near its center of gravity. In this way, the pressure of the convex-shaped surface 34 on the agar is minimal and the agar is not cut. By rotating the device 90 degrees, a fresh clean surface for streaking is provided. This insures a clear separation of bacteria on the agar.
Once the sample medium has been streaked as desired and incubated, it is then studied for bacterial growth. During such studying, the apex 32 of the head 28 may be used, as necessary, to transfer a colony from the culture medium to inoculate another fresh culture medium to purify growth. The plurality of convex-shaped surfaces of the head 28 is then used to streak the inoculation as previously described. The microbiologist does this with the same device which was used to inoculate the medium and to streak it.
As shown above, the same device may be used to inoculate bacteria onto a culture medium and to prepare a plurality of smeared areas on the medium. Alternatively, the same device can be used to pick and transfer a bacterial colony from the culture medium to inoculate another culture medium and to streak the culture medium to purify the growth. A new device is not required for each step because a fresh clean sterilized surface is already available. Accordingly, the microbiologist may efficiently perform all of the above steps with a minimum number of devices, instead of disposing of and obtaining a new sterilized device for each of the above steps.
Although the curved pyramidal-shaped head provides optimum results for performing the streaking and picking functions, other shapes for the streaking portion of the device provide significant advantages over prior streaking devices. FIG. 7 depicts a second preferred embodiment of the invention wherein the streaking portion has a square base 40 and four equilateral triangular surfaces 44 which terminate in a point or apex 42. The triangular surfaces 44 of the streaking portion are formed at an angle of 30 degrees from the axis of the device 10. FIG. 8 shows a third preferred embodiment wherein the triangular surfaces 54 are formed at an angle of 45 degrees from the axis of the device.
In each of the preferred embodiments, the angle between the axis of the device and a line intersecting the apex and a point on the periphery of the base of the head should not be so small as to unduly reduce the cross-sectional area of the convex-shaped surfaces (FIG. 6) or the triangular surfaces (FIGS. 7 and 8) which would result in carryover and contamination from one surface to another during the streaking process. Conversely, the angle also should not be so great as to make the device clumsy or as to form an apex which is too bulky to effectively isolate bacterial colonies.
As shown in the above embodiments, the present invention discloses a single inoculating device which performs a variety of functions. The foregoing drawings and specifications merely are illustrative and describe preferred embodiments of the invention. Many structural changes are possible and those changes are intended to be within the scope of this disclosure. Other embodiments and variations will occur to those skilled in the art and they are contemplated to be within the scope of the claims.
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An inoculating device having an inoculating loop, an improved streaking portion and a picker. The device is constructed of high impact polystyrene material which is injection molded to form a long thin member. One end of the device comprises a loop. The other end of the device forms a head having a plurality of distinct streaking surfaces. In the preferred embodiment, these distinct streaking surfaces have a convexity and come together to form a common point or apex, for example as in a curved pyramidal shape.
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BACKGROUND OF THE INVENTION
The present invention relates to high consistency disc refiners, and more particularly, to disc refiners which have confronting, counter-rotating discs defining two distinct refining zones therebetween.
In the field of rotating disc-type pulp refiners, a known refiner construction includes opposed, counter-rotating discs between which material, such as pulp, is introduced near the axis of rotation, and undergoes defibration as the material moves radially outwardly until discharged at the circumferential periphery of the discs. The defibration, or refining, of the fiber at high consistency produces considerable amounts of steam, which has two detrimental effects. First, the steam tends to carry the fiber radially outward to be discharged from between the discs, before refining has been completed. In other words, the steam generation tends to decrease the dwell time of the fiber in the refining zone between the discs. Secondly, the steam generated in the refining zone tends to push the discs axially apart, and therefore requires that the refining equipment produce a counter-thrust to maintain the gap between discs within a range that achieves defibration. The counter-thrust cannot be so great, however, to induce contact between the discs, which, due to the high rotation speeds, can damage the equipment and result in prolonged outages.
U.S. Pat. No. 4,283,016, issued Aug. 11, 1981 to Reinhall, discloses a method and apparatus for controlling the effect of centrifugal force on the pulp of a double disc defibrating apparatus. The grinding space includes a central portion, a first grinding zone defined between first and second rotating grinding discs and extending outwards from the central portion, and a second grinding zone extending angularly from the outer end of the first grinding zone and being defined between one of the rotatable grinding discs and a stationery grinding surface. Pulp stock to be ground is introduced into the central portion and accelerated through the first and second grinding zones by centrifugal force generated by the rotating discs. The angular second grinding zone serves to retard centrifugal force acting on the pulp in the second grinding zone to increase the dwell time of the pulp in the grinding space for achieving optimum refining efficiency.
The apparatus disclosed in the Reinhall patent is concerned primarily with retarding the flow of pulp in the refining zones, as a counter measure to the increase in centrifugal force associated with the increasing diameter of modern discs. Reinhall does not, therefore, address the effects on the refining process and apparatus, of the considerable amounts of steam generated in the refining zone.
Summary of the Invention
It is, accordingly, an object of the present invention to provide an improved method and apparatus for controlling the refining intensity in a high consistency double disc refiner, by the removal of steam between distinct refining zones.
This general object is achieved in accordance with the apparatus embodiment of the invention, by providing, in a double disc refiner having distinct, radially inner and radially outer refining zones, means, preferably an annular passageway, situated between the first refining zone and the second refining zone, for removing steam produced in the first refining zone while the material to be refined moves from the first refining zone to the second refining zone.
Preferably, refining intensity is controlled in part by adjusting the pressure in a bypass channel having one end in the steam separation region between the first and second refining zones, such that a controlled quantity of steam is drawn substantially axially from the separation region into a dedicated conduit for discharge outside the casing. The partially refined fibers in the separation region, being heavier than the steam and thus less affected by the reduced pressure in the bypass conduit, continue to move substantially radially from the separation region into the inlet of the second refining zone, for further defibration and eventual discharge from the casing through the fiber outlet.
Another preferred aspect of refiner intensity control, is the counter-rotation of the refiner discs, at different equilibrium speeds.
These additional aspects of refining intensity control--steam removal rate and different speed of counter-rotation--are preferably in addition to conventional control techniques such as adjustment of refining gap, and the selective spraying of water at key locations between the discs.
In general, the inventive method is implemented in a high consistency pulp refiner of the type having a pressurized casing containing opposed grinding discs mounted for counter-rotation about a common axis and between which material to be refined is introduced near the axis so as to move radially outwardly as it is refined and generates steam. The material first moves through an inner refining zone between the discs while producing steam, and then through an outer refining zone situated between one of the discs and a static grinding surface situated radially outwardly of the other disc, from which it is discharged from the casing through an outlet. The improved method comprises the step of removing from the casing, at least some of the steam generated in the first refining zone, before that steam enters the second refining zone.
Preferably, the method also includes the step of rotating the discs at different steady state speeds, for example, 1500 rpm and 3000 rpm.
In accordance with the present invention, high quality pulp from wood chips can be obtained with a single pass through a double-disc refiner, by passing the material to be refined through two refining stages or zones. The first, radially inner stage applies a proportionally small amount of energy at a high intensity to the fiber and the second, radially outer stage applies a proportionally larger amount of energy to the fiber, but at a lower intensity level. Thus, both the first stage and second stage refining within a single casing, avoids the necessity for the user to purchase and operate two distinct refiners. Also, a mill can obtain the benefits of dual intensity refining while avoiding the need to operate and maintain two distinctly different types of refiners.
The present invention, while appearing in overall construction as a double-disc refiner, actually combines the advantage of the counter-rotating discs of the first stage to provide the high intensity refining, while taking advantage of an effective single disc type of second stage for lower intensity fiber development. This hybrid construction is further enhanced by steam separation between refining zones, preferably with the capability to adjust the different speeds of rotation of the discs. Significant decreases in energy consumption for a given degree of refining are achieved by operating the control disc at increased speeds relative to the feed disc. The steam separation between refining zones assists fiber flow and reduces the required refining thrust.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and advantages of the invention are described in the context of the preferred embodiment, with reference to the accompanying drawings, in which:
FIG. 1 is a partially sectioned view of a double disc refiner showing the portion of the refiner containing the two refining zones and associated steam removal path, in accordance with the present invention;
FIG. 2 is a frontal view of the relationship of the inner and outer plates on the control disc and stationary plate holder, respectively, as viewed along line 2--2 of FIG. 1; and
FIG. 3 is an englarged view of a portion of FIG. 1, showing the transition between the first and second refining zones.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a sectional view of one-half of a portion of a so-called double disc refiner 10, illustrating the preferred embodiment of the present invention. In these types of refiner 10, a casing 12 containing a first, or feed end disc 14, driven by first shaft 16, confronts a second, or control end disc 18 driven by shaft 20. In a conventional manner, the shafts 16,20, are supported within respective shaft housings 22,24, which sealingly penetrate opposite sides of the casing along a common axis 26 of disc rotation. In this manner, the refining process within the casing 12 can be accomplished at superatmospheric pressure and temperature. Each shaft is driven by its own motor (not shown) or other source of power which, for reasons to be described more fully below, should permit the independent setting of the equilibrium speed of rotation of one shaft 16 relative to the other 20.
Further in a manner known in this art, the right side of the refiner 10, or feed end, includes means 28, such as inlet nozzle 30 and feed screw 32 or the like, for introducing high consistency material to be refined into a throat region 34 in the hub 36 of the feed end disc 14, adjacent the axis of rotation at a variable pressure P1. It may be appreciated that, upon introduction into the feed space 38 between the discs, the material, such as wood chips, would as a result of centrifugal force move generally radially outwardly into an inner refining zone 40 defined between a first grinding plate 42 carried by the feed end disc 14, and a second grinding plate 44 carried by the control end disc 18. The first and second plates are arranged annularly around the respective feed end and control end discs, in confronting relation to each other.
As shown in FIGS. 1 and 3, the plates 42,44 define an inlet region 46 which captures and funnels the chips toward the active grinding surfaces between the plates. As the partially refined material continues to move generally radially outwardly, it is discharged from the inner refining zone 40 to a transition, or separation region 48.
A second, or outer refining zone 50, is situated generally radially outwardly relative to the inner refining zone 40, and includes a third plate 52 carried by the feed end disc, and a fourth plate 54 carried by a generally annular, stationary plate holder 56 which is supported by the casing as at 58, rather than by either of the rotating shafts 16,20. Thus, it may be appreciated that the feed end disc 14 has a larger diameter than the control end disc 18, because it carries the third plate 52 which annularly surrounds the first plate 42 on the feed end disc. The fourth plate 54 annularly surrounds the second plate 44, but is not carried by the control end disc 18.
The third and fourth plates 52,54 define another inlet region 60 substantially co-extensive with the transition, or discharge region 48 of the inner refining zone, such that the partially refined fibers that are discharged from the inner refining zone 40 are funneled inwardly so as to pass between the grinding surfaces defined by the third and fourth plates 52,54. The substantially fully refined pulp is then discharged at a pressure P2 through the discharge opening 62 in the casing 12.
As mentioned in the background portion of the present specification, the grinding of the chips and pulp produces considerable quantities of steam which, in general, adversely affects the refining process. In accordance with the present invention, a steam flow path 64 is established from the transition or separation region 48 between the inner and outer refining zones 40,50, to a steam discharge conduit or opening 66 in the casing, independent of the pulp discharge opening 62. By adjusting the pressure P3 in the steam discharge conduit 66, or elsewhere along the steam flow path 64, the pressure difference between the transition, or separation region 48 and the conduit 66 can be controlled. This pressure difference produces an axial force on the material in the transition region 48, in addition to the centrifugal force acting on the material due to the rotation of the discs. Because the steam is lighter than the pulp material and fibers, the steam is preferentially drawn through the steam path 64, and thereby separated from the pulp and fiber, the latter continuing to move in a generally radial direction into the second refining zone 50.
FIG. 2, when viewed in conjunction with FIG. 3, shows that, preferably, the outer edge 68 of the plate 44 is scalloped. The radially outer portion of the blade 70 is at a distance from the axis that is only slightly less than that of the radially inner surface defined by opposed blades 72 of plate 54. The scalloped edge permits steam to travel axially whereas the blades 70 maintain the fibers on a generally radial trajectory. This helps assure that fibers discharged from the inner refining zone 40, although influenced to some extent by the axial force component induced by the pressure differential between region 48 and P3, will be captured by the radially inner surfaces of the third and fourth plates 52,54 that define the inlet 60 to the outer refining zone 50. The steam in the transition region 48, can more easily than the pulp or fibers, travel the path 73 from the transition region 48 to the annular space 74 between the circumferential periphery 76 of the control end disc 18, and the radially inner surface of the stationary plate holder 56.
The preferred form of the first and second plates 42, 44, includes radially inner portion 78 defining a series of relatively large (thick) bars 80 and grooves 82 which taper inwardly, thereby defining a funnel, or inlet 46. The inlet 60 is defined by the lower portion 89 of the third and fourth plates 52,54, which carries the spaced-apart, wide bars or blades 72.
The first and second plates have relatively fine, or closely spaced, bars 84 and grooves 86 along their radially outer portion 88, and similarly, the third and fourth plates 52,54 have relatively fine, closely spaced bars 90 and grooves 92 over the radially outer portion 94.
The preferred configuration of the inner and outer refining zones, as shown in FIG. 1, provides that the annular refining gap between the plates of the inner refining zone 40, is substantially coplanar with the annular gap between the plates in the outer refining zone 50. In other words, it is preferred that the inner and outer refining zones 40,50 be substantially coplanar, along a plane that is perpendicular to the axis of rotation 26.
It should be appreciated, however, that as used in this specification, the condition that the outer refining zone 50 is situated "generally radially outwardly" from the inner refining zone 40, includes configurations wherein the refining gaps are not coplanar. For example, the gaps could both be vertical but offset somewhat axially, or the gap of the outer refining zone 50 could be oriented somewhat obliquely to the gap 40 of the inner refining zone. The significant feature of the present invention, is that the inner and outer refining zones 40,50 are arranged with a transition region 48 between them, such that centrifugal force propels the partially refined material from the inner refining zone 40, through the transition region 48, into the outer refining zone 50 while the steam produced in the inner refining zone 40 is drawn from the transition region 48 so as not to enter the outer refining zone 50.
Even in the ideal configuration shown in FIG. 1, it is possible that some partially refined pulp or fiber material will be drawn through the steam bypass path 64 and thus have a chance to enter the space 96 behind the control disc 18, i.e., at the side of the control disc 18 opposite the first refining zone 40. To assure that such fibers are removed from the casing 12 and do not accumulate on the back side of the control disc, a plurality of radially extending vanes 98 are provided at the back side of the control disc 18, to propel such fibers radially outwardly and toward a collection chamber or channel 100 that is annularly disposed near the outer portion of the casing 12, and which is in fluid communication with the steam discharge conduit 66. This chamber collects steam as well as bypassed fibers.
The extent of pulp or fiber content in the steam bypass flow 64 will depend in large part on the kind of refining control that is implemented by adjustment of the relationship of pressures P1, P2, P3, and P4. This fine control is achieved with the present invention, as an overlay to the two-stage refining in which the first stage, inner refining zone 40 operates with low energy at high intensity, due to the counter-rotation and resulting high relative speeds between the first and second plates 42,44, and the second stage in the outer refining zone 50, where high energy, low intensity refining occurs due to the rotation of only the third plate 52 relative to the stationery fourth plate 54. As in conventional double-disc refiners, the control disc 18 is axially adjustable 102 relative to the feed end disc 14, and, in accordance with the present invention, the stationary plate holder 56 and therefore third plate 56 are axially adjustable 104 relative to the third plate 52 carried by the feed end disc 14.
As a further control option in accordance with the present invention, the relative speeds of the counter-rotating discs can be adjusted. Preferably, the feed end disc 14 is rotated at a conventional speed, such as 1500 rpm, whereas the control end disc 18 operates at a high speed, for example, 3000 rpm. The discs are preferably rotated so that one rotates at a speed that is between 25% and 100% greater than the other. The energy savings and other advantages resulting from the rotation of the two discs at significantly different equilibrium speeds, is more fully described in U.S. patent application Ser. No. 683,750, "Controlled Intensity High Speed Double Disc Refiner", filed Jan. 8, 1991 (now U.S. Pat. No. 5,167,373) the disclosure of which is hereby incorporated by reference, and which is assigned to the assignee of the present application. Similarly, the advantages of steam removal between multiple refining zones in a single or twin refiner are described in co-pending U.S. patent application Ser. No. 681,049, "Three Zone Multiple Intensity Refiner", filed Apr. 5, 1991, now U.S. Pat. No. 5,248,099 and assigned to the assignee of the present application, the disclosure of which is hereby also incorporated by reference.
The present invention for the first time, provides steam separation between distinct refining zones in a double disc refiner, with variable intensity control available from a variety of adjustment parameters including steam separation fraction and rotation speed differential between the counter-rotating discs.
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A high consistency pulp refiner of the type having a pressurized casing (12) containing opposed grinding discs (14,18) mounted for counter-rotation about a common axis (26) and between which material to be refined is introduced near the axis so as to move generally radially outwardly through an inner refining zone (40) between the discs while producing steam as a result of the refining action. The partially refined material and steam then move through a generally radially outer refining zone (50) between one of the discs (14) and a stationary grinding surface (54) situated generally radially outwardly of the other disc (18), whereupon the refined material and steam are discharged from the casing through a material outlet (62). A generally axially extending flow path (64) originates between the first refining zone (40) and the second refining zone (50), for diverting steam produced in the first refining zone away from the second refining zone while the partially refined material moves from the first refining zone to the second refining zone.
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SUMMARY OF THE INVENTION
A composite rocking horse cart with mechanism for forward and backward movement control, characterized by its ability to convert reactive impulses as produced by the rocking of the horse on a wheeled cradle or cart into a momentum to move the cart forward or backwards. This ability is due to inner action between the mechanism on the front shaft or axle of the cart which controls the cart to effect an automatic reversal of travel upon reaching a designated distance, complete with a braking system to protect the safety of the rider, especially children, so that the cart may be brought to a complete halt in case of an impending emergency. Preferably the constituent parts of the device are made of wood and are screw fastened together so that they may be undone into components for simplifying storing or transporting the device.
BACKGROUND OF THE INVENTION
A rocking horse cart is a very popular toy for children everywhere, and almost everybody has had the experience of a ride on a rocking horse cart sometime in his childhood. It is well known that children love to ride on a rocking horse which may be accounted for by reason of the fact that it is satisfying and pleasurable to be astride of the horse's back like a conqueror rocking and swaggering back and forth.
However for many years there has been little breakthrough or improvement in the structure and operation of a conventional rocking horse. Typically a rocking horse is made of wood and has its constituent parts assembled with nails. While assembled it is useful for giving children rides, but occupies a bulky space while not in use with little ease for handling and transporting. It is also bulky and requires quite a bit of space. The modes of playing with a conventional stationary wooden horse cart have remained unchanged for many years and the rider's interest will become diverted to other sorts of entertainments, because of the monotony or lack of novelty of what a stationary rocking horse cart can offer in terms of riding pleasure. With rising living standards many children will not long be satisfied with out of date and old fashioned playing tools or toys. For this reason the present invention was developed with years of study and experimentation to provide a more intriguing toy for children everywhere.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of a rocking horse toy embodying the present invention;
FIG. 2 is a fragmentary perspective view of the inverted cart of the toy embodying the present invention;
FIG. 3 is a partial perspective of the braking device enlarged from its showing in FIG. 2;
FIG. 4 is an enlarged elevational fragmentary sectional view of a portion of the mechanism; and
FIG. 5 is an enlarged elevational fragmentary sectional view of a portion of the mechanism in a slightly different part of the operating cycle.
DETAILED DESCRIPTION
A primary object of the present invention is to provide a means whereby the rocking horse cart may move forward or backward by means of the reacted impulses from the action of vibration or rocking, such that the enjoyment of a horse cart will be enhanced to a dynamic mode instead of the static mode of operation. Because the horse cart of the present invention provides forward and reverse movement of the cart in addition to the rocking pleasures, the rider may feel like he is actually riding a moving horse.
Still another object of the present invention is to achieve an automatic reversal of the cart upon reaching a prescribed distance by virtue of the mechanism which can be adjusted to conform to the space that is available, thus avoiding hitting a surrounding wall and allowing the child rider to play in safety.
Still another object of the present invention is to provide for a braking device such that the child rider himself may have the cart under control while getting on or getting off of the horse cart, and to enable the horse cart to be stopped all at once in the presence of an impending emergency during the ride.
Another object of the present invention is to achieve an assembly and disassembly of the parts by screw locking techniques to facilitate handling and transportation with minimum space requirements, and so that the child rider standing by may observe the fitting and dismounting procedures and have an early chance to learn about mechanics.
To give a better understanding of the present invention there follows a detailed description with reference to the accompanying drawings.
FIG. 1 shows a three-dimensional exploded perspective of the present invention showing a wooden rocking horse indicated generally by the numeral 1 comprising an arcuate base 11 a horse body 12, a seat support member 13, a back-rest board 14, and a plurality of pedals 15 disposed beneath the hind and front legs 16 of the horse. Each lower end of the front and back legs 16 is provided with a crosswise flute 161 to interfit with two cross-set batten members 111. The legs 16 of the horse are secured with screws to the battens 111 through screw holes 112 and 113 to secure the horse body 12 to the arcuate base member 11. The cross battens 111 are notched as indicated at 114 to fit onto two arcuate rocking bows 115 at each of the ends thereof. This serves to reinforce the stability of the rocking bows 115 so that they may remain in vertical position, and are sturdily held. The ends, of each of the pedal members 15 is screwed by screws 151 to the middle portions of the arc bows 115 to further reinforce the stability of the arc bows 115. The seat member 13 is fixed to the horse body 12 with screws through the screw holes 131. The front of the seat with respect to the horse's neck 121. The back rest 14 rests against the horse's body 12 in a gap between the seat member and the tail 122 of the horse. The back rest may be locked to the horse's tail 122 by screws passing through screw holes 141 in the back rest and may also be secured to the seat member by screws passing through the holes 142 in the back rest which are aligned with holes 133 of the seat member. A hole 124 is provided in the horse's head 123 through which a handle 125 may pass and be secured by a screw 126. The horse 1 is linked to the cradle or cart 2 by means of two hinges 21 which serve to guide and control the direction and location at which the horse will rock; at the same time not permitting the horse to be tilted to an irrecoverable condition.
The inverted fragmentary perspective of the chassis of the cart in FIG. 2 shows the front axle 31 mounted for rotation in the body of the cart 2. A forward ratchet wheel 32 and a reverse ratchet wheel 33 complimentary to each other but opposite in direction are fixed to the front wheel axle 31. Axially spaced along the axle 31 is a guide ring set 34 mounted for rotation on the axle with each of the plurality of guide rings spaced apart by washers 35. Connected to and extending from each guide ring 34 is a projecting L-shaped rod 36 whose axial length is enough to contact and push an adjacent L-spaced rod of an adjacent guide ring. The terminal guide ring 37 is dimensioned and positioned to contact the automatic guide lever 38 which is mounted on shaft 41 and may be locked thereto by such screw 46.
A discharge shaft 41 is journaled in the frame of the cart and is disposed parallel to the shaft 31. The guide ring set 34 is located between the two fixed ringlets 39 and 40 on the shaft 31. The terminal guide ring 37 is designed to take into account the automatic guide rod 38 so that it will interact therewith. On the ringlet 39 approaching the terminal end of the first guide there is also provided an L-shaped rod 72 to engage and move the rod 73 on the first guide ring. The end of the shaft 41 carries a crank arm 42. Adjacent the crank is a fixed arm 44 secured to and extending upwardly from the shell of the cart 2 and the end of the arm 44 is attached to the crank 42 by a tensile spring 43. At the other end of the shaft 41 a control lever 47 is secured to a boss on the shaft and may be locked thereto by a set spring 45.
In FIG. 3 it may be seen that an annular cam 48 is fixed to the shaft 41 opposite the left hand ratchet wheel 32 and carries an outwardly projecting lug 49. Adjacent the annualar cam 48 is a sleeve 50 mounted on the shaft 41. Welded to stand perpendicular to the shaft at a point near the end of the sleeve 50, a bent arm 53 is mounted on the shaft 41. The bent arm 53 and a free arm 51 mounted on the sleeve 50, are notched so that the ends of a closure coil spring 55 wrapped around the sleeve 50 may be connected so that the free arm 51 will be urged to remain adjacent to the arm 53 by the spring action. At a point on the sleeve 50 opposite the reverse ratchet wheel 33 there is provided an annular cam 56 with a lug 57. Pawls or check claws 58 and 59 respectively are attached at one end to cross bars 60 mounted on shaft 41 the other ends of which pass beyond the upper side and under side of the discharge shaft 41. A closure spring 61 is provided on the cross bar 60 so that each of the pawls or check claws 58 and 59 may be attached thereto so that they can engage and interact with the ratchet wheels 32 and 33 and that the check claws can be held together resiliently to maintain their respective positions. A U-shaped board or strap 62 mounted to the chassis of the cart 2 encloses the ends of the cross bars 60.
A braking rod 63 is mounted on and controls the rotation of braking shaft 64. This shaft has a rocker arm 65 opposite and in between the ratchet wheels 32, 33. The terminal end of the rocker arm 65 is attached to two lever arms called bumper levers 66 and 67 which also have windows or slots 68 and 69 to accommodate a gliding coupling with the free arm 53 and the bent arm 51 the rocker arm 65 being pivoted to the two bumper levers 66, 67.
Manual control of the present invention is as follows. First turn tight screw 45 to achieve a tight coupling between the control lever 47 and the discharge shaft 41, then loosen screw 46 so that the automatic lever 38 is free on the discharge shaft 41 (to facilitate description, the position of the screws is shown at the bottom but they should be located in the top in practical operations). With the control lever 47 in the position shown in the drawings then the discharge shaft 41 can be rotated which rotates lug 49 as well because the sleeve 50 will follow in rotation with the discharge shaft 41 so that lug 49 will react to release the thrusting effects borne against the check claws 58, 59 to result in setting the check claw 58 to thrust upwards and catch hold of the forward ratchet wheel 32 by the elasticity of the closure spring 61 whereas the other check claw 59 will part from the reverse ratchet wheel 33 under the thrusting stress borne by lug 57. That is, the checking function of the check claw 58 being applicable against the returning trend it is possible to bring the right ratchet wheel 32 to rotate solely in the direction given in the drawings and the cart wheel including the wooden horse cart will move either forward or backward but never altogether at the same time. When the control lever 47 is shifted to the opposite position then the check claw 59 will be in a position to exert thrusting stress against the right ratchet wheel and the wooden horse cart will turn to move in reverse direction. A stabilized condition is achieved after running of the discharge shaft 41 by virtue of the contracting resilience of the stretching spring 43 that is, because after the completion of one rotation of the shaft the crank 42 will be bound to pass by the upper dead point of the longitudinal journey as the stretching spring 43 is stretched out full and the stop 71 serves to control and stop the angular displacement of the discharge shaft in each rotation.
Now follows a description of operation in the automation mode. Tighten the set screw 46 so that the automatic lever 38 is locked onto the discharge shaft 41 that drives the axle 31 to rotate in one direction. As the cart moves, the L-shaped rod 72 on the ring 39 will react to push on an L-shaped rod 73 provided on the first guide ring so that the first guide ring will rotate in step with the axle 31. Following that the L-shaped rod 73 on the first guide ring will give traction to the L-shaped rod on the second guide ring and the second guide ring will turn to give traction to the third guide ring in sequence like a chained traction transmission until the L-shaped rod on the last guide ring accomplish transmission of the automatic guide rod 38 to bring about an angular displacement of the discharge shaft 41 in a longitudinal direction which will cause a change in the direction in which the horse cart moves. Now as the wheel axle 31 makes one turn in the opposite axial direction, the L-shaped rod 73 on top of the guide rings will react to give movement to the first guide ring in the reverse direction. The first guide ring after accomplishing one turn of rotation in a direction counter to the movement of the axle due to L-shaped rod 72 will start to give transmission to the second guide ring, and eventually resulting in pushing the automatic guide rod 38 back to its original position under the transmission of the last guide ring 37. The result is that the wooden horse cart will again move in the direction prevailing in the first instance. Thus by determining the peripheral circumference of the wheel axle and selecting the correct number of guide rings 34 the distance of the journey traveled by the horse cart in the course of one change of the cycle in the automatic operation can be controlled.
One essential principle in the present invention is to achieve having the check claws 58, 59 exercising thrust against the ratchet wheels all at once so that the wheel axle will not rotate but hold stand still. Referring to FIG. 2 it is seen there are two syles of braking operations, one for cases where the command of the braking lever 63 is desired when ratchet wheel 32 alone is thrust caught by check claw 58 a detailed illustration of the procedure is given in FIG. 4. It may be seen that the braking shaft 64 will rotate with the braking lever 63 thus rotating the rocker arm 65, pulling the bumper levers 66, 67. The position relationship between the free arm 51 and the bent arm 53 and the bumper levers at this juncture will be such that the bent arm 53 can enjoy a free gliding movement in the window slot 68 in the bumper lever 66, and the free arm 51 will be pulled up instantly by the bumper lever 67 to rotate the sleeve 50 so that the lug 57 as attached to the sleeve 50 will rotate in the direction A, and the check claw 59, activated as it is by lug 57, will exert a thrusting catch of the ratchet wheel 33 by spring force of the spring 61. Since when the braking action commenced, check claw 58 and ratchet wheel 32 were in locking engagement, now both check claws 58, 59 are in locking engagement with ratchet wheels 32, 33, the wheel axle 31 will not be free to rotate in either direction and a braking action has been attained at this time. However, the closure spring 55 which was driven open by the rotation of sleeve 50, will attempt to force the sleeve to return back to its original position, but the spring 55 will not be allowed to exert this force. The shaft 41 did not follow the sleeve 50 in rotating owing to the larger pull produced by the stretching spring 43 than that of the spring 55. If the braking action were to persist, spring 55 would return sleeve 50 to its original position and lug 57 will move in direction B and thrust claw 59 will free itself from the right ratchet wheel 33. Alternatively, the braking lever 63 may be returned to its original position, and the horse cart may progress in one-way direction again.
The second form of braking operation is in case where the ratchet wheel 33 alone is in operating engagement with check claw 59 to progress in the opposite direction and a braking action is desired, reference should be made to FIG. 5. When the braking lever is turned, the relationship covering the free arm 51 and the bent arm 53 and the bumper levers 66 and 67 at the moment is shown. Due to the angular displacement of the discharge shaft 41, the turning of the braking shaft 64 by the rod 63 will turn the crank 65 pulling on the bumper lever 66, will pull the arm 53 to set the discharge shaft 41 in rotation and lug 49 will follow in direction C. Bumper lever 67 will not move arm 51 due to slot 69, but lug 49 will cause check claw 58 to be in locking engagement with ratchet wheel 32, thus effecting the complete braking action. To prevent the spring 61 from allowing check claw 59 from disengagement with ratchet wheel 33, or from over stretching spring 43, the proper angular turn of braking shaft 64 can cause a bumper fin 77 affixed to shaft 64 to turn into notch 73 provided in an elastic cross bar 75 adjacent the braking shaft 64.
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A toy rocking horse cart with forward and backward controls for children's entertainment consisting of an arc shaped base mounting, chassis, horse body, seat, back resting board, handle, reinforcement battens on the arc shaped base mounting, and other constituent parts, characterized by the fact that conversion of impulses and impetuses produced by the horse rocking on the cart into one-way momentums by the actions of the ratchet wheel sets and check claws therefor so that the cradle will be driven to move forward or else backward, with means to control and to change the direction in which the cart moves. The cart is also provided with braking means to protect the safety of a child rider in getting on or getting off the horse.
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CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of International Application No. PCT/SE00/01954, filed Oct. 9, 2000 and published in English pursuant to PCT Article 21(2), now abandoned, and which claims priority to Swedish Application No. 9903655-0, filed Oct. 8, 1999, and U.S. Provisional Application No. 60/158,465, filed Oct. 8, 1999, now abandoned. The disclosures of all applications are expressly incorporated herein by reference in their entirety.
BACKGROUND OF INVENTION
1. Technical Field
The present invention relates to a method and arrangement of detecting a number of photons in an x-ray detecting arrangement having a number of spaced apart sensors, wherein the detected photons indirectly create an amount of free charges proportional to the photon energy.
2. Background Information
Although the technique of x-ray imaging was discovered a long time ago, imaging systems of today still use the following simple procedure. Photons from a spectrum of energies are passed through an object and then detected. If a massive body such as a tumor is included in this object, a shadow (i.e., fewer photons) will fall on the detector, creating an image. Obviously, stochastic fluctuations occur in the number of photons that pass through the tissues. A sufficient amount of radiation is needed so that these fluctuations are small relative to the difference in the expected number of photons passing through the different tissues.
Preferably, the most efficient use of the detected photons is made so as to minimize the patient dose. Better detectors have been created for this purpose, with less radiation containing information about the object escaping undetected. However, very little attention has been drawn to the possibilities of increasing or improving efficiency by using information about the energy spectrum after the object. Digital systems open up new possibilities concerning this idea.
U.S. Pat. No. 5,665,969 to Beusch (“the '969 patent”) describes an x-ray detector, designed to operate as an imaging spectrometer for imaging of a subject. The x-ray detector measures energy of individual x-ray photons in each of a plurality of pixels in the x-ray detector. The pixels of the x-ray detector are readout at a rate such that the likelihood of arrive of more than one x-ray photon in each pixel during a readout period is negligible. Because x-ray photons with different energy levels will create different magnitude responses in the x-ray detector, the measurements made by the x-ray detector can be weighted according to the energy level of the detected x-ray photons. Thus, responses due to noise or x-ray photons which contribute little or no x-ray attenuation information can be discarded or weighted to eliminate or reduce their effect on any resulting image. Conversely, measurements due to x-ray photons which provide significant attenuation information can be weighted significantly.
According to the '969 patent, the optimal energy weighting one should use is the theoretical optimal one, that is approximately proportional to the negative third power of energy. There is nothing mentioned about charge shares and the optimal weight curve which can be used in reality. To be able to weight the photons with respect to the information content in a realistic way for semiconductor detectors, the signal sharing between the detector pixels must be considered. This has not been obvious until now. The '969 patent does not consider this possibility. If charge sharing is used in this case for energy weighting, the resultant image will be deteriorated, especially in case of mammography. The suggested method works for detectors having large pixels, in which charge sharing can be neglected and hence this is not a problem. In case of small detectors with spatial resolution the charge sharing will affect the output signal.
In traditional detectors, the signal is usually integrated for each pixel and each individual photon is not considered. In these types of detectors, normally used in hospitals and x-ray examination of material, the charge sharing between the pixels is positive, which increases the signal quality. It is also inherited in the detector structure which is not considered in signal processing. However, for photon-counting detectors, the signal sharing causes problems.
Examples of detectors, on which the present invention can be applied to, are disclosed in U.S. Pat. No. 4,937,453 to Nelson (“the '453 patent”) and Swedish Patent Application No. 9900856-7. The '453 patent discloses a method and apparatus for detecting x-ray radiation in a radiographic imaging context using so-called “edge-on” detectors. It is particularly useful in conjunction with slit and slot scan radiography. In accordance with this invention, detectors are constructed and arranged such that substantially all of the energy from an x-ray to be detected is discharged in the detector. In this way a detector is provided which provides a direct electronic read out, high x-ray stopping power and high spatial resolution while obtaining good signal collection efficiency without the use of excessively high voltage levels. In the preferred embodiment, solid-state x-ray detectors are constructed such that the thickness of the detector along the direction of incident x-rays is long enough that substantially all of the x-ray energy is discharged in the detector.
Swedish Patent Application No. 9900856-7 refers to a method of obtaining improved radiographic images consisting of orienting a semiconductor radiation detector. The orienting step comprises a selection of an acute angel between the direction of incident radiation and a side of the detector such that the incident radiation mainly hits the side.
FIG. 1 is a schematic illustration of a detector 100 comprising a semi-conducting substrate 110 and spatially arranged sensor or electrode strips 120 . Common for these detectors is that stripes of sensors are arranged spaced from each other on a silicon substrate and the x-rays incident onto both the sensors and the space between them.
The article Marks, D. G. et al, “ A 48×48 CdZnTe array with multiplexer readout” , Nuclear Science, IEEE Transactions, vol. 43, issue 3, part 2, June 1996, pp. 1253-59, describes charge spreading in an array of pixels in an x-ray detector on a single substrate. A method of summing nearest-neighbor pixels is disclosed. The photons are only weighted with regard to the amount of charge. The photon energy is re-created with respect to a certain level. Energy levels above a threshold value are not weighted.
SUMMARY OF INVENTION
The present invention enhances the prior art methods by means of a simple but yet efficient arrangement. In doing so, the present invention provides a novel method and arrangement for detecting and analyzing x-rays in an efficient and accurate manner.
The present invention also reduces the effects of charge sharing and trapping in a photon charge detector arrangement. The invention detects photon transmissions through a tissue and amplifier the contrast through weighting.
A method is provided for enhancing contrast information from an x-ray detecting arrangement when detecting a number of photons in the arrangement. The method includes providing at least two adjacently arranged sensors on one substrate. Each sensor has a corresponding output signal, each of which can be influenced due to shared charge from a photon detected in one of the adjacent sensors. The detected photon indirectly creates an amount of free charges proportional to the photon energy. The influence on the signal is considered by weighting the photon with respect to possible photon charge-share between the at least two adjacent sensors.
The method further includes the step of disregarding the smaller signal, or adding together two signals when signals from the sensors appear within a small time window on at least two neighboring strips.
The method further includes the step of providing an optimal weighting curve by calculating distributions of charge sharing for each energy bin in a photon spectrum that enters the detector and using an optimal theoretical weight curve for said spectrum. Moreover, for each energy bin of the incoming spectrum, how a large fraction of photons that will be recorded in preferably all different bins in a recorded spectrum is calculated, as well as how many photons that are not counted and the distribution of signals in the neighboring sensor. The method further includes the step of calculating the distribution of real photon energies that belong to a recorded energy bin, wherein the weight belongs to a certain bin being the convolution of said distribution and theoretical weight factors.
In one embodiment a weight curve for trapped photon charges is computed, which further includes a distribution of signals, e.g., through simulation, from each energy bin in the photon spectrum, which also includes trapping, and through backwards calculation, calculating for each bin in a detected pulse amplitude spectrum how the photons that contributed to the bin are distributed in its energy spectrum.
In a preferred embodiment the method further includes the steps of irradiating an object through an x-ray source, detecting the beam having a spatial object information and a spectrum filtered by the object by means of said sensors, wherein the signal from the sensors is a signal deriving from a detected photon, signal from each x-ray detector for each sensor being readout and an amplitude of the signal being compared to a threshold level, generating an output for signals above or below said threshold value as an output for an amount of time, which relates to the time the signal is above or below the threshold levels, and if the signal from an x-ray photon is shared between two sensors and triggers an adjacent comparator, the two comparators outputs generating a simultaneous signal. The method further includes the step of detecting the simultaneous signal and initiating a charge sharing, indicating if the amplitude of a signal is high or low, for indicating if the x-ray photon is high energy or low energy, and counting the number of photons through the indication representing spectrums of signal amplitudes for each image pixel.
A preferred arrangement for detecting and counting photons in an x-ray beam includes a detector arrangement having sensors, and at least to each sensor coupled amplification unit, comparator means, logic unit and counter. Preferably, the counter comprises a first and a second counter for each sensor and the first and second counters correspond to high and low energy photons, respectively. Moreover, the comparator is connected to a threshold value and if the signal exceeds a predetermined threshold level the output of a comparator is a logical signal as output for an amount of time, which relates to the time, the signal exceeds the threshold levels. If the signal from an x-ray photon is shared between two sensors and two adjacent comparators, the signal generated is same at simultaneously. Additionally, simultaneous signals are detected by the logic units and if at least two adjacent comparators have same signals charge sharing is indicated. Moreover, it includes interface means for connection to further processing means.
BRIEF DESCRIPTION OF DRAWINGS
Following, the invention will be further described in a non-limiting way with reference to the accompanying drawings in which:
FIG. 1 schematically illustrates a detector arrangement for detecting x-rays,
FIG. 2 is an example of a weight curve,
FIG. 3 is a schematic block diagram of a detector arrangement embodiment, according to the present invention, and
FIG. 4 is a block diagram illustrating the steps of a method according to the present invention.
DETAILED DESCRIPTION
The difference in absorption probability between the normal tissue and the tumor becomes larger with decreasing photon energy. Therefore, a low energy photon carries more contrast information and should be given a higher statistical weight after detection. Mathematically, it can be shown that the photons should be given statistical weights that are approximately proportional to the negative third power of their energy.
In addition to the examples of detectors disclosed above, a gaseous detector, such as a Parallel Plate Chamber where the gas volume is oriented edge-on to the incident X-rays can be employed.
Imaging systems are normally integrating, that is, the signals created from individual photons in the detector are added together. Since the signals are proportional to the photon energy, the statistical weights differ four powers of the energy from the optimal weighting. In digital photon counting systems, all photons are given unity statistical weights, which is therefore a more efficient way of obtaining information describing the object. The optimal way would be to use a detector with high-energy resolution, and to register the detected spectrum. The energy bins in this spectrum can then be added together in the optimal weighting manner. A simplifying compromise to this method is to record the spectrum into only a few bins. An extreme case of this is to use only two energy bins, each one with an associated weight factor (dual weighting).
In reality, the spectrum that would be registered is not the correct one that is entering the detector. The reason is photons that are detected indirectly create an amount of free charges proportional to the photon energy. These charges are collected on electrodes, with the signal created being proportional to the number of charges collected. This is used in an energy sensitive detector system where the signals are sorted into a spectrum according to their sizes. When a photon is transformed into free charges, those charges flow towards electrodes. Ideally, all free charges of the type that are collected (electrons or holes) are collected at the nearest electrode (sensor) strip, so it contributes in the right image pixel. In general however, an amount of charges will be shared with the strip that is the second nearest to the interaction (charge sharing). Yet, another amount of free charge will become trapped inside the detector volume, and will not reach the electrode in time to contribute to the signal (trapping). The trapping effects are significant between the electrodes (same as charge sharing), which depends on the flow of free charges in an area between the electrodes and immediately under the surface of the electrodes. In the mentioned area the electrical potential drop is affected by the charges in the oxide layer between the electrodes. Consequently, the electrical drop is low and the free charges are slowed down and trapped. However, outside the electrodes the trapping effect is insignificant. Theoretically, it is possible to disregard the trapping, but trapping depends on the electrode geometry, specially the distance between the electrodes exposed to the oxide layer, bias voltage on the detector and manufacturing. The charge sharing occurs in both silicon and gas micro-strip electrodes (and others).
The effects of these two mechanisms are that the photons, in general, will be registered having less energy than they really had, and subsequently, they will be given large statistical weights. The electronic readout has a threshold for discriminating real signals from noise (mainly appearing in the pre-amplifier). This threshold level is well below the least energetic photons in the spectrum entering the detector but, because of the charge losses, some photons give rise to signals below this threshold and are not registered at all. Additionally, charges that are shared will be interpreted as a low energy photon. Moreover, the trapped charges will partly be scattered in time and partly be all too few to be able to pass the threshold. This is of course a drawback, since it is a false photon that will acquire a large weight.
One possible way to reduce these problems is to use anti coincidence when reading out the detector signal, i.e., when signals appear within a small time window on two neighboring strips, the smaller signal is disregarded. Another way would be to add the two signals together, and thereby reconstruct the initial photon energy. It is not possible to fully reconstruct the right spectrum in this way. For example, the charge lost by trapping is not considered. The trapping depends on many factors, such as detector material, material purity, the sensor or electrode width, the space between the sensors, etc.
This distortion of the spectrum suggests that the theoretical optimal weighting calculated before is not optimal in reality. One significant difference is that the lowest end of the spectrum should have low statistical weight instead of highest, since a large fraction derives from false photons (if anti-coincidence is not used).
The optimal weighting curve can be found after calculating the distributions of charge sharing for each energy bin in the photon spectrum that enters the detector. It is desirable to use the optimal theoretical weight curve for this spectrum, although this is not the spectrum that is recorded. For each energy bin of the incoming spectrum, it is calculated how a large fraction of photons that will be recorded in all the different bins in the recorded spectrum, how many photons that were never counted at all (because their signals were reduced below the electronic threshold level), and the distribution of signals in the neighboring strip. Then it is possible to calculate the distribution of real photon energies that belongs to a recorded energy bin. The weight belonging to a certain bin is then the convolution of this distribution and the old theoretical weight factors. The fraction of false photons is given zero weight. The fractions are normalized, so that the sum of fractions in the real spectrum plus the fraction of false photons are considered equal. The fractions of undetected photons with energy corresponding to the considered bin are then added to the convolution after being multiplied with the corresponding weight factor.
FIG. 2 is an example of an optimal weight curve for a 5 mm tumor when anti-coincidence has not been used to be compared with E −3 according to prior art.
In a preferred embodiment shown in FIG. 3, an arrangement according to the invention includes a set of detector arrays 300 having sensors 310 that are connected to an amplification block 330 , a comparator block 340 , a logic block 350 and a counter block 360 .
Referring to the block diagram of FIG. 4, the operative steps according to the present invention in conjunction with FIG. 3 are as follows. An x-ray source 410 irradiates an object. The beam from the x-ray source has a spectrum characteristic of the source. Referring to step 420 , the beam is collimated or refracted onto an object to be examined. The beam filtered by the object 430 obtains spatial object information and a spectrum, and incident 440 onto the detectors. The signal from the detectors is a signal deriving from a detected photon. The signal shape depends on the photon energy and conversion position in the detector. One photon can produce signals in more than one channel due to the charge sharing.
The signal from each x-ray detector 300 for each channel, i.e., each sensor 310 , is readout 450 by first being amplified by an amplifier 330 ′. After being amplified, the amplitude of the signal is compared to threshold levels in a comparator 340 ′. If the signal exceeds a predetermined threshold level, the output of comparators is sat, e.g., by means of a logic one, as an output for an amount of time, which relates to the time the signal exceeds the threshold levels. If the signal from an x-ray photon is shared between two channels and triggers an adjacent comparator, these two comparators then signal (“1”) at the same time. To determine a low or high-energy photon, there are preferably two threshold values—a first low value and a second high value. A low energy photon is detected if the signal exceeds the low threshold but not the high threshold. A high-energy photon threshold is detected if both low and high thresholds are exceeded.
The simultaneous signals will be detected by the logic units 350 ′ following the comparators “1”, a flag is set for charge sharing. This can be achieved by standard logic such an AND gate for signals from adjacent comparators. Another flag can be set indicating if the amplitude is high or low, i.e., if the x-ray photon is high energy or low energy.
After logic block 350 , there are the counters 360 . In a simple embodiment there is one counter 361 for high-energy photons and one counter 362 for low energy photons. Alternatively, it is possible to use several counters if more accurate measurement of the energy is desired. Normally, there is not a charge-sharing phenomenon, the flag is not set, and the counter corresponding to the energy of the photon is incremented. If the charge sharing flag is set, only the counter for one channel is updated, which could be any of the two channels. However, it is important that two channels are not incremented at the same time. In this case, only the counter corresponding to the highest photon energy is updated. Because of charge sharing, the energy is not known and the weighting of a high-energy photon as a low energy photon is avoided, as this severely degrades the DQE. Weighting a few low energy photons as high-energy photons is not as severe.
The content of the counters, which are spectrums of signal amplitudes for each image pixel, can then be readout 460 , e.g., through a shift register or similar, by a computer for storing data, making energy weighting with optimal weight-function, image processing and presentation. Compensation for charge losses and charge sharing in the detector is included in the optimal weight function.
Obviously, the above described arrangement is given as an example and other arrangements, e.g., including A/D-converters, microprocessors, etc., can occur.
With respect to the trapping, the trapped charges will be handled as the “false” electrons in the charge sharing case, i.e., the share of the trapped charges is counted and this share is weighted zero. However, it is not possible to discriminate the trapped charges using anti-coincidence. As a result of the trapping, the signal from an electrode decreases regardless of whether it is effected by the charge sharing or not.
The weight curve for trapping is computed in same way as above. Firstly, a distribution of signals, e.g., through simulation, from each energy bin in the photon spectrum is computed, which also includes trapping. Then, through backwards calculation, it is calculated for each bin in the detected pulse amplitude spectrum how the photons which contributed to the bin are distributed in its energy spectrum.
New optimal weighting curves are calculated taking into account charge sharing, and achieved efficiency for different weighting methods are determined based on simulations. In the following the results of simulations of 100 and 50 micron pitch detectors are disclosed. Charge sharing is included, but not trapping. The efficiencies are expressed as DQE (Detective Quantum Efficiency). The reference is the signal to noise ratio (SNR) squared in an ideal detector without charge losses and using the theoretical optimal weighting curve. The DQE depends on the object that is imaged, and in the simulations, a 40 mm thick breast with a 5 mm tumor and a 250 micron calcification were modeled. In reality, of course, it is not possible to choose the weighting curve that is optimal for the tissue in a particular pixel. Optimal weight curves are, however, not that different. Preferably, it is best to choose the curve that corresponds to the most difficult tissue (and significant for diagnosing purpose) to detect in an image.
In addition, the DQE depends on the electronic threshold level. The results disclosed below are those for the threshold level that gives the highest DQE, that is, optimal threshold levels have also been determined in this study. A 30 keV tungsten spectrum was used in the simulations. In all weighting methods disclosed in tables 1-3 below, except for the “optimal” case as disclosed in the tables, a signal corresponding to less than 14 keV was weighed as a 14 keV photon. This improves the efficiencies since it is known that no photon below 14 keV passes unabsorbed through the object. The optimal weighting, however, assigns the best individual weights also for these lowest energy bins. The uncertainties in the DQEs stated below are approximately 1%, and the threshold levels are within about 200-300 electrons.
Table 1 discloses DQEs and optimal threshold levels for different weighting methods in the case where no anti-coincidence is used. The results for a detector with 100 micron pitch and 50 micron pitch, respectively, are shown in their respective column. The threshold levels should be multiplied with 3.6/1000 to convert from electrons to keV.
TABLE 1
Optimal
Optimal
threshold
threshold
level
level for
Weighting
DQE for
DQE for
for tumor
calcification
method
tumor
calcification
(electrons)
(electrons)
micron pitch
100
50
100
50
100
50
100
50
Old theoretical
0.76
0.64
0.80
0.67
4000
4000
4000
4000
Counting
0.77
0.72
0.80
0.75
2800
2800
2800
2800
Integrating
0.70
0.69
0.72
0.72
2400
2000
2400
2000
Dual weighting
0.82
0.75
0.85
0.78
3200
3200
3200
3200
Optimal
0.86
0.79
0.87
0.81
2400
2400
2400
2400
The DQEs dropped from 1 to 0.76 and 0.80 for tumor and calcification respectively when the old theoretical weighting curve was used and charge sharing was introduced. The efficiency becomes worse than for a photon counting system. The two weighting bins have been optimized in the case of dual weighting. If the signal corresponds to energy higher than 22-23 keV, then it should be given a weight that is about 0.61 or about 0.68 for 100 and 50 micron pitch, respectively, in the case of tumor and about 0.64 and about 0.71 in the case of calcification. Otherwise, the weight is unity.
Table 2 shows DQEs and optimal threshold levels for different weighting methods in the case when anti-coincidence is used. The results for a detector with 100 micron pitch and 50 micron pitch, respectively, are shown in separate columns. The threshold levels should be multiplied with 3.6/1000 to convert from electrons to keV.
TABLE 2
Optimal
Optimal
threshold
threshold
level
level for
Weighting
DQE for
DQE for
for tumour
calcification
method
tumor
calcification
(electrons)
(electrons)
micron pitch
100
50
100
50
100
50
100
50
Old theoretical
0.79
0.8
0.84
0.82
2000
2000
2000
2000
Counting
0.81
0.8
0.84
0.85
2000
2000
2000
2000
Integrating
0.7
0.7
0.73
0.73
2000
2000
2000
2000
Dual weighting
0.88
0.9
0.9
0.88
2000
2000
2000
2000
Optimal
0.9
0.9
0.92
0.9
2000
2000
2000
2000
The cut in the spectrum should now be made at about 22-23 keV in case of dual weighting and 100 micron pitch. The higher energy weight factors are about 0.58 and about 0.62. In case of 50 micron pitch, the cut should be at about 21-22 keV and the weight factors about 0.62 and about 0.66. The threshold levels should know be set as low as possible without allowing false counts due to electronic noise. Two thousand electrons were chosen, allowing all photons to be detected, even if charge sharing is 50% (which should be considered correct when trapping is not considered.)
Table 3 includes DQEs and optimal threshold levels for different weighting methods where coincident signals on two neighboring strips are added. The results for a detector with 100 and 50 micron pitches, respectively, are in separate columns. The threshold levels should be multiplied with 3.6/1000 to convert from electrons to keV.
TABLE 3
Optimal
Optimal
threshold
threshold
level
level for
Weighting
DQE for
DQE for
for tumor
calcification
method
tumor
calcification
(electrons)
(electrons)
micron pitch
100
50
100
50
100
50
100
50
Old theoretical
0.92
0.91
0.94
0.9
2000
2000
2000
2000
Counting
0.81
0.82
0.85
0.8
2000
2000
2000
2000
Integrating
0.69
0.7
0.74
0.7
2000
2000
2000
2000
Dual weighting
0.9
0.89
0.93
0.9
2000
2000
2000
2000
Optimal
0.94
0.94
0.95
0.9
2000
2000
2000
2000
The cut in the spectrum should now be made at about 21-22 keV (100 micron pitch) and about 18-19 keV and about 19-20 keV (50 micron, tumor and micro-calcification respectively) in case of dual weighting. The higher energy weight factors are about 0.57 and about 0.61 for 100 micron pitch, and about 0.60 and about 0.65 for 50 micron pitch. Again, the threshold levels should be set as low as possible. Accidental coincidence of independent photons has not been considered.
The reason why the optimal weighting is still a few percent better than the old theoretical is that the optimal method compensates for the fact that photons only detected on one strip in general creates lower signal than corresponds to its energy.
The invention is not limited the shown embodiments but can be varied in a number of ways without departing from the scope of the appended claims and the arrangement and the method can be implemented in various ways depending on application, functional units, needs and requirements etc.
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The present invention relates a method of enhancing contrast information from an x-ray detecting arrangement, when detecting a number of photons in said arrangement comprising at least two adjacently arranged sensors provided on one substrate, each sensor having a corresponding output signal, each of which can be influenced due to shared charge from a photon detected in one of said adjacent sensors, which detected photon indirectly creates an amount of free charges proportional to the photon energy, wherein said influence on said signal is considered by weighting said photon with respect to possible said photon charge-share between said at least two adjacent sensors.
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RELATION TO OTHER APPLICATIONS
[0001] The present application claims the benefit of the filing date of U.S. Provisional Patent Application Ser. No. 60/175,358 filed Jan. 10, 2000.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to structures and materials used in the formation of orthopedic casts. The present invention relates more specifically to a layered, open cell, fabric material impregnated with a curable polymer or pre-polymer resin that may be shaped and formed prior to curing into a rigid cast.
[0004] 2. Description of the Related Art
[0005] Orthopedic casting materials have evolved over time from the earlier plaster of Paris and cotton gauze based casts to the more recent synthetic orthopedic casting tapes. Plaster of Paris based casts suffered from many difficulties that included being generally air impermeable, being subject to deterioration in contact with water, and being very heavy and bulky. The basic structure of the more recent synthetic casts involves a fabric sheet or tape, usually of fiberglass, that is impregnated with a liquid resin that cures and hardens in air over a short period of time. Alternate materials include thermoplastic resins that are formable at a temperature higher than room temperature but not so high as to be uncomfortable to the patient or the individual putting the cast material in place. In either case the result is a strong, relatively lightweight cast that, after curing, is not subject to deterioration in contact with water.
[0006] Fiberglass/Polymer Resin based cast materials typically come in two structural forms. The basic form involves a roll of tape anywhere from one to five inches wide that is applied by wrapping the tape around the limb to be cast. A second general structural form involves a pre-cut sheet of the material sized and shaped to fit around a specific appendage such as a wrist and forearm or an ankle and foot. The latter configuration is typically easier to apply but less conformable to the variety of sizes and shapes of limbs. The former structure (tape) is more versatile but is generally more difficult to apply.
[0007] The optimal characteristics of casting materials can be countervailing or conflicting in many cases. Obviously the material must result in a cast of sufficient strength to protect the healing limb. There is also however the desire for the cast to be lightweight and less bulky. As indicated above, it is desirable for the casting material to be readily formable prior to curing so as to more closely support and guard the limb. The resin-based materials should not overly adhere to the patient's skin or to the hands or gloves of the individual putting the extensible foam. The pre-cut casting blank is sized and shaped to fit a particular limb and is initially held in place (prior to curing) by a number of clips that secure an edge of the material to the surface of the material upon wrapping around the limb.
[0008] U.S. Pat. No. 3,998,219 issued to Mercer et al. on Dec. 21, 1976 entitled ORTHOPEDIC SPLINT AND METHOD FOR FORMING SAME describes a multi-layered cast material comprising a central cellular core and inner and outer layers that sandwich the core and which when cured are rigid and supportive. Optional layers of foam material may be placed between the core and the inner and outer layers to provide better interlock between the layers (to reduce shifting between the layers).
[0009] Although a number of the materials described in the above references have as their stated goal a certain amount of air permeability, such properties remain less than optimal given the small size (on the order of 1 mm or less) of the apertures formed. In addition, none of the above materials accomplish much in the way of significantly reducing the size and weight of the finished cast. In general it is the resin (in a cured state) that provides the structural strength to the cast it is also the resin that contributes the most to the weight of the cast. Because of this problem, prior efforts have greatly limited the size of the openings or apertures in the fabric in order to maintain a sufficient amount of hardenable resin dispersed throughout the cast tape or sheet.
SUMMARY OF THE INVENTION
[0010] It is therefore an object of the present invention to provide a material for use constructing orthopedic casts of the fiberglass and hardenable resin type that significantly reduces the size and weight of the resultant cast structure.
[0011] It is another object of the present invention to provide a material for use in forming orthopedic casts that incorporates apertures of a size, number and arrangement that significantly increases the amount of air flow through the cast in comparison to existing open mesh cast materials.
[0012] It is a further object of the present invention to provide an open mesh cast material that incorporates foundational fabric material compositions and additive hardenable resin compositions that are known and utilized in the art.
[0013] It is a further object of the present invention to provide an open mesh cast material that provides sufficient rigidity without increased weight and size. It is a related object to address the foregoing through cast materials having optimal geometries.
[0014] It is a further object of the present invention to provide a material for use in forming orthopedic casts that may be precut and partially preformed to accommodate standard limb sizes and shapes.
[0015] It is a further object of the present invention to provide a material for use in forming orthopedic casts that while providing a rigid protective enclosure for the injured limb, may still be easily removed through the use of scissors or cast saws.
[0016] It is a further object of the present invention to provide a material for use in forming orthopedic casts that incorporates a continuous hexagonal conduit array within which are positioned microbeads or the like and which when subjected to a negative pressure differential becomes rigid.
[0017] Other objects and advantages will be apparent to those of ordinary skill in the art from the following disclosure.
[0018] In fulfillment of these and other objectives the present invention provides a fiberglass and hardenable resin based orthopedic casting material made from layers of resin impregnated fiberglass fibers that are shaped, cut, or otherwise formed into a skeletal hexagonal cellular mesh array. The material forms a generally sheet-like element having an array of apertures there through to permit the flow of air through the cast as well as the visual and physical monitoring of the condition of the patient's injured limb. The size of the hexagonal apertures in the material may vary according to the specific application of the cast but is generally large in comparison to the cross sectional size of the fiberglass sections that define the sides of the hexagonal apertures. Reinforcing strand components, such as stainless steel and Kevlar® fibers may be incorporated into the casting material. Optionally the mesh may incorporate a lining that prevents the resin from adhering to the skin. The sheet-like material may be cut and trimmed both prior to application in its pliable state and subsequent to application in its rigid state. The apertures in the material serve to receive the fingers or toes of the individual receiving the cast in a manner that facilitates the application of the material. Furthermore, the apertures serve the primary purpose of allowing nearly complete air flow through the cast to permit the rapid drying of the cast and the skin after wetting occurs. The skeletal structure of the material greatly reduces the size and weight of the cast without unduly sacrificing strength and protection.
[0019] Further objects and advantages of the invention will be readily apparent to those skilled in the art from the following description taken in conjunction with the accompanying drawings. The drawings constitute part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a plan view of a section of the material of the present invention.
[0021] FIG. 2 is a detailed cross sectional view of the multi-layer structure of the material of the present invention.
[0022] FIG. 3 is a perspective view of a typical application of a section of the material of the present invention as used in conjunction with the formation of a wrist and forearm cast.
[0023] FIG. 4 is a detailed view of a clip used in association with the application of the material of the present invention.
[0024] FIG. 5 is a plan view of an alternative embodiment of the material of the present invention.
[0025] FIG. 6 is a detailed cross sectional view of the alternative embodiment shown in FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] The basic structure of the material of the present invention is characterized by a specific geometry that is determined to provide the strength and rigidity necessary for an orthopedic cast while at the same time decreasing the weight and overall discomfort of the cast. In fulfilling these goals, variations on the specific geometric shapes involved and variations in the diametrical measurements of the structures are anticipated. The following description therefore provides but a few of the best examples of the application of the structures and the materials of the present invention.
[0027] Reference is made first to FIG. 1 for a brief description of the basic structure of open cell mesh fabric 10 comprising the material of the present invention. Mesh fabric 10 , in its fundamental configuration, is a screen or mesh formed from layers of resin impregnated fiberglass fibers 20 that are shaped, cut, or otherwise formed into a skeletal hexagonal cellular array. This construction forms the hexagonal apertures 22 between fiber bundles 20 . The actual layered structure of mesh fabric 10 is described in more detail below with respect to FIG. 2 .
[0028] The construction of mesh fabric 10 may be accomplished according to a number of different, equally appropriate, methods. In a first method, layered bundles of fiberglass material (the construction of which is described in more detail below) may be woven into the hexagonal configuration shown in FIG. 1 . A variety of fiber bundle weaving and knotting methods are known in the fabric industry that would create apertures similar to those shown in FIG. 1 . A second method involves the cutting of a layered sheet of fiberglass material in a manner that creates hexagonal apertures 22 by the removal of a hexagonal section of the layered sheet material. In either case, the result is an open cell mesh fabric having relatively large hexagonal apertures there through. The connecting skeleton of the fabric is comprised of resin impregnated fiber bundles.
[0029] As indicated above, there are a number of different materials that are suitable for both the foundation of the open cell mesh fabric 10 and the resin that impregnates the fibers of the mesh fabric. Fiberglass fiber bundles or fabric materials, as are known in the art, provide the basic foundation in the preferred embodiment of the present invention. The structure of the present invention lends itself to use with a variety of resins that include both prepolymer resins that cure upon exposure to air and thermoplastic resins that are pliable above certain elevated temperatures. As indicated, there are many different resins well known in the art that appropriately flow by capillary action in between the fibers of the fiberglass fabric material and provide sufficient rigidity when cured or cooled to establish a hard and protective cast material.
[0030] Reference is now made to FIG. 2 for a detailed description of the layered construction of resin impregnated fiber bundles 20 shown externally in FIG. 1 . In FIG. 2 , the thickness dimension of the mesh fabric has been exaggerated with respect to the longitudinal dimensions of the mesh fabric, in order to clearly show the various layers in the construction of the fabric. In FIG. 2 a plurality of resin impregnated fiberglass layers 34 a through 34 n are shown as forming the core of the mesh fabric material. In the preferred embodiment there are 6-12 layers of fiberglass material which form a “bundle” core of about 5-15 mm in thickness. A layer of synthetic breathable material 30 is adhered to a “top” surface of the mesh fabric material and a breathable but water impermeable layer 32 is adhered to a second or “bottom” surface of the mesh fabric material. Layer 32 is intended to come into contact with the skin of the patient to which the cast is applied and therefore is intended to provide a nonabrasive surface. Commonly available materials such as Goretex® Cast Liner or the like are appropriate for use on this lower layer of the mesh fabric that comes in contact with the patient. The upper layer of synthetic breathable material 30 is positioned on the mesh fabric primarily for the purpose of easing the application of the cast material prior to its hardening.
[0031] In the cross sectional view shown in FIG. 2 , resin impregnated fiberglass bundles 20 are shown in diametrical cross sections as are hexagonal apertures 22 . In this view, it can be seen how air flow moves through aligned hexagonal apertures 22 between resin impregnated fiber bundles 20 .
[0032] A modification of the cross sectional structure shown in FIG. 2 is anticipated wherein top layer 30 and bottom layer 32 extend around the plurality of fiberglass layers 34 a - 34 n so as to effectively enclose the fiberglass material. Top layer 30 and bottom layer 32 may be sealed or sewn together where their edges meet. This modification reduces the exposure of the sometimes abrasive edge of the fiberglass material after hardening.
[0033] Reference is now made to FIG. 3 for a description of the manner in which a section of the cast material of the present invention is positioned and fixed on an injured limb of a patient. The limb section shown in FIG. 3 is that of a patient's forearm 40 and includes the patient's hand 42 and the patient's thumb 44 . In this view, a section 10 of open cell mesh fabric of the present invention has been cut and configured to form around the forearm 40 , wrist (not shown), hand 42 , and thumb 44 of the patient. The hexagonal structure of the open cell mesh fabric 10 can be clearly seen both in its relative shape and size with respect to the human hand.
[0034] In the preferred embodiment of the present invention, the diametrical cross section of resin impregnated fiber bundles 20 is in the range of 0.5 to 1.5 centimeters. The diametrical cross section of hexagonal apertures 22 in the preferred embodiment is in the range of 2.5 to 4.5 centimeters. This diametrical measurement for the hexagonal apertures is an average between the wall-to-wall diameter and the apex-to-apex diameter of the hexagonal shape.
[0035] The mesh fabric section shown in FIG. 3 has been cut into a generally rectangular shape having a first dimension equal to the length of the area to be covered along the patient's forearm, wrist and hand. The second dimension for the rectangular section comprises approximately 80%-100% of the maximum circumference around the patient's forearm, wrist and hand in an injured condition. In this manner, the rectangular section readily covers the injured area, providing sufficient support above and below the injured area on the limb, and provides the ability to gradually “close” the cast once the rectangular section has been initially wrapped around the limb. It is recognized that the circumference of an injured limb is frequently greater than that of the healed limb. For this reason it is anticipated that a gap on the order of 2.5 cm may be left between the edges of the material once it has initially been wrapped around the limb. The closure clips, described below, permit the gradual closure of the cast as swelling of the limb reduces over time.
[0036] One benefit of the open cell hexagonal structure of the present invention is to provide an aperture through which the thumb or other small appendage of the patient may be passed in order to secure the initial placement of the material on the patient. Application of the material would therefore comprise passing the thumb 44 (and in some cases the individual fingers of the patient's hand 42 ) through a selection of appropriate hexagonal apertures 22 in the mesh fabric material. This provides an initial means for securing the material to the patient and allows the remaining portion of the material to be drawn securely around the limb. In the view shown in FIG. 3 , the initial (first positioned) edge of the mesh fabric material 10 is secured by attachment to the thumb 44 as described above and then wrapped over the wrist and forearm (into the drawing page), around the wrist and forearm (and then out from the drawing page), to end at the point shown on the near side of the patient's wrist and forearm. Leading edge 38 of the cast material is shown just meeting the initially placed layer of cast material and secured thereto by a number of cast clips 46 which are described in more detail below. The open cell hexagonal structure of the material of the present invention provide readily accessible apertures through which the cast closure clips may be placed. These closure clips 46 are structured so that they may progressively draw the cast closed even after the resin in the cast material has hardened. The cured or hardened fiberglass/resin material remains flexible enough to follow the reduced circumference of the limb as it heals under the progressive closure of the closure clips.
[0037] It is anticipated that a variety of preformed, precut shapes of the material of the present invention might be used for standard cast locations such as that shown in FIG. 3 . Similar applications to ankles, elbows, hands, feet and lower leg sections are anticipated. In conjunction with these “custom” shapes, specifically placed appendage apertures may be cut or formed into the cast material. These appendage apertures may be specifically positioned, sized and shaped as appropriate for the finger, thumb, toe or other appendage they are intended to engage. Alternately, sufficiently large “blanks” of the material may be provided with the caregiver cutting and forming the material to the needed area prior to application. Depending upon the type of hardenable resin utilized, it is anticipated that a large sheet of the material of the present invention may be placed around the injured limb area on the patient and then trimmed to an appropriate size and shape before the hardening process is initiated.
[0038] The structure of the cast clip or closure 46 shown in FIG. 3 is described in more detail with respect to FIG. 4 . The clip shown in FIG. 4 is but one example of an appropriate device for securing leading edge 38 of the cast material back onto an adjacent, overlapped section of the cast material. Clip 50 in FIG. 4 is comprised of a polymer plastic strap having a first end 52 with aperture 58 therein that is designed to receive and engage a second end 54 that incorporates a plurality of barbs 56 . Clips of this type that incorporate a number of barbs so as to secure the clip in a number of degrees of closure are well known in the art. Although the closure shown in FIG. 4 is structured to accommodate the hexagonal apertures in the preferred embodiment, alternate types of cable tie wrap closures may be used.
[0039] The above-described preferred embodiment of the present invention makes use of fabric materials whose chemical compositions are well known in the art. Likewise, the resins used, as described herein, are well known and have characteristics desirable for the formation of orthopedic casts. Again, it is the geometries and dimensions of the structures formed from these compositions that are described in the present invention and which address many of the problems present in the prior art. Although a hexagonal geometry has been described and emphasized herein, alternate geometries are anticipated. The hexagonal geometry provides a structure that is strong and stiff when subjected to forces from many directions. The hexagonal geometry also maximizes strength while limiting the amount of skeletal structure. Other aperture and bridge geometries are anticipated that meet these same objectives. Alternative compositions that utilize the same geometries and dimensions are further anticipated by the present invention.
[0040] FIGS. 5 and 6 provide a second example of the application of the geometries and dimensions of the open mesh material of the present invention, constructed with alternate elements. FIG. 5 is similar to the view shown in FIG. 1 but with the alternative compositions mentioned. It is known in the art of splints and casts that a layered sheet of material comprising a core of microbeads contained within a polymer envelope may be subjected to a vacuum that removes most of the air surrounding the microbeads and thereby forms a relatively rigid structure that is maintained as long as a negative pressure differential is maintained. Typically, such microbead technologies are utilized in large sheets that are initially pliable and subsequently are flat and firm after being subjected to a vacuum. In the present invention, this basic structure and technology is implemented in the manner shown in FIG. 5 . This external view shows open cell mesh sheet material 60 made up of an array of channeled sections 62 whose cross sectional structure is described in more detail below.
[0041] These channeled sections 62 comprise interior channel 64 which is bounded on either side by sealed seam 66 . In this manner, a continuous hexagonal array of conduit is formed between two layers of polymer sheets 69 a and 69 b . Within the open conduit thus formed are positioned a plurality of microbeads 68 . The composition and size of microbeads 68 may vary and is not particularly important in the present application. Such microbeads and evacuation layers are well known in the art and the compositions and sizes as commonly used in the field are appropriate here.
[0042] The construction shown in FIG. 5 forms the same hexagonal aperture 70 as is formed in the first described preferred embodiment. Seams 66 are exaggerated in FIG. 5 in order to clarify the position of the open channel contained between the layers of the polymer sheet material.
[0043] Reference is now made to FIG. 6 for a description of the cross sectional structure of the web shown generally in FIG. 5 . Channel section 62 is seen to be comprised of two layers of polymer sheeting 69 a and 69 b that are sealed together into the form shown in FIG. 5 . This sealing process creates the open channels 64 within which microbeads 68 are placed. The process typically involves placement of the microbeads and then heat sealing the layers together over the beads. Alternately, the layers may be sealed together with the beads introduced into the open volume there between. Typically, hexagonal aperture 70 would be cut through the layers of the material after the sealing process has been carried out.
[0044] Microbeads 68 generally fill the open channel 64 in a loose packed manner prior to the evacuation of air from the channel. In this state, the web material created is pliable and formable around the limb of the patient much in the same manner as described above in FIG. 3 . Once positioned around the limb of the patient, evacuation of the channels with an appropriate vacuum pump through a valve structure (not shown) creates a rigid skeleton structure similar in many respects to the rigid structure formed by the hardenable resin in the first described embodiment. As long as a negative pressure differential is maintained, rigidity of the structure is maintained. As with the layered structure shown in FIG. 2 , it is desirable to have a less abrasive layer 72 positioned on the inside or lower surface of the cast material. This surface, which comes in contact with the patient, is preferably layered with a breathable but water impermeable material.
[0045] Although the present invention has been described in conjunction with first and second preferred embodiments, it is anticipated that a variety of other compositions for the foundational fabric material and the hardenable additive to the foundation, are possible. The important elements of the present invention include the cellular geometry of the open mesh fabric and the generally larger dimensions of the apertures thereby formed. A variety of compositions for both the foundational fabric and the hardenable material are anticipated.
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A fiberglass and hardenable resin based orthopedic casting material that is shaped, cut, or otherwise formed into a skeletal hexagonal cellular mesh array. The material forms a generally sheet-like material having an array of aligned apertures Reinforcing strand components, such as stainless steel and Kevlar® fibers may be incorporated into the casting material. The apertures serve the primary purpose of allowing nearly complete air flow through the cast to permit the rapid drying of the cast and the skin after wetting occurs. The apertures also serve to allow close visual and physical monitoring of the condition of the patient's skin and limb. The sheet-like material may be trimmed both prior to application in its pliable state and subsequent to application in its rigid state. The size of the hexagonal apertures in the material may vary, but is generally large in comparison to the size of sides of the hexagonal apertures.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional application of co-pending application Ser. No. 11/702,810, entitled Single Phase Fluid Sampling Apparatus and Method for Use of Same, filed on Feb. 6, 2007, which is a continuation-in-part application of co-pending application Ser. No. 11/438,764, entitled Single Phase Fluid Sampling Apparatus and Method for Use of Same, filed on May 23, 2006, which is a continuation-in-part application of application Ser. No. 11/268,311, entitled Single Phase Fluid Sampler Systems and Associated Methods, filed on Nov. 7, 2005, now U.S. Pat. No. 7,197,923 B1, issued Apr. 3, 2007.
TECHNICAL FIELD OF THE INVENTION
[0002] This invention relates, in general, to testing and evaluation of subterranean formation fluids and, in particular to, a single phase fluid sampling apparatus for obtaining multiple fluid samples and maintaining the samples near reservoir pressure via a common pressure source during retrieval from the wellbore and storage on the surface.
BACKGROUND OF THE INVENTION
[0003] Without limiting the scope of the present invention, its background is described with reference to testing hydrocarbon formations, as an example.
[0004] It is well known in the subterranean well drilling and completion art to perform tests on formations intersected by a wellbore. Such tests are typically performed in order to determine geological or other physical properties of the formation and fluids contained therein. For example, parameters such as permeability, porosity, fluid resistivity, temperature, pressure and bubble point may be determined. These and other characteristics of the formation and fluid contained therein may be determined by performing tests on the formation before the well is completed.
[0005] One type of testing procedure that is commonly performed is to obtain a fluid sample from the formation to, among other things, determine the composition of the formation fluids. In this procedure, it is important to obtain a sample of the formation fluid that is representative of the fluids as they exist in the formation. In a typical sampling procedure, a sample of the formation fluids may be obtained by lowering a sampling tool having a sampling chamber into the wellbore on a conveyance such as a wireline, slick line, coiled tubing, jointed tubing or the like. When the sampling tool reaches the desired depth, one or more ports are opened to allow collection of the formation fluids. The ports may be actuated in variety of ways such as by electrical, hydraulic or mechanical methods. Once the ports are opened, formation fluids travel through the ports and a sample of the formation fluids is collected within the sampling chamber of the sampling tool. After the sample has been collected, the sampling tool may be withdrawn from the wellbore so that the formation fluid sample may be analyzed.
[0006] It has been found, however, that as the fluid sample is retrieved to the surface, the temperature of the fluid sample decreases causing shrinkage of the fluid sample and a reduction in the pressure of the fluid sample. These changes can cause the fluid sample to approach or reach saturation pressure creating the possibility of asphaltene deposition and flashing of entrained gasses present in the fluid sample. Once such a process occurs, the resulting fluid sample is no longer representative of the fluids present in the formation. Therefore, a need has arisen for an apparatus and method for obtaining a fluid sample from a formation without degradation of the sample during retrieval of the sampling tool from the wellbore. A need has also arisen for such an apparatus and method that are capable of maintaining the integrity of the fluid sample during storage on the surface.
SUMMARY OF THE INVENTION
[0007] The present invention disclosed herein provides a single phase fluid sampling apparatus and a method for obtaining fluid samples from a formation without the occurrence of phase change degradation of the fluid samples during the collection of the fluid samples or retrieval of the sampling apparatus from the wellbore. In addition, the sampling apparatus and method of the present invention are capable of maintaining the integrity of the fluid samples during storage on the surface.
[0008] In one aspect, the present invention is directed to an apparatus for obtaining a plurality of fluid samples in a subterranean well that includes a carrier, a plurality of sampling chambers and a pressure source. In one embodiment, the pressure source is selectively in fluid communication with at least two sampling chambers thereby serving as a common pressure source to pressurize fluid samples obtained in the at least two sampling chambers. In another embodiment, the carrier has a longitudinally extending internal fluid passageway forming a smooth bore and a plurality of externally disposed chamber receiving slots. Each of the sampling chambers is positioned in one of the chamber receiving slots of the carrier. The pressure source is selectively in fluid communication with each of the sampling chambers such that the pressure source is operable to pressurize each of the sampling chambers after the fluid samples are obtained.
[0009] In another aspect, the present invention is directed to a method for obtaining a plurality of fluid samples in a subterranean well. The method includes the steps of positioning a fluid sampler in the well, obtaining a fluid sample in each of a plurality of sampling chambers of the fluid sampler and pressurizing each of the fluid samples using a pressure source of the fluid sampler that is in fluid communication with each of the sampling chambers.
[0010] In a further aspect, the present invention is directed to an apparatus for obtaining a fluid sample in a subterranean well. The apparatus includes a housing having a sample chamber defined therein. The sample chamber is selectively in fluid communication with the exterior of the housing and is operable to receive the fluid sample therefrom. A debris trap piston is slidably disposed within the housing. The debris trap piston includes a debris chamber and, responsive to the fluid sample entering the sample chamber, the debris trap piston receives a first portion of the fluid sample in the debris chamber then displaces relative to the housing to expand the sample chamber.
[0011] In one embodiment, the debris trap piston includes a passageway having a cross sectional area that is smaller than the cross sectional area of the debris chamber. In this embodiment, the first portion of the fluid sample passes from the sample chamber through the passageway to enter the debris chamber. Also in this embodiment, the first portion of the fluid sample is retained in the debris chamber due to pressure from the sample chamber applied to the debris chamber through the passageway. Alternatively or additionally, a check valve may be disposed in an inlet portion of the debris trap piston to retain the first portion of the fluid sample in the debris chamber.
[0012] In another embodiment, the debris trap piston may include a first piston section and a second piston section that is slidable relative to the first piston section such that the debris chamber is expandable responsive to the fluid sample entering the debris chamber. In this embodiment, as engagement device may be disposed between the first piston section and the second piston section to prevent additional movement of the first piston section relative to the second piston section after expanding the debris chamber to a preselected volume.
[0013] In an additional aspect, the present invention is directed to a method for obtaining a fluid sample in a subterranean well. The method includes the steps of disposing a sampling chamber within the subterranean well, actuating the sampling chamber such that a sample chamber within the sampling chamber is in fluid communication with the exterior of the sampling chamber, receiving a first portion of the fluid sample in a debris chamber of a debris trap piston slidably disposed within the sampling chamber, displacing the debris trap piston within the sampling chamber to expand the sample chamber and receiving the remainder of the fluid sample in the sample chamber.
[0014] The method may also include passing the first portion of the fluid sample through the sample chamber and through a passageway of the debris trap piston before entering the debris chamber and retaining the first portion of the fluid sample in the debris chamber by applying pressure from the sample chamber to the debris chamber through the passageway. Additionally or alternatively, a check valve disposed in an inlet portion of the debris trap piston may be used to retain the first portion of the fluid sample in the debris chamber.
[0015] In certain embodiments, the method may include expanding the debris chamber responsive to the fluid sample entering the debris chamber by sliding a first piston section relative to a second piston section and preventing additional movement of the first piston section relative to the second piston section after expanding the debris chamber to a preselected volume.
[0016] In yet another aspect, the present invention is directed to a downhole tool including a housing having a longitudinal passageway. A piston, including a piercing assembly, is disposed within the longitudinal passageway. A valving assembly is also disposed within the longitudinal passageway. The valving assembly includes a rupture disk that is initially operable to maintain a differential pressure thereacross. The valving assembly is actuated by longitudinally displacing the piston relative to the valving assembly such that at least a portion of the piercing assembly travels through the rupture disk, thereby allowing fluid flow therethrough.
[0017] In one embodiment, the piercing assembly includes a piercing assembly body and a needle that is held within the piercing assembly body by compression. In this embodiment, the needle has a sharp point that travels through the rupture disk. In addition, the needle may have a smooth outer surface, a fluted outer surface, a channeled outer surface or a knurled outer surface. In certain embodiments, the valving assembly may include a check valve that allows fluid flow in a first direction and prevents fluid flow in a second direction through the valving assembly once the valving assembly is actuated by the piercing assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] For a more complete understanding of the present invention, including its features and advantages, reference is now made to the detailed description of the invention, taken in conjunction with the accompanying drawings in which like numerals identify like parts and in which:
[0019] FIG. 1 is a schematic illustration of a fluid sampler system embodying principles of the present invention;
[0020] FIGS. 2A-H are cross-sectional views of successive axial portions of one embodiment of a sampling section of a sampler embodying principles of the present invention;
[0021] FIGS. 3A-E are cross-sectional views of successive axial portions of actuator, carrier and pressure source sections of a sampler embodying principles of the present invention;
[0022] FIG. 4 is a cross-sectional view of the pressure source section of FIG. 3C taken along line 4 - 4 ;
[0023] FIG. 5 is a cross-sectional view of the actuator section of FIG. 3A taken along line 5 - 5 ;
[0024] FIG. 6 is a schematic view of an alternate actuating method for a sampler embodying principles of the present invention;
[0025] FIG. 7 is a schematic illustration of an alternate embodiment of a fluid sampler embodying principles of the present invention;
[0026] FIG. 8 is a cross-sectional view of the fluid sampler of FIG. 7 taken along line 8 - 8 ; and
[0027] FIGS. 9A-G are cross-sectional views of successive axial portions of another embodiment of a sampling section of a sampler embodying principles of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0028] While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts which can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention, and do not delimit the scope of the invention.
[0029] Referring initially to FIG. 1 , therein is representatively illustrated a fluid sampler system 10 and associated methods which embody principles of the present invention. A tubular string 12 , such as a drill stem test string, is positioned in a wellbore 14 . An internal flow passage 16 extends longitudinally through tubular string 12 .
[0030] A fluid sampler 18 is interconnected in tubular string 12 . Also, preferably included in tubular string 12 are a circulating valve 20 , a tester valve 22 and a choke 24 . Circulating valve 20 , tester valve 22 and choke 24 may be of conventional design. It should be noted, however, by those skilled in the art that it is not necessary for tubular string 12 to include the specific combination or arrangement of equipment described herein. It is also not necessary for sampler 18 to be included in tubular string 12 since, for example, sampler 18 could instead be conveyed through flow passage 16 using a wireline, slickline, coiled tubing, downhole robot or the like. Although wellbore 14 is depicted as being cased and cemented, it could alternatively be uncased or open hole.
[0031] In a formation testing operation, tester valve 22 is used to selectively permit and prevent flow through passage 16 . Circulating valve 20 is used to selectively permit and prevent flow between passage 16 and an annulus 26 formed radially between tubular string 12 and wellbore 14 . Choke 24 is used to selectively restrict flow through tubular string 12 . Each of valves 20 , 22 and choke 24 may be operated by manipulating pressure in annulus 26 from the surface, or any of them could be operated by other methods if desired.
[0032] Choke 24 may be actuated to restrict flow through passage 16 to minimize wellbore storage effects due to the large volume in tubular string 12 above sampler 18 . When choke 24 restricts flow through passage 16 , a pressure differential is created in passage 16 , thereby maintaining pressure in passage 16 at sampler 18 and reducing the drawdown effect of opening tester valve 22 . In this manner, by restricting flow through choke 24 at the time a fluid sample is taken in sampler 18 , the fluid sample may be prevented from going below its bubble point, i.e., the pressure below which a gas phase begins to form in a fluid phase. Circulating valve 20 permits hydrocarbons in tubular string 12 to be circulated out prior to retrieving tubular string 12 . As described more fully below, circulating valve 20 also allows increased weight fluid to be circulated into wellbore 14 .
[0033] Even though FIG. 1 depicts a vertical well, it should be noted by one skilled in the art that the fluid sampler of the present invention is equally well-suited for use in deviated wells, inclined wells or horizontal wells. As such, the use of directional terms such as above, below, upper, lower, upward, downward and the like are used in relation to the illustrative embodiments as they are depicted in the figures, the upward direction being toward the top of the corresponding figure and the downward direction being toward the bottom of the corresponding figure.
[0034] Referring now to FIGS. 2A-2H and 3 A- 3 E, a fluid sampler including an exemplary fluid sampling chamber and an exemplary carrier having a pressure source coupled thereto for use in obtaining a plurality of fluid samples that embodies principles of the present invention is representatively illustrated and generally designated 100 . Fluid sampler 100 includes a plurality of the sampling chambers such sampling chamber 102 as depicted in FIG. 2 . Each of the sampling chambers 102 is coupled to a carrier 104 that also includes an actuator 106 and a pressure source 108 as depicted in FIG. 3 .
[0035] As described more fully below, a passage 110 in an upper portion of sampling chamber 102 (see FIG. 2A ) is placed in communication with a longitudinally extending internal fluid passageway 112 formed completely through fluid sampler 100 (see FIG. 3 ) when the fluid sampling operation is initiated using actuator 106 . Passage 112 becomes a portion of passage 16 in tubular string 12 (see FIG. 1 ) when fluid sampler 100 is interconnected in tubular string 12 . As such, internal fluid passageway 112 provides a smooth bore through fluid sampler 100 . Passage 110 in the upper portion of sampling chamber 102 is in communication with a sample chamber 114 via a check valve 116 . Check valve 116 permits fluid to flow from passage 110 into sample chamber 114 , but prevents fluid from escaping from sample chamber 114 to passage 110 .
[0036] A debris trap piston 118 separates sample chamber 114 from a meter fluid chamber 120 . When a fluid sample is received in sample chamber 114 , piston 118 is displaced downwardly. Prior to such downward displacement of piston 118 , however, piston section 122 is displaced downwardly relative to piston section 124 . In the illustrated embodiment, as fluid flows into sample chamber 114 , an optional check valve 128 permits the fluid to flow into debris chamber 126 . The resulting pressure differential across piston section 122 causes piston section 122 to displace downward, thereby expanding debris chamber 126 .
[0037] Eventually, piston section 122 will displace downward sufficiently far for a snap ring, C-ring, spring-loaded lugs, dogs or other type of engagement device 130 to engage a recess 132 formed on piston section 124 . Once engagement device 130 has engaged recess 132 , piston sections 122 , 124 displace downwardly together to expand sample chamber 114 . The fluid received in debris chamber 126 is prevented from escaping back into sample chamber 114 by check valve 128 in embodiments that include check valve 128 . In this manner, the fluid initially received into sample chamber 114 is trapped in debris chamber 126 . This initially received fluid is typically laden with debris, or is a type of fluid (such as mud) which it is not desired to sample. Debris chamber 126 thus permits this initially received fluid to be isolated from the fluid sample later received in sample chamber 114 .
[0038] Meter fluid chamber 120 initially contains a metering fluid, such as a hydraulic fluid, silicone oil or the like. A flow restrictor 134 and a check valve 136 control flow between chamber 120 and an atmospheric chamber 138 that initially contains a gas at a relatively low pressure such as air at atmospheric pressure. A collapsible piston assembly 140 in chamber 138 includes a prong 142 which initially maintains another check valve 144 off seat, so that flow in both directions is permitted through check valve 144 between chambers 120 , 138 . When elevated pressure is applied to chamber 138 , however, as described more fully below, piston assembly 140 collapses axially, and prong 142 will no longer maintain check valve 144 off seat, thereby preventing flow from chamber 120 to chamber 138 .
[0039] A floating piston 146 separates chamber 138 from another atmospheric chamber 148 that initially contains a gas at a relatively low pressure such as air at atmospheric pressure. A spacer 150 is attached to piston 146 and limits downward displacement of piston 146 . Spacer 150 is also used to contact a stem 152 of a valve 154 to open valve 154 . Valve 154 initially prevents communication between chamber 148 and a passage 156 in a lower portion of sampling chamber 102 . In addition, a check valve 158 permits fluid flow from passage 156 to chamber 148 , but prevents fluid flow from chamber 148 to passage 156 .
[0040] As mentioned above, one or more of the sampling chambers 102 and preferably nine of sampling chambers 102 are installed within exteriorly disposed chamber receiving slots 159 that circumscribe internal fluid passageway 112 of carrier 104 . A seal bore 160 (see FIG. 3B ) is provided in carrier 104 for receiving the upper portion of sampling chamber 102 and another seal bore 162 (see FIG. 3 C) is provided for receiving the lower portion of sampling chamber 102 . In this manner, passage 110 in the upper portion of sampling chamber 102 is placed in sealed communication with a passage 164 in carrier 104 , and passage 156 in the lower portion of sampling chamber 102 is placed in sealed communication with a passage 166 in carrier 104 .
[0041] In addition to the nine sampling chambers 102 installed within carrier 104 , a pressure and temperature gauge/recorder (not shown) of the type known to those skilled in the art can also be received in carrier 104 in a similar manner. For example, seal bores 168 , 170 in carrier 104 may be for providing communication between the gauge/recorder and internal fluid passageway 112 . Note that, although seal bore 170 depicted in FIG. 3C is in communication with passage 172 , preferably if seal bore 170 is used to accommodate a gauge/recorder, then a plug is used to isolate the gauge/recorder from passage 172 . Passage 172 is, however, in communication with passage 166 and the lower portion of each sampling chamber 102 installed in a seal bore 162 and thus servers as a manifold for fluid sampler 100 . If a sampling chamber 102 or gauge/recorder is not installed in one or more of the seal bores 160 , 162 , 168 , 170 then a plug will be installed to prevent flow therethrough.
[0042] Passage 172 is in communication with chamber 174 of pressure source 108 . Chamber 174 is in communication with chamber 176 of pressure source 108 via a passage 178 . Chambers 174 , 176 initially contain a pressurized fluid, such as a compressed gas or liquid. Preferably, compressed nitrogen at between about 7,000 psi and 12,000 psi is used to precharge chambers 174 , 176 , but other fluids or combinations of fluids and/or other pressures both higher and lower could be used, if desired. Even though FIG. 3 depicts pressure source 108 as having two compressed fluid chambers 174 , 176 , it should be understood by those skilled in the art that pressure source 108 could have any number of chambers both higher and lower than two that are in communication with one another to provide the required pressure source. As best seen in FIG. 4 , a cross-sectional view of pressure source 108 is illustrated, showing a fill valve 180 and a passage 182 extending from fill valve 180 to chamber 174 for supplying the pressurized fluid to chambers 174 , 176 at the surface prior to running fluid sampler 100 downhole.
[0043] As best seen in FIGS. 3A and 5 , actuator 106 includes multiple valves 184 , 186 , 188 and respective multiple rupture disks 190 , 192 , 194 to provide for separate actuation of multiple groups of sampling chambers 102 . In the illustrated embodiment, nine sampling chambers 102 may be used, and these are divided up into three groups of three sampling chambers each. Each group of sampling chambers can be referred to as a sampling chamber assembly. Thus, a valve 184 , 186 , 188 and a respective rupture disk 190 , 192 , 194 are used to actuate a group of three sampling chambers 102 . For clarity, operation of actuator 106 with respect to only one of the valves 184 , 186 , 188 and its respective one of the rupture disks 190 , 192 , 194 is described below. Operation of actuator 106 with respect to the other valves and rupture disks is similar to that described below.
[0044] Valve 184 initially isolates passage 164 , which is in communication with passages 110 in three of the sampling chambers 102 via passage 196 , from internal fluid passage 112 of fluid sampler 100 . This isolates sample chamber 114 in each of the three sampling chambers 102 from passage 112 . When it is desired to receive a fluid sample into each of the sample chambers 114 of the three sampling chambers 102 , pressure in annulus 26 is increased a sufficient amount to rupture the disk 190 . This permits pressure in annulus 26 to shift valve 184 upward, thereby opening valve 184 and permitting communication between passage 112 and passages 196 , 164 .
[0045] Fluid from passage 112 then enters passage 110 in the upper portion of each of the three sampling chambers 102 . For clarity, the operation of only one of the sampling chambers 102 after receipt of a fluid sample therein is described below. The fluid flows from passage 110 through check valve 116 to sample chamber 114 . An initial volume of the fluid is trapped in debris chamber 126 of piston 118 as described above. Downward displacement of the piston section 122 , and then the combined piston sections 122 , 124 , is slowed by the metering fluid in chamber 120 flowing through restrictor 134 . This prevents pressure in the fluid sample received in sample chamber 114 from dropping below its bubble point.
[0046] As piston 118 displaces downward, the metering fluid in chamber 120 flows through restrictor 134 into chamber 138 . At this point, prong 142 maintains check valve 144 off seat. The metering fluid received in chamber 138 causes piston 146 to displace downward. Eventually, spacer 150 contacts stem 152 of valve 154 which opens valve 154 . Opening of valve 154 permits pressure in pressure source 108 to be applied to chamber 148 . Pressurization of chamber 148 also results in pressure being applied to chambers 138 , 120 and thus to sample chamber 114 . This is due to the fact that passage 156 is in communication with passages 166 , 172 (see FIG. 3C ) and, thus, is in communication with the pressurized fluid from pressure source 108 .
[0047] When the pressure from pressure source 108 is applied to chamber 138 , piston assembly 140 collapses and prong 142 no longer maintains check valve 144 off seat. Check valve 144 then prevents pressure from escaping from chamber 120 and sample chamber 114 . Check valve 116 also prevents escape of pressure from sample chamber 114 . In this manner, the fluid sample received in sample chamber 114 is pressurized.
[0048] In the illustrated embodiment of fluid sampler 100 , multiple sampling chambers 102 are actuated by rupturing disk 190 , since valve 184 is used to provide selective communication between passage 112 and passages 110 in the upper portions of multiple sampling chambers 102 . Thus, multiple sampling chambers 102 simultaneously receive fluid samples therein from passage 112 .
[0049] In a similar manner, when rupture disk 192 is ruptured, an additional group of multiple sampling chambers 102 will receive fluid samples therein, and when the rupture disk 194 is ruptured a further group of multiple sampling chambers 102 will receive fluid samples therein. Rupture disks 184 , 186 , 188 may be selected so that they are ruptured sequentially at different pressures in annulus 26 or they may be selected so that they are ruptured simultaneously, at the same pressure in annulus 26 .
[0050] Another important feature of fluid sampler 100 is that the multiple sampling chambers 102 , nine in the illustrated example, share the same pressure source 108 . That is, pressure source 108 is in communication with each of the multiple sampling chambers 102 . This feature provides enhanced convenience, speed, economy and safety in the fluid sampling operation. In addition to sharing a common pressure source downhole, the multiple sampling chambers 102 of fluid sampler 100 can also share a common pressure source on the surface. Specifically, once all the samples are obtained and pressurized downhole, fluid sampler 100 is retrieved to the surface. Even though certain cooling of the samples will take place, the common pressure source maintains the samples at a suitable pressure to prevent any phase change degradation. Once on the surface, the sample may remain in the multiple sampling chambers 102 for a considerable time during which temperature conditions may fluctuate. Accordingly, a surface pressure source, such a compressor or a pump, may be used to supercharge the sampling chambers 102 . This supercharging process allows multiple sampling chambers 102 to be further pressurized at the same time with sampling chambers 102 remaining in carrier 104 or after sampling chambers 102 have been removed from carrier 104 .
[0051] Note that, although actuator 106 is described above as being configured to permit separate actuation of three groups of sampling chambers 102 , with each group including three of the sampling chambers 102 , it will be appreciated that any number of sampling chambers 102 may be used, sampling chambers 102 may be included in any number of groups (including one), each group could include any number of sampling chambers 102 (including one), different groups can include different numbers of sampling chambers 102 and it is not necessary for sampling chambers 102 to be separately grouped at all.
[0052] Referring now to FIG. 6 , an alternate actuating method for fluid sampler 100 is representatively and schematically illustrated. Instead of using increased pressure in annulus 26 to actuate valves 184 , 186 , 188 , a control module 198 included in fluid sampler 100 may be used to actuate valves 184 , 186 , 188 . For example, a telemetry receiver 199 may be connected to control module 198 . Receiver 199 may be any type of telemetry receiver, such as a receiver capable of receiving acoustic signals, pressure pulse signals, electromagnetic signals, mechanical signals or the like. As such, any type of telemetry may be used to transmit signals to receiver 199 .
[0053] When control module 198 determines that an appropriate signal has been received by receiver 199 , control module 198 causes a selected one or more of valves 184 , 186 , 188 to open, thereby causing a plurality of fluid samples to be taken in fluid sampler 100 . Valves 184 , 186 , 188 may be configured to open in response to application or release of electrical current, fluid pressure, biasing force, temperature or the like.
[0054] Referring now to FIGS. 7 and 8 , an alternate embodiment of a fluid sampler for use in obtaining a plurality of fluid samples that embodies principles of the present invention is representatively illustrated and generally designated 200 . Fluid sampler 200 includes an upper connector 202 for coupling fluid sampler 200 to other well tools in the sampler string. Fluid sampler 200 also includes an actuator 204 that operates in a manner similar to actuator 106 described above. Below actuator 204 is a carrier 206 that is of similar construction as carrier 104 described above. Fluid sampler 200 further includes a manifold 208 for distributing fluid pressure. Below manifold 208 is a lower connector 210 for coupling fluid sampler 200 to other well tools in the sampler string.
[0055] Fluid sampler 200 has a longitudinally extending internal fluid passageway 212 formed completely through fluid sampler 200 . Passageway 212 becomes a portion of passage 16 in tubular string 12 (see FIG. 1 ) when fluid sampler 200 is interconnected in tubular string 12 . In the illustrated embodiment, carrier 206 has ten exteriorly disposed chamber receiving slots that circumscribe internal fluid passageway 212 . As mentioned above, a pressure and temperature gauge/recorder (not shown) of the type known to those skilled in the art can be received in carrier 206 within one of the chamber receiving slots such as slot 214 . The remainder of the slots are used to receive sampling chambers and pressure source chambers.
[0056] In the illustrated embodiment, sampling chambers 216 , 218 , 220 , 222 , 224 , 226 are respectively received within slots 228 , 230 , 232 , 234 , 236 , 238 . Sampling chambers 216 , 218 , 220 , 222 , 224 , 226 are of a construction and operate in the manner described above with reference to sampling chamber 102 . Pressure source chambers 240 , 242 , 244 are respectively received within slots 246 , 248 , 250 in a manner similar to that described above with reference to sampling chamber 102 . Pressure source chambers 240 , 242 , 244 initially contain a pressurized fluid, such as a compressed gas or liquid. Preferably, compressed nitrogen at between about 10,000 psi and 20,000 psi is used to precharge chambers 240 , 242 , 244 , but other fluids or combinations of fluids and/or other pressures both higher and lower could be used, if desired.
[0057] Actuator 204 includes three valves that operate in a manner similar to valves 184 , 186 , 188 of actuator 106 . Actuator 204 has three rupture disks, one associated with each valve in a manner similar to rupture disks 190 , 192 , 194 of actuator 106 and one of which is pictured and denoted as rupture disk 252 . As described above, each of the rupture disks provides for separate actuation of a group of sampling chambers. In the illustrated embodiment, six sampling chambers are used, and these are divided up into three groups of two sampling chambers each. Associated with each group of two sampling chambers is one pressure source chamber. Specifically, rupture disk 252 is associated with sampling chambers 216 , 218 which are also associated with pressure source chamber 240 via manifold 208 . In a like manner, the second rupture disk is associated with sampling chambers 220 , 222 which are also associated with pressure source chamber 242 via manifold 208 . In addition, the third rupture disk is associated with sampling chambers 224 , 226 which are also associated with pressure source chamber 244 via manifold 208 . In the illustrated embodiment, each rupture disk, valve, pair of sampling chambers, pressure source chamber and manifold section can be referred to as a sampling chamber assembly. Each of the three sampling chamber assemblies operates independently of the other two sampling chamber assemblies. For clarity, the operation of one sampling chamber assembly is described below. Operation of the other two sampling chamber assemblies is similar to that described below.
[0058] The valve associated with rupture disk 252 initially isolates the sample chambers of sampling chambers 216 , 218 from internal fluid passageway 212 of fluid sampler 200 . When it is desired to receive a fluid sample into each of the sample chambers of sampling chambers 216 , 218 , pressure in annulus 26 is increased a sufficient amount to rupture the disk 252 . This permits pressure in annulus 26 to shift the associated valve upward in a manner described above, thereby opening the valve and permitting communication between passageway 212 and the sample chambers of sampling chambers 216 , 218 .
[0059] As described above, fluid from passageway 212 enters a passage in the upper portion of each of the sampling chambers 216 , 218 and passes through an optional check valve to the sample chambers. An initial volume of the fluid is trapped in a debris chamber as described above. Downward displacement of the debris piston is slowed by the metering fluid in another chamber flowing through a restrictor. This prevents pressure in the fluid sample received in the sample chambers from dropping below its bubble point.
[0060] As the debris piston displaces downward, the metering fluid flows through the restrictor into a lower chamber causing a piston to displace downward. Eventually, a spacer contacts a stem of a lower valve which opens the valve and permits pressure from pressure source chamber 240 to be applied to the lower chamber via manifold 208 . Pressurization of the lower chamber also results in pressure being applied to the sample chambers of sampling chambers 216 , 218 .
[0061] As described above, when the pressure from pressure source chamber 240 is applied to the lower chamber, a piston assembly collapses and a prong no longer maintains a check valve off seat, which prevents pressure from escaping from the sample chambers. The upper check valve also prevents escape of pressure from the sample chamber. In this manner, the fluid samples received in the sample chambers are pressurized.
[0062] In the illustrated embodiment of fluid sampler 200 , two sampling chambers 216 , 218 are actuated by rupturing disk 252 , since the valve associated therewith is used to provide selective communication between passageway 212 the sample chambers of sampling chambers 216 , 218 . Thus, both sampling chambers 216 , 218 simultaneously receive fluid samples therein from passageway 212 .
[0063] In a similar manner, when the other rupture disks are ruptured, additional groups of two sampling chambers (sampling chambers 220 , 222 and sampling chambers 224 , 226 ) will receive fluid samples therein and the fluid samples obtained therein will be pressurize by pressure sources 242 , 244 , respectively. The rupture disks may be selected so that they are ruptured sequentially at different pressures in annulus 26 or they may be selected so that they are ruptured simultaneously, at the same pressure in annulus 26 .
[0064] One of the important features of fluid sampler 200 is that the multiple sampling chambers, two in the illustrated example, share a common pressure source. That is, each pressure source is in communication with multiple sampling chambers. This feature provides enhanced convenience, speed, economy and safety in the fluid sampling operation. In addition to sharing a common pressure source downhole, multiple sampling chambers of fluid sampler 200 can also share a common pressure source on the surface. Specifically, once all the samples are obtained and pressurized downhole, fluid sampler 200 is retrieved to the surface. Even though certain cooling of the samples will take place, the common pressure source maintains the samples at a suitable pressure to prevent any phase change degradation. Once on the surface, the samples may remain in the multiple sampling chambers for a considerable time during which temperature conditions may fluctuate. Accordingly, a surface pressure source, such a compressor or a pump, may be used to supercharge the sampling chambers. This supercharging process allows multiple sampling chambers to be further pressurized at the same time with the sampling chambers remaining in carrier 206 or after sampling chambers have been removed from carrier 206 .
[0065] It should be understood by those skilled in the art that even though fluid sampler 200 has been described as having one pressure source chamber in communication with two sampling chambers via manifold 208 , other numbers of pressure source chambers may be in communication with other numbers of sampling chambers with departing from the principles of the present invention. For example, in certain embodiments, one pressure source chamber could communicate pressure to three, four or more sampling chambers. Likewise, two or more pressure source chambers could act as a common pressure source to a single sampling chamber or to a plurality of sampling chambers. Each of these embodiments may be enabled by making the appropriate adjustments to manifold 208 such that the desired pressure source chambers and the desired sampling chambers are properly communicated to one another.
[0066] Referring now to FIGS. 9A-9G and with reference to FIGS. 3A-3E , an alternate fluid sampling chamber for use in a fluid sampler including an exemplary carrier having a pressure source coupled thereto for use in obtaining a plurality of fluid samples that embodies principles of the present invention is representatively illustrated and generally designated 300 . Each of the sampling chambers 300 is coupled to a carrier 104 that also includes an actuator 106 and a pressure source 108 as depicted in FIG. 3 .
[0067] As described more fully below, a passage 310 in an upper portion of sampling chamber 300 (see FIG. 9A ) is placed in communication with a longitudinally extending internal fluid passageway 112 formed completely through the fluid sampler (see FIG. 3 ) when the fluid sampling operation is initiated using actuator 106 . Passage 112 becomes a portion of passage 16 in tubular string 12 (see FIG. 1 ) when the fluid sampler is interconnected in tubular string 12 . As such, internal fluid passageway 112 provides a smooth bore through the fluid sampler. Passage 310 in the upper portion of sampling chamber 300 is in communication with a sample chamber 314 via a check valve 316 . Check valve 316 permits fluid to flow from passage 310 into sample chamber 314 , but prevents fluid from escaping from sample chamber 314 to passage 310 .
[0068] A debris trap piston 318 is disposed within housing 302 and separates sample chamber 314 from a meter fluid chamber 320 . When a fluid sample is received in sample chamber 314 , debris trap piston 318 is displaced downwardly relative to housing 302 to expand sample chamber 314 . Prior to such downward displacement of debris trap piston 318 , however, fluid flows through sample chamber 314 and passageway 322 of piston 318 into debris chamber 326 of debris trap piston 318 . The fluid received in debris chamber 326 is prevented from escaping back into sample chamber 314 due to the relative cross sectional areas of passageway 322 and debris chamber 326 as well as the pressure maintained on debris chamber 326 from sample chamber 314 via passageway 322 . An optional check valve (not pictured) may be disposed within passageway 322 if desired. Such a check valve would operate in the manner described above with reference to check valve 128 in FIG. 2B . In this manner, the fluid initially received into sample chamber 314 is trapped in debris chamber 326 . Debris chamber 326 thus permits this initially received fluid to be isolated from the fluid sample later received in sample chamber 314 . Debris trap piston 318 includes a magnetic locator 324 used as a reference to determine the level of displacement of debris trap piston 318 and thus the volume within sample chamber 314 after a sample has been obtained.
[0069] Meter fluid chamber 320 initially contains a metering fluid, such as a hydraulic fluid, silicone oil or the like. A flow restrictor 334 and a check valve 336 control flow between chamber 320 and an atmospheric chamber 338 that initially contains a gas at a relatively low pressure such as air at atmospheric pressure. A collapsible piston assembly 340 includes a prong 342 which initially maintains check valve 344 off seat, so that flow in both directions is permitted through check valve 344 between chambers 320 , 338 . When elevated pressure is applied to chamber 338 , however, as described more fully below, piston assembly 340 collapses axially, and prong 342 will no longer maintain check valve 344 off seat, thereby preventing flow from chamber 320 to chamber 338 .
[0070] A piston 346 disposed within housing 302 separates chamber 338 from a longitudinally extending atmospheric chamber 348 that initially contains a gas at a relatively low pressure such as air at atmospheric pressure. Piston 346 includes a magnetic locator 347 used as a reference to determine the level of displacement of piston 346 and thus the volume within chamber 338 after a sample has been obtained. Piston 346 included a piercing assembly 350 at its lower end. In the illustrated embodiment, piercing assembly 350 is threadably coupled to piston 346 which creates a compression connection between a piercing assembly body 352 and a needle 354 . Alternatively, needle 354 may be coupled to piercing assembly body 352 via threading, welding, friction or other suitable technique. Needle 354 has a sharp point at its lower end and may have a smooth outer surface or may have an outer surface that is fluted, channeled, knurled or otherwise irregular. As discussed more fully below, needle 354 is used to actuate the pressure delivery subsystem of the fluid sampler when piston 346 is sufficiently displaced relative to housing 302 .
[0071] Below atmospheric chamber 348 and disposed within the longitudinal passageway of housing 302 is a valving assembly 356 . Valving assembly 356 includes a pressure disk holder 358 that receives a pressure disk therein that is depicted as rupture disk 360 , however, other types of pressure disks that provide a seal, such as a metal-to-metal seal, with pressure disk holder 358 could also be used including a pressure membrane or other piercable member. Rupture disk 360 is held within pressure disk holder 358 by hold down ring 362 and gland 364 that is threadably coupled to pressure disk holder 358 . Valving assembly 356 also includes a check valve 366 . Valving assembly 356 initially prevents communication between chamber 348 and a passage 380 in a lower portion of sampling chamber 300 . After actuation the pressure delivery subsystem by needle 354 , check valve 366 permits fluid flow from passage 380 to chamber 348 , but prevents fluid flow from chamber 348 to passage 380 .
[0072] As mentioned above, one or more of the sampling chambers 300 and preferably nine of sampling chambers 300 are installed within exteriorly disposed chamber receiving slots 159 that circumscribe internal fluid passageway 112 of carrier 104 . A seal bore 160 (see FIG. 3B ) is provided in carrier 104 for receiving the upper portion of sampling chamber 300 and another seal bore 162 (see FIG. 3C ) is provided for receiving the lower portion of sampling chamber 300 . In this manner, passage 310 in the upper portion of sampling chamber 300 is placed in sealed communication with a passage 164 in carrier 104 , and passage 380 in the lower portion of sampling chamber 300 is placed in sealed communication with a passage 166 in carrier 104 .
[0073] As described above, once the fluid sampler is in its operable configuration and is located at the desired position within the wellbore, a fluid sample can be obtained into one or more of the sample chambers 314 by operating actuator 106 . Fluid from passage 112 then enters passage 310 in the upper portion of each of the desired sampling chambers 300 . For clarity, the operation of only one of the sampling chambers 300 after receipt of a fluid sample therein is described below. The fluid flows from passage 310 through check valve 316 to sample chamber 314 . It is noted that check valve 316 may include a restrictor pin 368 to prevent excessive travel of ball member 370 and over compression or recoil of spiral wound compression spring 372 . An initial volume of the fluid is trapped in debris chamber 326 of piston 318 as described above. Downward displacement of piston 318 is slowed by the metering fluid in chamber 320 flowing through restrictor 334 . This prevents pressure in the fluid sample received in sample chamber 314 from dropping below its bubble point.
[0074] As piston 318 displaces downward, the metering fluid in chamber 320 flows through restrictor 334 into chamber 338 . At this point, prong 342 maintains check valve 344 off seat. The metering fluid received in chamber 338 causes piston 346 to displace downwardly. Eventually, needle 354 pierces rupture disk 360 which actuates valving assembly 356 . Actuation of valving assembly 356 permits pressure from pressure source 108 to be applied to chamber 348 . Specifically, once rupture disk 360 is pierced, the pressure from pressure source 108 passes through valving assembly 356 including moving check valve 366 off seat. In the illustrated embodiment, a restrictor pin 374 prevents excessive travel of check valve 366 and over compression or recoil of spiral wound compression spring 376 . Pressurization of chamber 348 also results in pressure being applied to chambers 338 , 320 and thus to sample chamber 314 .
[0075] When the pressure from pressure source 108 is applied to chamber 338 , pins 378 are sheared allowing piston assembly 340 to collapse such that prong 342 no longer maintains check valve 344 off seat. Check valve 344 then prevents pressure from escaping from chamber 320 and sample chamber 314 . Check valve 316 also prevents escape of pressure from sample chamber 314 . In this manner, the fluid sample received in sample chamber 314 is pressurized.
[0076] While this invention has been described with a reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative embodiments as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to the description. It is, therefore, intended that the appended claims encompass any such modifications or embodiments.
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An apparatus for actuating a pressure delivery system of a fluid sampler. The apparatus includes a housing ( 302 ) having a longitudinal passageway and defining first and second chambers ( 338, 348 ). A piston ( 346 ) is disposed within the longitudinal passageway between the first and second chambers ( 338, 348 ). A valving assembly ( 356 ) is disposed within the longitudinal passageway. The valving assembly ( 356 ) is operable to selectively prevent communication of pressure from a pressure source of the fluid sampler to the second chamber ( 348 ). The valving assembly ( 356 ) is actuated responsive to an increase in pressure in the first chamber ( 338 ) which longitudinally displaces the piston ( 346 ) toward the valving assembly ( 356 ) until at least a portion of the piston ( 346 ) contacts the valving assembly ( 356 ), thereby releasing pressure from the pressure source into the second chamber ( 348 ) and longitudinally displacing the piston ( 346 ) away from the valving assembly ( 356 ).
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This is a continuation of application Ser. No. 08/058,992, filed on May 6, 1993, now abandoned which is a Continuation of application Ser. No. 07/786,026, filed Oct. 31, 1991, now abandoned which is a continuation-in-part of application Ser. No. 07/557,516, filed Jul. 24, 1990, now U.S. Pat. No. 5,278,189 which is a continuation-in-part of application Ser. No. 07/533,129, filed Jun. 4, 1990, now abandoned.
FIELD OF THE INVENTION
The present invention relates generally to compositions effective in the prevention and treatment of cardiovascular disease and more particularly to compositions based on lysine and/or pharmaceutically acceptable salts of lysine.
References
Armstrong et al. 1986. Atherosclerosis 62:249-257.
Berg, K. 1963. Acta Pathologica 59:369-382.
Blumberg et al. 1962. J. Clin. Investigations 41:1936-1944.
Dahlem et al. 1986. Circulation 74:758-765.
Eaton et al. 1987. PNAS USA 84:3224-3228.
Gonzales-Gronow et al. 1989. Biochemistry 28:2374-2377.
Hajjar et al. 1989. Nature 339:303-305.
Harpel et al. 1989. PNAS USA 86:3847-3851.
McLean et al. 1987. Nature 300:132-137.
Miles et al. 1989. Nature 339:301-302.
Salonen et al. 1989. EMBO Journal 8:4035-4040.
Zenker et al. 1986. Stroke 17:942-945.
BACKGROUND OF THE INVENTION
Lipoprotein(a) ("Lp(a)") structurally resembles low density lipoprotein ("LDU") in that both share a lipid apoprotein composition, apolipoprotein B-100 ("apo-B"), the ligand by which LDL binds to LDL receptors present on the interior surfaces of arterial walls. (Berg, Blumberg) The unique feature of Lp(a) is an additional glycoprotein, designated apoprotein(a) ("apo(a)"), which is linked to apo-B by disulfide group. The cDNA sequence of apo(a) shows a striking homology to plasminogen, with multiple repeats of kringle 4, one kringle 5, and a protease domain. The isoforms of apo(a) vary in range of 300 to 800 kD and differ mainly in their genetically determined number of kringle 4 structures. (McLean) Apo(a) has no plasmin-like protease activity. (Eaton) Serine protease activity, however, has been demonstrated. (Salonen) Like plasminogen, Lp(a) has been shown to bind lysine-sepharose, immobilized fibrin and fibrinogen, and the plasminogen receptor on endothelial cells. (Gonzales-Gronow, Hajjar, Harpel, Miles) Furthermore, Lp(a) has been demonstrated to bind to other components of the arterial wall like fibrinectin and glycosaminoglycans. The nature of these bindings, however, is poorly understood.
Essentially all human blood contains Lp(a). There can, however, be a thousand-fold range in its plasma concentration between individuals. High levels of Lp(a) are associated with a high incidence of cardiovascular disease. (Armstrong, Dahlem, Miles, Zenker) The term "cardiovascular disease" is intended to refer to all pathological states leading to a narrowing and/or occlusion of blood vessels throughout the body, but particularly atherosclerosis, thrombosis and other related pathological states, especially as occurs in the arteries of the heart muscle and the brain.
For some time, conventional medical treatment of cardiovascular disease has focused on LDL, the so called "bad cholesterol," and strategies for lowering its concentration in the bloodstream. A great many studies have been published ostensibly linking cardiovascular disease with elevated levels of LDL. As a result, most therapies for the prevention and treatment of cardiovascular disease rely on drugs that reduce serum levels of LDL in the bloodstream. More recent studies have found the beneficial effects of lowering LDL levels to be somewhat equivocal. Thus, the efficacy of these drugs and therapies continues to be a source of major debate within the medical community.
There exists therefore a need for a drug therapy for preventing or treating cardiovascular disease by (i) reducing damage to blood vessel walls, thereby reducing the binding potential Lp(a) to blood vessel walls and thus diminishing the deleterious effects of high levels of Lp(a) in the bloodstream.
There further exists a need for a treatment that employs compounds that are safe to use with few if any complicating and undesired side effects.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a pharmaceutical composition that is inexpensive, has few or no undesired side effects and is available without a doctor's prescription for the prevention and treatment of cardiovascular disease.
It is another object of the present invention to provide a method of prevention and treatment of cardiovascular disease that can be both prophylactic or therapeutic, depending upon the progression of disease within a particular patient.
It is yet another object of the invention to provide a method of preventing or treating cardiovascular disease that results in few if any undesired side effects and that is inexpensive to carry out.
According to one aspect of the invention, a lysine-based pharmaceutical composition is provided. The composition includes in addition to a lysine or salt thereof, one or more forms of ascorbic acid and tocopherol. More particularly, the composition also includes other compounds having an antioxidant effect such as carotene, N-acetyl cysteine and nicotinic acid.
In another aspect of the invention, a method for preventing or treating cardiovascular disease is described, comprising the step of administering to a subject a therapeutically effective amount of the lysine-based composition. The treatment has prophylactic value in that it tends to prevent oxidative damage to the interior walls of arteries, thereby decreasing the potential for Lp(a) binding and ultimately plaque accumulation. The treatment has therapeutic value in that it appears to halt and perhaps reverse the progress of arterial narrowing by inhibiting further binding of Lp(a) and perhaps by promoting the release of Lp(a) already bound.
These and other features and advantages of the invention will become more readily understood upon consideration of the following detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an immunoblot of the plasma of guinea pigs from the test described in Example 1.
FIG. 2A is a picture of an aorta of a guinea pig that received an adequate amount of dietary ascorbate, as described in Example 1.
FIG. 2B is a picture of an aorta of a guinea pig receiving a hypoascorbic diet over a three week period, as described in Example 1.
FIG. 3 is an immunoblot of plasma and tissue of guinea pigs receiving a variety of dietary intact of ascorbate, as described in Example 2.
DETAILED DESCRIPTION OF THE INVENTION
Our invention is based in part on our discovery that animals that have lost the ability to produce ascorbate, such as higher primates and guinea pigs, uniformly produce Lp(a), whereas animals that possess this ability generally do not produce Lp(a). Further, we have found that ascorbate deficiency in humans and guinea pigs tends to raise Lp(a) levels and causes atherosclerosis through deposition of Lp(a) on the inner surface of the arterial wall.
We have also discovered that substances that inhibit binding of Lp(a) to components of the arterial wall, particularly to fibrinogen, fibrin and fibrin degradation products herein identified as binding inhibitors, such as lysine, cause release of Lp(a) from the arterial wall. Thus, ascorbate and such binding inhibitors are not only useful in the prevention of cardiovascular disease, but also for the treatment of such disease. The present invention provides a novel pharmaceutical composition based on lysine that is safe to use and available without a doctor's prescription. This compound can be used in a method to slow or prevent the onset of cardiovascular disease, as well as slow, stop or even reverse the progress of the disease.
A. Lysine-Based Composition.
According to one aspect of the present invention, a pharmaceutical composition based on a lysine compound is provided. In one embodiment, the composition comprises a combination of an ascorbate compound, nicotinic acid and a lysine compound, along with a pharmaceutically acceptable carrier.
The ascorbate compound may be ascorbic acid, a pharmaceutically acceptable form of an ascorbate salt or a mixture thereof. The lysine compound may be lysine in its electrically neutral form or a pharmaceutically acceptable salt of lysine. Some acceptable salt forms of lysine include lysine hydrochloride, lysine dihydrochloride, lysine succinate, lysine glutamate, and lysine orotate.
The relative percentages of each class of compounds in the compositions may be varied to some degree, although ascorbate should be present in amounts several times greater than either nicotinic acid or lysine compounds. A preferred ration of ascorbate to nicotinic acid to lysine is 4:1:1. It will be understood that each class of compound may be present exclusively in one chemical form, or may be present as a mixture of chemical forms as set forth and described above.
In addition to ascorbate, nicotinic acid and lysine, it is preferred to add other vitamins and compounds with demonstrated antioxidative properties. Thus, in another embodiment of the composition of the invention, carotene and tocopherol may be added.
It will also be appreciated that the composition just described may consist of a simple mixture of the individual compounds described, or they may be covalently linked or present as ionically bound salts of one another. For example, ascorbate may be covalently linked to lysine.
The constituents described above are generally mixed with a pharmaceutically acceptable carrier, to form tablets or capletts for oral administration. The carrier may contain a binder such as tragacanth, corn starch or gelatin; a disintegrating agent, such as alginic acid, and/or a lubricant such as magnesium stearate. If administration in liquid form is desired, use of sweetening and/or flavoring agents may be used. It will be understood that the composition of the invention may also be delivered parenterally by injection or IV, wherein the carrier may be an isotonic saline solution, a phosphate buffered solution or similar carrier.
B. Methods of Use.
The composition described above may be used as a prophylactic agent to halt or delay the onset of cardiovascular disease or may be employed to treat an existing cardiovascular condition.
In the case of preventative treatment, it is preferred to administer a composition containing ascorbate, nicotinic acid and a lysine compound to block any initial Lp(a) binding with the arterial wall, as well as to prevent damage to the vessel wall resulting from a degeneration of the extracellular matrix. In another teatment, both tocopherol and a cavotene, preferably β-caotone, are added. Table I sets forth preferred ranges of dosages of the individual components of the composition of the present invention. The protocol for prophylactic treatment of patients at risk for cardiovascular disease calls for administration of the doses listed in Table I on a daily basis. Because ascorbate is so quickly cleared from the system, and because it can be irritating to the intestinal lining in high doses until tolerance is reached, it may be preferable to divide the preferred dose into two to four smaller doses that can be administered with meals.
TABLE I______________________________________DOSAGES OF COMPONENTS OF THEDRUG COMPOSITION OF THE INVENTION Oral Parenteral Administration AdministrationComponent Dosage †______________________________________Ascorbate 5-2500 25-2500Lysine 5-300 5-500Nicotinic Acid 1-300 1-300Tocopherol 1-50 1-50Carotene 1-300 1-300______________________________________ †mg/kg of body weight per day
In the treatment of an existing condition of cardiovascular disease, it will be understood that the therapeutic composition described above should include at least ascorbate, nicotinic acid and lysine but with each in a higher dosage. It is also preferred to add a carotene and tocopherol as additional antioxidants. Suitable dosages are listed in Table I. It should be noted that the concentrations of the individual constituents vary, depending on whether administration is oral or parenteral, and depending on the severity of the disease. It will be appreciated therefore that a subject diagnosed with advanced stages of atherosclerosis should receive a dosage at the higher end of the ranges set forth in Table I.
The composition of the present invention is also useful in the treatment of diseases arising from a degeneration of the extracellular matrix, particularly metastasis of cancel. While not wishing to be bound by a particular theory of operation, it appears that lysine is available to inhibit both plasminogen and plasmin, which eventually stimulates the production of collagenase and, ultimately, the collagen network in the extracellular matrix. Such degradation also exacerbates advances cases of atherosclerosis. Thus, lysine is effective not only to block potential Lp(a) binding sites, but also to inhibit the action of certain proteolytic enzymes that may ultimately result in damage to arterial walls. Thus, in another embodiment of the present invention, natural inhibitors of proteolytic enzymes, such as are found in soybeans, may be added to the composition.
Experimental
Having disclosed the preferred embodiment of the invention, the following examples are provided by way of illustration only and are not intended to limit the invention.
Guinea pigs are similar to man in their inability to synthesize ascorbate and in their ability to synthesize Lp(a). Guinea pigs are therefore selected as a suitable test animal to test the compositions and methods of the present invention.
Example 1A: Guinea Pig Study Model Development of Atherosclerosis in Female Guinea Pigs
Three female Hartley guinea pigs with an average weight of 800 gm and an approximate age of 1 year were selected for study. One animal received an extreme hypoascorbic diet with approximately 1 mg ascorbate per kg body weight per day. One of the other animals received a diet containing 4 mg ascorbate per kg body weight per day. The remaining animal served as a control and received 40 mg ascorbate per kg body weight per day.
Once after ten days and then again after three weeks, blood was drawn by ear puncture from the anaesthetized animals and collected into EDTA containing tubes. Subsequent to drawing blood at the three weeks, the animals were sacrificed. Plasma was stored at -80° C. until analysis could be conducted. Lp(a) was detected in the plasma by use of an SDS-polyacrylamide gel according to the techniques of Neville (J. Biol. Chem. 257:13150-13156. 1982), the contents of which are incorporated herein by reference. Forty μL of plasma and 20 mg of arterial wall homogenate were applied in delipidated form per lane of the gel.
Lp(a) presence in the gel was detected by immunological assay using polyclonal anti-human apo(a) antibody (available from Immuno, Vienna, Austria) followed by a rabbit anti-sheep antibody with subsequent silver enhancement (available from Bio-Rad). The determinations of cholesterol and triglycerides were conducted at California Veterinary Diagnostics (Sacramento) using the enzyme assay of Boehringer Mannheim. Plasma ascorbate concentration was determined by the dinitrophenylhydrazine method of Shaffer et al. (J. Biol. Chem. 212:59. 1955).
Vitamin C deficiency in the diet led to an increase of Lp(a) in the plasma of the guinea pig, as indicated by a clear band in the immunoblot of the plasma after 10 and 20 days on a hypoascorbic diet (see FIG. 1). At necropsy the animals were anaesthetized with metophase and exsanguinated. Aorta, heart and various other organs were taken for biochemical and histological analysis. The aorta was excised, the adventitial fat was carefully removed, and the vessel was opened longitudinally. Subsequently the aorta was placed on a dark metric paper and a color slide was taken. The picture was projected and thereby magnified by an approximate factor of 10. The circumference of the ascending aorta, the aortic arch and thoracic aorta as well as the atherosclerotic lesions in this area were marked and measured with a digitalized planimetry system. The degree of atherosclerosis was expressed by the ration of plaque area in relation to the total aortic area defined. The difference in the 3 one-year old animals of the experiment was significant and pronounced lesions were observed in the ascending aorta and the arch of the ascorbate deficient animal (see FIG. 2b).
Example 1B: Guinea Pig Study Model Development of Atherosclerosis in Male Guinea Pigs
33 male guinea pigs with a mean weight of 550 gm and an approximate age of 5 months were selected. One group of 8 animals served as a control and received 40 mg ascorbate per kg of body weight per day ("Group A"). To induce hypoascorbemia, 16 animals were fed a diet containing 2 mg of ascorbate per kg body weight per day ("Group B"). Group A and half of Group B were sacrificed after five weeks as described above. The remaining half of Group B was kept alive for 2 more weeks, receiving daily intraperitoneal injection of 1.3 gms of sodium ascorbate per kg of body weight per day. After this period, these animals were sacrificed.
Plasma ascorbate levels were negatively correlated with the degree of atherosclerotic lesion. Total cholesterol levels increased significantly during periods of ascorbate deficiency (see Table II).
The aortas of the guinea pigs receiving a sufficient amount of ascorbate were essentially plaque free, with minimal thickening of the intima in the ascending region. In contrast, the ascorbate-deficient animals exhibited fatty streak-like lesions, covering most parts of the ascending aorta and the aortic arch. In most cases the branching regions of the intercostal arteries of the aorta exhibited similar lipid deposits. The difference in the percentage of lesion area between the control animals and the hypoascorbic diet animals was 25% deposition of lipids and lipoproteins in the arterial wall.
TABLE II______________________________________MEAN PLASMA PARAMETERS OF THE DIFFERENT GUINEAPIG GROUPS IN RELATION TO THE AREA OF AORTICLESIONS Regression Scurvy (after Control (progress) scurvy)______________________________________Plasma 39 54 33cholesterol(mg/dl)Total plasma 5.03 3.01 20.64ascorbic acid(μg/ml)Atheroscl. -- 25 19lesion(as a % ofaorta thoracicsurface)______________________________________
Example 2
Effect of Lysine Composition on Disease
Human arterial wall tissue is obtained post mortem from the aorta ascendens of a patient suffering from cardiovascular disease showing an atherosclerotic lesion as evidenced by homogenous intimal thickening. The arterial wall is cut into pieces, with about 100 mg of the cut up tissue homogenized in a glass potter for 1 minute in 2.5 ml of an isotonic solution containing ascorbate alone, ascorbate combined with lysine. The arterial wall segments are then placed in the solution and allowed to incubate. The solution is then decanted off and the concentration of Lp(a) measured according to the techniques discussed above.
It is now apparent that the methods and compositions of the present invention meet longstanding needs in the field of prevention and treatment of cardiovascular disease. Although the invention has been described with respect to preferred embodiments, it will be apparent that various changes and modifications may be made without departing from the invention as set forth in the accompanying claims.
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A therapeutic lysine-based composition and methods for its use in the prevention and treatment of cardiovascular disease is disclosed. The composition includes at least one ascorbate compound, nicotinic acid and at least one lysine compound. The ascorbate compound, nicotinic acid and the lysine compound are preferentially present in a ratio of 8:1:1. The composition may also include N-acetyl cysteine, a carotene and/or nicotinic acid. A patient at risk of developing or with a pre-existing cardiovascular disease is treated by administering orally or parenterally a desired dosage of the composition on a daily basis.
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